Coordination Chemistry Reviews 347 (2017) 48–76

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Hydroxyapatite: A review of syntheses, structure and applications in

heterogeneous catalysisq
Aziz Fihri a,⇑, Christophe Len b, Rajender S. Varma c, Abderrahim Solhy d,⇑
a
MAScIR Foundation, VARENA Center, Rabat Design, Rue Mohamed El Jazouli, Madinat Al Irfane, 10100 Rabat, Morocco
b
Sorbonne Universités, Université de Technologie Compiègne, Centre de Recherche Royallieu, CS 60319, F-60203 Compiègne Cedex, France
c
Regional Centre of Advanced Technologies and Materials, Faculty of Science, Department of Physical Chemistry, Palacky University, Šlechtitelů 11, 783 71 Olomouc, Czech Republic
d
Mohamed VI Polytechnic University, Lot 660 – Hay Moulay Rachid, 43150 Benguerir, Morocco

a r t i c l e i n f o a b s t r a c t

Article history: The synthesis of hydroxyapatite (HAP) and its applications in heterogeneous catalysis are abridged in
Received 1 April 2017 view of its demonstrated prowess and utility in chemical, material and industrial industry. This overview
Accepted 13 June 2017 documents the strengths and weaknesses of the synthetic routes that have been applied to the synthesis
Available online 15 June 2017
of hydroxyapatite with description of salient structural properties of hydroxyapatite responsible for its
reactivity. The significant applications of hydroxyapatite both, as an inorganic support and as a catalyst
Keywords: are described with an emphasis on its performance, stability and reusability. Several newer findings as
Hydroxyapatite
well as the current challenges pertaining to the use of hydoxyapetite are summarized.
Modified hydroxyapatite
Structure-activity
Ó 2017 Elsevier B.V. All rights reserved.
Catalysis

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2. Principal methods for the synthesis of HAP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.1. Dry methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.2. Wet methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.2.1. Co-precipitation method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.2.2. Sol–gel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.2.3. Emulsion methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.2.4. Hydrolysis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.2.5. Hydrothermal methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3. Alternate energy input methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3.1. Microwave (MW)-assisted methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3.2. Ball-milling method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.3.3. Sonochemical method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.4. Other methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3. Structure-reactivity studies of hydroxyapatite related to catalysis performances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4. Catalytic applications of hydroxyapatite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4.1. Cross-coupling reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4.2. Condensation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2.1. Knoevenagel reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2.2. Claisen-Schmidt reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2.3. Michael addition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.3. Oxidation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.3.1. Oxidation of alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.3.2. Oxidations of silanols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

q
This article is dedicated to the memory of Fihri Bouchaib, admirable father and an irreplaceable person.
⇑ Corresponding authors.
E-mail addresses: [email protected] (A. Fihri), [email protected] (A. Solhy).

http://dx.doi.org/10.1016/j.ccr.2017.06.009
0010-8545/Ó 2017 Elsevier B.V. All rights reserved.
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 49

4.3.3. Epoxidation reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

4.3.4. Oxidative dehydrogenation of ethane and propane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.4. Photocatalytic reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.5. Othermiscellaneous reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.5.1. Multicomponent reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.5.2. Alkylation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.5.3. Hydration of nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.5.4. Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.5.5. Hydroformylation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.5.6. Hydrogenolysis reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.5.7. Hydrogenation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

1. Introduction tance, HAP is studied for various applications such as fluorescent

lamps [17], material for fuel cell [18], or an adsorption and stabi-
Heterogeneous catalysis is the cornerstone of the chemical lization matrix for radioactive waste and harmful metals [19]; sig-
industry and without it the existing technological society would nificant catalytic activities of HAP are a subject matter of numerous
not be what it is today [1]; several processes in the chemical indus- publications and patents [20,21].
try involve heterogeneous catalysis. More than 90% of oil and gas This present review aims to provide insights into the field of
molecules encounter a catalyst in refineries, generating fuels and synthesis and catalytic applications of HAP. The reason for our
large number of chemical intermediates [2]. Additionally, the efforts is its wide accessibility to chemical community, including
heterogeneous catalysis is implicated in many other varied indus- non-specialists in material sciences area. The first section of the
trial processes, ranging from inorganic chemistry (NH3, H2SO4, review gives an overview of the different synthetic routes that
HNO3. . .), to the synthesis of fine chemicals, and drug molecules, were applied to the synthesis of HAP. The second section is devoted
and environmental treatment of emissions and polluted dis- to structure-reactivity studies of HAP related to its catalysis perfor-
charges, etc. [3]. The study of heterogeneous catalysis requires a mances. The main section of this review covers the important
good understanding of solid catalysts and their preparation, char- applications of HAP in catalysis.
acterization, shape selectivity including the kinetics and mecha-
nisms of reaction [4–9]. On the economic front, in the year 2010,
2. Principal methods for the synthesis of HAP
the annual market value of solid catalysts was approximately 29
billion USD [10]. This value is expected to increase by an average
The synthesis of HAP, with its various structures, morphologies
of 7% by the year 2015, regardless of the current financial and eco-
and textures, has stimulated a great deal of interest in academic
nomic crisis [11]. Aside from economic considerations, another
and industrial research for numerous heterogeneous catalysis
driving reason for the development of heterogeneous catalysis is
applications. In the past thirty years, a number of synthetic routes
its ecological impact [12]. Present-day manufacturers have to sat-
for producing HAP powders have been developed. Production of
isfy increasingly severe legislations to develop manufacturing pro-
HAP powders is classified under four different methods: i) dry
cesses that release the minimum amount of possible waste. In this
methods, ii) wet methods, iii) microwave (MW)-assisted methods,
context, use of cleaner catalytic reactions can lead to a substantial
ball-millingor ultrasound and iv) miscellaneous methods. In each
reduction of the amount of toxic chemical pollution by reducing
category, there are several variations depending on the conditions
the formation of by-products [13].
of synthesis and reagents deployed. In this part of review, the most
At present, it is well known that a heterogeneous catalyst must
important synthetic methods used to obtain HAP powder are
have three characteristics: high activity, high selectivity and high
documented.
stability. Thus, the development of a new generation of solid cata-
lysts is a subject of increasing interest in the manufacture of fine
chemicals, refinery operations as well as in the domain of energy 2.1. Dry methods
and environmental protection [14]. In the past few years, the
design of materials with a controlled porosity or possessing hierar- The dry route preparation of HAP is based on the heat treatment
chical texture has garnered great interest due to their wide appli- of finely ground mixed precursors. Extensive research on this
cations in a number of fields, especially heterogeneous catalysis method has shown that variation of some factors can influence
[15]. the ensuing results. The essential requirement for the dry route
Hydroxyapatite (HAP) is a catalyst that may address the afore- method is to have a mixture that is perfectly homogenous for the
mentioned needs. Indeed, HAP is a material of varying properties completion of reaction. The purity of the final product is dependent
depending on its mode of preparation. Phosphate comprising the upon precise weighing procedures during preparation; the forma-
ideal formula of Ca10(PO4)6(OH)2 belongs to the apatite family; tion of a very stable intermediate phase can occur. These variable
HAP is one of the most usual forms of calcium phosphate. The factors can potentially limit the formation of the final desired
special attribute of this structure lies in its ability to form solid compound. Tromel et al. identified the optimum conditions for
solutions and to accept a large number of anionic and cationic sub- the formation of HAP via calcination of the mixture of reagents at
stituents. The variability of properties in HAP enables the possibil- 1050 °C in air (Scheme 1) [22,23].
ity to use the material in diverse applications. For instance, due to In general, the reactions in the solid state usually yield well-
HAP’s similarity in chemical composition to the mineral phase of crystallized stoichiometric products. Adversely, this method
bone tissues, it is known for its applications in medicine as syn- requires a relatively high temperature which can penalize in terms
thetic bone substitutes [16]. In addition to its biological impor- of the porosity of product [24,25].
50 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

precise control of the morphology and distribution of grain size.

In general, this technique was originally developed to create a por-
ous material as well as to overcome the issue of particle agglomer-
ation. Several sources of calcium and phosphate have been tested,
Scheme 1. Dry synthesis route to HAP [22].
but most often calcium nitrate and phosphoric acid are used [44] in
terms of the reports of reaction media, more organic solvents are
blended with water. Among the surfactants used to prepare emul-
2.2. Wet methods sion, some examples include: dioctyl sodium sulfosuccinate salt,
dodecyl phosphate, polyoxyethylene(5) nonylphenol ether, poly-
Wet methods comprising double decomposition or co- oxyethylene(12) ether nonylphenol, polyoxyethylene and polysor-
precipitation, emulsion, hydrolysis method, sol-gel method and bate 80, cetyltrimethylammonium bromide and sodium dodecyl
hydrothermal approach, are widely used due to the simplicity of sulfate [45]. The main synthesis parameters focus on the type of
procedures. These methods allow for perfect control over the struc- surfactant, ratio of aqueous and organic phases, pH and
ture, texture and morphology, and lead to a high yield of HAP. Wet temperature.
methods can be performed in water, or in organic solvents by sev-
eral reactions involving diverse reagents and auxiliary additives 2.2.4. Hydrolysis methods
and apparatus. They can be performed at ambient temperature The aqueous hydrolysis of calcium phosphates that forms HAP
or elevated temperatures, under atmospheric pressure or under crystallites usually follows two stages: dissolution and precipita-
high pressures. The major drawback of the wet methods is that tion [46–49]. Many calcium phosphate phases are used as precur-
they sometimes give rise to structures that are not crystallograph- sors to prepare HAP especially octacalcium phosphate, dicalcium
ically pure; other phases of phosphates are present with HAP. In phosphate dihydrate and tricalcium phosphate [50,51]. The
addition, various ions in aqueous solution can be incorporated into hydrolysis process applicable to these precursors depends strongly
the crystal structure, leading to trace impurities. on pH and temperature. The additions of other calcium and phos-
phate sources are sometimes required in the order to obtain the
stoichiometric HAP, the porous texture is dependent upon these
2.2.1. Co-precipitation method
parameters.
Co-precipitation is the most straightforward and frequently
used method for the preparation of HAP. This chemical process
2.2.5. Hydrothermal methods
consists of a reacting source of PO34 ligand with a source of cal-
The hydrothermal process is a rather mature technique for the
cium in the presence of other additives (e.g., base or acid) [26–
growth of crystalline HAP [52–54]. This process is the generic term
28]; several sources of these two reagents are used. The conditions
used to describe a reaction between the calcium source and the
of the co-precipitation method are variable, but in general, this
phosphate precursor in the presence of the following: i) water or
process is usually carried out at pH values ranging from 3 to 12
organic solvent, or ii) a mixture of water/organic solvent (water:
and at temperatures ranging from room temperature to the boiling
hydrothermal, organic solvent: solvothermal, water/organic sol-
temperature of water. In addition, this method is sometimes per-
vent: solvo-hydrothermal). The process occurs in a confined envi-
formed in the presence of templates [29–33].
ronment with a higher temperature and pressure greater than
autogenously ambient pressure, inside an autoclave or a pressure
2.2.2. Sol–gel method vessel; the medium could be subcritical or supercritical, depending
The sol–gel process is a method of mineralization from precur- on the pressure and temperature. Through the effect of condensa-
sors in a solution, preferably organometallic compounds or other tion and an increase in reactivity, and depending on the value of
suitable precursors. This exemplary method for the synthesis of pressure and temperature, the hydrothermal method creates
porous HAP occurs under conditions called soft-chemistry condi- chemical bonds and forms nuclei that ensure a relatively stoichio-
tions that are significantly lower than those of conventional syn- metric and highly crystalline synthesis of HAP [55–58]. It should be
thetic routes in terms of temperature. The sol–gel process has noted that high pressure permits the formatting of HAP in the form
limitations that hinder its expansion into industrial scale produc- of micro or nano-sized crystallites, with controlled morphology
tion. The main obstacles are: i) the high cost and scarcity of often and porosity. The hydrothermal method serves to modulate the
used alkoxide-based precursors and ii) the delicate process control interactions between solid/solvent, especially in terms of solubility
culminating in usually time consuming processes. This protocol and also functions as a conduit in the control of the nucleation and
involves hydrolysis of the precursors and the formation of micelles growth processes [59,60]. Moreover, this technique is often com-
around templates in either an aqueous or an organic phase fol- bined with conventional methods such as co-precipitation or sol–
lowed by the polycondensation of these species via formation of gel protocols.
a 3D inorganic network [34,35]. However, the rate of gel formation
depends strongly on: i) the nature of the solvent; ii) the tempera- 2.3. Alternate energy input methods
ture and pH used during the process and iii) the chemical nature of
the reagents used. In addition, lack of control of certain parameters These assisted methods are often combined with other conven-
during the growth of HAP may cause the appearance of secondary tional methods to create a synergy between the different tech-
phases such as CaO, Ca2P2O7, Ca3(PO4)2 and CaCO3 [36,37]. It niques to increase the yield in an expeditious fashion[61–66].
should be noted that a non-alkoxide sol–gel process for synthesis
of HAP, without need to adjust the pH, has also been developed; 2.3.1. Microwave (MW)-assisted methods
only the conventional sources of calcium and phosphate have been Due to enormous progress in this field of alternative heating
used in these methods [38–40]. technique, there has been a continued interest in methods involv-
ing MW activation. The MW-assisted preparation of HAP produces
2.2.3. Emulsion methods an increased yield of perfectly crystalline powder that is particu-
Among methods developed for the synthesis of HAP, the emul- larly homogeneous in terms of size, porosity and morphology
sion process is considered to be more efficient, simple and suitable [67–71]. The activation results from two contributing factors: i) a
for producing a nano-structured HAP powder [41–43] allowing purely thermal origin, resulting in molecular agitation that is
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 51

caused by the inversion of dipole with the extremely rapid alterna- adopting their functional expressions [87–90]. Developed under
tions of the electric field, and ii) an electrostatic origin, involving the realm of bio-inspired chemistry, these two methods to prepare
interactions like dipole–dipole between polar molecules and the HAP are combustion and pyrolysis or spray pyrolysis; the combus-
electric field. This has a direct effect on the kinetics of the decrease tion process is a promising method for preparation of HAP [91–93].
in the activation energy. Our research group has developed a tech- The fundamental principle of this method comes from the thermo-
nique that uses sol–gel followed by a hydrothermal treatment chemical concepts used in the field of propellants and explosives
assisted by MW irradiation [72,73]. chemistry. Exothermic and self-sustaining redox reaction occurs
in an aqueous phase between precursors and a suitable organic
2.3.2. Ball-milling method fuel (e.g., glycerin, urea, sucrose, citric acid, and succinic acid)
The ball-milling method, also termed mechanochemical pro- [94–97]. The pyrolysis process consists of evaporated liquid
cess, has been widely used to synthesize HAP with the advantages reagents (precursors and calcium phosphate) [98–100] and
such as simplicity, reproducibility, and large-scale production of involves spraying of the precursor solutions into a flame or a hot
HAP [74,75]. The control of the growth of HAP by this technique zone of an electric furnace using an ultrasonic generator [101,102].
closely depends on the type of reagents used, the milling medium,
the diameter of the milling balls, the type of atmosphere, the dura-
3. Structure-reactivity studies of hydroxyapatite related to
tion of the milling steps and interval pauses, the powder-to-ball
catalysis performances
mass ratio and the rotational speed [76–79].
HAP belongs to a large family of isomorphic compounds and is
2.3.3. Sonochemical method one of the most common forms of calcium phosphate. HAP crystal-
The sonochemical approach is based on the reactions activated lizes in the hexagonal system (space group P63/m) with the follow-
by powerful ultrasound radiation [80–82]. This method invariably ing crystallographic parameters: a = 9.418 Ǻ, c = 6.881 Ǻ,
delivers nanosized products and elicits perfect control of morphol- b = 120 °C (JCPDS No. 9-432) [103]. The crystalline network of the
ogy, porosity and size [83,84]; enhanced stimulation of the reac- stoichiometric HAP can be described as a compact assemblage of
tion between the calcium and phosphate precursors accelerate tetrahedral PO4 groups, where P5+ ions are in the center of the
the rate of reaction in a remarkable manner [85,86]. tetrahedrons and whose tops are occupied by 4 oxygen atoms.
Each PO4 tetrahedron is shared by a column and delimits two types
2.4. Other methods of unconnected channels (Fig. 1). The first channel has a diameter
of 2.5 Å and is surrounded by Ca2+ ions, denoted Ca(I) (4 per unit
Bio-inspired chemistry is a field of chemistry that is aimed at cell). They are in coordination 9 with the oxygen atoms of the
creating materials that mimic efficient biological systems by PO4 tetrahedrons resulting in the formation of a polyhedron as

Fig. 1. (a) Projection of the unit cell of HAP according to plan (0 0 1); (b) projection showing the arrangement of octahedrons [Ca(1)O6] in the HAP structure; (c) projection
showing the sequence of octahedral [Ca(1)O6] and tetrahedral [PO4] in the HAP structure; and (d) projection showing the sequence of octahedral: [Ca(1)O6] and [Ca(2)O6], and
also tetrahedral [PO4] in the HAP structure.
52 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

shown in Fig. 1a. The second type of channel plays an important tury [108–111]. These reactions are often catalyzed using homoge-
role in the properties of apatites. It has a diameter larger than neous catalytic systems because of their high reactivity, higher
the previous one (3–4.5 Å), and contains six other Ca2+ ions, turnover numbers, and notably the possibility of coupling the
referred to as Ca(II). The latter are located at the periphery of the widely available and relatively low-cost aryl chlorides [112–117].
channel. These ions are located in two dimensions 1/4 and 3/4 of However, these traditional systems continue to pose difficulties
the unit cell along c axis and form alternate equilateral triangles related to product purification and toxic waste produced after sep-
around the helicoidal senary axis. Their coordination is 7, and they aration of palladium (Pd) catalyst. One of the most favorable ways
are surrounded by six atoms of oxygen belonging to [XO4] tetrahe- to overcome these issues is the use of heterogeneous catalysis
dron and one OH anion in position 2a (Fig. 1b) [103]. The exis- because it offers a number of advantages namely excellent stabil-
tence of two different calcium sites is of special interest because ity, easy separation from the reaction mixture by filtration or
the properties of HAP can be tuned by specific modification of decantation, recyclability often with minimal loss of activity, and
the site [104]. These channels host OH groups along the c axis the wide accessibility of support [118–120]. Relatively few studies
to balance the positive charge of the matrix. The OH ions are pre- have reported the use of hydroxyapatite as catalysts for cross-
sent in columns perpendicular to the unit cell face, at the center of coupling reactions. In this context, Kaneda and colleagues reported
the large channels type II. The oxygen present in the hydroxyl the preparation of two types of PdHAP by selecting appropriate
group is located at 0.4 Å out of the plane formed by the calcium Ca/P molar ratios to give the stoichiometric Ca10(PO4)6(OH)2
ion, and the hydrogen of the hydroxyl group is located at 1 Å, (Ca/P = 1.67, HAP-0) and the non-stoichiometric Ca-deficient
which is almost on the triangle plane of calcium. The dimension hydroxyapatite Ca9(HPO4)(PO4)5(OH) (Ca/P = 1.50, HAP-1) [121].
of the tunnel endows certain mobility to these ions and conse- The treatment of the HAP-0 with PdCl2(PhCN)2 in acetone afforded
quently allows their circulation along the tunnels in the direction the HAP-bound Pd complex PdHAP-0, while the PdHAP-1 complex
of OZ axis (Fig. 1c). The HAP is a highly non-stoichiometric calcium was obtained using HAP-1 by the same method. The PdHAP-1 was
phosphate compound with a Ca/P molar ratio ranging from 1.50 to found to be an outstanding catalyst for Suzuki-Miyaura cross-
1.67 [105]. The Ca/P molar ratio of a stoichiometric form of hydrox- coupling reaction of activated and deactivated aryl bromides, with
yapatite is 1.67. The preparation of the non-stoichiometric hydrox- phenylboronic acid using K2CO3 as the base and o-xylene as the
yapatite can be rationalized by the fact that the loss of Ca2+ ions solvent at 120 °C (Table 2). Additionally, the catalyst could be recy-
and the ensuing electrical imbalance are corrected by the introduc- cled, and there was not any Pd leaching observed.
tion of H+ ions and depletion of OH ions, denoted by the formula In a subsequent study, the same research group expanded the
Ca10-Z(HPO4)Z(PO4)6-Z(OH)2-Z; 0 < Z  1 [106]. Moreover, the envi- promising initial results of the application of the PdHAP-1 to
ronment surrounding the OH sites is very attractive for substitu- Suzuki–Miyaura coupling reactions of aryl chlorides [122]. Under
tions as it enables one to control the ratio between acid-base sites. the various conditions explored, the prepared catalysts proved
With a Ca/P ratio of 1.50, HAP acts as an acid catalyst with the exis- effective in coupling reactions of aryl chlorides bearing electron-
tence of basic sites. In contrast, with a Ca/P ratio of 1.67, HAP acts withdrawing substituents with phenyl boronic acid (Table 3).
as a basic catalyst while acid sites are still present [107]. However, chlorobenzene was not active and only a moderate yield
However, a key element of the apatite structure is that it allows was obtained, even when the catalyst loading was increased to
a great number of substitutions that leave the crystallographic 0.3 mol%. The PdHAP-1 catalyst system exhibited higher catalytic
structure unchanged. Table 1 shows some examples of possible activity compared to other conventional heterogeneous catalysts
substitutions in consideration of the following general chemical such as Pd/Carbon, Pd/Al2O3, and Pd/SiO2. It is interesting to note
formula: Me10(XO4)6(Y)2, wherein Me is a monovalent, divalent that for the chloride substrates, the addition of tetrabutylammo-
or trivalent cation (alkaline earth metal, d-block elements, alkali nium bromide and a small amount of water was required for better
metal, or lanthanide, . . .), XO4 a trivalent anion (PO34 , AsO34 , . . .) conversion.
and Y a monovalent anion (OH , F , . . .). XO34 groups may also The same catalytic system was employed to investigate the
be substituted by divalent or tetravalent groups, but the existence Mizoroki-Heck reaction of aryl bromides with styrene and n-
of apatite containing XO34 deficient sites has never been reported. butyl acrylate. In the presence of 0.002 mol% of Pd catalyst, the best
The second anionic Y site can also be occupied by monovalent ions, results were obtained with K2CO3 as the base in N-
divalent. The possibility of substitution allows the existence of methylpyrrolidone (NMP) at 130 °C (Table 4). In addition, the recy-
non-stoichiometric hydroxyapatites. Non-stoichiometry results cling of the PdHAP-1 was briefly investigated in the coupling of
in: i) the presence of a vacancy defect in cationic site and OH , bromobenzene with styrene. The results showed that the catalyst
ii) a state of crystallinity that is especially poor the further hydrox- could be recycled at least three times without any loss of activity.
yapatite is from stoichiometry, and iii) more solubility with Unfortunately, the Heck reaction of aryl chlorides was not reported
increasing distance from stoichiometry. for this catalytic system under these conditions.
Paul and colleagues reported the preparation of HAP-supported
4. Catalytic applications of hydroxyapatite palladium particles (average size = 20 nm) by treating hydroxyap-
atite and Pd(OAc)2 in ethanol, followed by reduction with hydra-
4.1. Cross-coupling reactions zine hydrate. The ensuing material was investigated as a catalyst
and its application in Suzuki-Miyaura coupling reactions [123].
Carbon-carbon cross-coupling reactions are among the most Using 0.33–0.55 mol% of Pd catalyst and K2CO3 as the base in the
important synthetic transformations developed in the 20th cen- presence of TBAB as phase-transfer agent, this catalyst provided

Table 1
Examples of substitutions in the apatite structure [ref].

Me2+ XO34 Y
2+ 2+
Mg Cd PO34 SiO34 AsO34 OH F Cl
Sr2+ Cu2+ Pb2+ SO34 MnO34 VO34 Br I
Ba2+ Zn2+ CrO34 CO23 HPO24 S2 O2 CO23
Na+ K+ Eu3+
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 53

Table 2
Coupling of aryl bromides with phenylboronic acid catalyzed by PdHAP-1 [121].

Entry R1 Time (h) Yield (%) TON

1 H 4 80 40000
2 OMe 6 91 45500
3 (CO)Me 4 94 47000

Table 3
Coupling of aryl chlorides and phenylboronic acids using PdHAP-1 [122].

Entry R Time (h) Yield (%) TON

1 H 5 30 100
2 CHO 2 70 233
3 (CO)Me 1 92 613
4 NO2 1 > 99 > 660

Table 4
Heck reactions of aryl bromides with olefins catalyzed PdHAP-1 [122].

Entry R1 R2 Time (h) Yield (%) TON

1 H Ph 24 94 47000
2 OMe Ph 24 90 45000
3 (CO)Me Ph 20 96 48000
4 H (CO)O-nBu 20 91 45500
5 OMe (CO)O-nBu 24 94 47000
6 (CO)Me (CO)O-nBu 20 98 49000

good yields for the synthesis of biaryls, polyaryls and heteroaryls desired product in good to excellent yields using water as the sol-
by coupling aryl bromides with arylboronic acids (Scheme 2). vent, but with slower kinetics compared to methanol as the sol-
The catalyst was recyclable over at least five cycles without any vent. The recyclability of this catalyst was examined in the
apparent deactivation in the coupling of 4-bromoacetophenone coupling of ethyl 4-bromobenzoate or 4-bromoanisole with potas-
with phenylboronic acid. This result demonstrated the chemical sium phenyltrifluoroborates. The catalyst was found to be recy-
stability of the HAP-supported Pd catalyst. In a scale-up study, clable ten times with only a slight loss of activity for the reaction
9 g of 4-acetylbiphenyl was isolated in a 92% yield starting from of ethyl 4-bromobenzoate; its activity began to drop appreciably
a mixture of 50 mmol of 4-bromoacetophenone, 75 mmol of after the sixth cycle for the reaction of 4-bromoanisole.
phenylboronic acid, 12 g of catalyst, 50 mmol of TBAB, and Despite being outside of the main scope of the present review,
150 mmol of K2CO3, in 250 mL of H2O during 7.5 h at 100 °C. Unfor- the first example of the exploration of highly basic fluorapatite as
tunately, additional information concerning the Pd leaching and support in Suzuki-Miyaura reactions by Kantam and colleagues is
the nature of active species was not reported for this system. A worth mentioning [125]; they synthesized a fluorapatite-
study on a more diverse array of substrates would be necessary supported Pd catalyst by treatment of fluorapatite with
to determine the scope of this catalyst. PdCl2(PhCN)2 in acetone. Under optimized conditions that involve
In a recent study, Masuyama and colleagues prepared PdHAP by 0.15 mol% of the palladium catalyst, Na2CO3 as the base, and MeOH
introduction of Pd via ion-exchange with calcium in HAP matrices as the solvent, aryl iodides and bromides were successfully coupled
[124] wherein Pd could be firmly supported by the chelation of with aryl boronic acids at room temperature. However, the cou-
phosphate moieties of HAP, which suppresses the leaching of the pling of the widely available and low-cost aryl chlorides with
Pd(II) or in situ reduced Pd(0) into the reaction medium. The per- phenylboronic acid required higher PdFAP loading, elevated tem-
formance of this heterogeneous catalyst was evaluated in peratures and the use of TBAB as an additive (Table 5). The hetero-
Suzuki–Miyaura-type cross-coupling reaction of aryl bromides geneous Pd catalyst could easily be recovered by simple filtration; it
and potassium aryltrifluoroborates, in the presence of triph- could also be reused at least three times with consistent activity.
enylphosphine and K2CO3 as a base, at 50 °C using methanol as More recently, the synthesis of a new HAP supported Pd catalyst
the solvent (Scheme 3). The catalyst was shown to provide the and its use as efficient catalyst in the Suzuki-Miyaura
54 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

Scheme 2. Selected examples of Suzuki-Miyaura reaction using Pd/HAP as catalyst [123].

Scheme 3. PdHAP-catalyzed Suzuki-Miyaura-type cross-coupling reactions of aryl bromides and potassium phenyltrifluoroborates [124].

Table 5
Suzuki–Miyaura coupling of aryl chlorides using PdFAP catalyst [125].

Entry R Time (h) Yield (%) TON

1 NO2 6 94 335
2 CN 6 92 328
3 (CO)Me 6 94 335
4 H 30 45 160
5 OMe 30 32 114

cross-coupling reactions in water have been reported [126]. This 4.2. Condensation reactions
heterogeneous catalyst was obtained by immobilizing dichloro(1,
5-cyclooctadiene)palladium on the HAP. Using this catalyst, 4.2.1. Knoevenagel reaction
electron-rich, electron-neutral, electron-poor and sterically hin- Recently, solid base materials have attracted increased interest
dered aryl boronic acids were efficiently coupled with aryl halides due to their potential application as environmentally friendly cat-
containing electron-donating and electron withdrawing sub- alysts in a number of important industrial reactions, especially fine
stituents. This included aryl chlorides in the presence of potassium in chemical synthesis [127–129]. In this context, Knoevenagel con-
carbonate as the base and tetrabutylammonium bromide as the densations of aldehydes with active methylene compound are
phase-transfer agent (Scheme 4). The catalyst could be recycled among the most important processes in organic chemistry, their
several times without any detectable deactivation or leaching of use ranging from the synthesis of small molecules, to the elegant
the catalyst. Heterogeneity tests clearly indicated that the reaction intermediates for anti-hypertensive drugs and calcium antagonists
occurred at the surface of the support through a truly heteroge- [130–132]. These reactions allow the synthesis of cinnamic acid, in
neous catalysis. Importantly, under similar reaction conditions, which its ester and carboxylic functional derivatives are very
this catalyst exhibited superior catalytic properties compared to important components in flavors, perfumes, synthetic indigo and
catalyst prepared by reduction of HAP supported Pd(2+) catalyst pharmaceuticals. These reactions were mostly carried out by
with sodium borohydride in ethanol. homogeneous catalytic systems using weak bases like primary,

R3 R1
0.034 mol% of catalyst
R1 Cl + R4 B(OH) 2 R3 R4
H2O, 60°C, 24h
R2 TBAB, K 2CO3 R2
R1 = H, Me, NO 2 Yield = 82-94%
R 2 = Me R 3 = Me

Scheme 4. Suzuki coupling of chloroarenes with arylboronic acids catalyzed by Pd(0)HAP [126].
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 55

secondary, tertiary amine and ammoniums salts and Lewis acids Table 8
[133–138]. However, these catalysts have numerous disadvantages Knoevenagel condensation catalyzed by modified HAP [145].

such as waste production, corrosion and lack of catalyst recovery.

As a result of these shortcomings, other heterogeneous catalysts
have been developed in recent years [139–143]. Boulaajaj and col-
leagues investigated the Knoevenagel reaction using hydroxyap-
atite at room temperature in the absence of any solvents and
Entry Catalyst Yield (%)
reported the use of hydroxyapatite as a heterogeneous catalyst
1 KF 5
[144]. The HAP catalyst was able to promote the reaction, although
2 FAP 60
longer reaction times were required. By adding water and benzyl- 3 HAP 50
triethylammonium chloride (BTEAC) separately, there was a signif- 4 KF/FAP 80
icant improvement in the scope and mildness of this catalyst 5 KF/HAP 91
system; excellent yields were obtained by simultaneous addition
of these components (Tables 6 and 7). It is believed that the addi-
tion of water dissolved the ammonium salt and facilitated its inter- Table 9
action with HAP, which therefore allowed the activation of Knoevenagel condensation catalyzed by modified HAP [145].
catalyst. This heterogeneous catalyst can be readily recovered by
filtration and subsequently calcined at 700 °C before being reused
nine times without marked loss of catalytic activity.
Another independent study examined Knoevenagel condensa-
tion using HAP prepared by the co-precipitation method [145]
Entry Catalyst Yield (%)
where methanol was found to be the best solvent among those that
1 KF 17
were surveyed. The catalyst displayed superior to fluorapatite in
2 FAP 13
the condensation of benzaldehyde with methylcyanoacetate as a 3 HAP 25
model reaction; doping of HAP with potassium fluoride was bene- 4 KF/FAP 79
ficial for the rate and reaction yield (Tables 8 and 9). It was shown 5 KF/HAP 95
that the reactions took place at the surface of the catalyst in
heterogeneous media and the catalyst could be reused, washed,
and dried after filtration; catalyst maintained good catalytic activ- unique physico-chemical properties including negligible vapor
ity after three runs. pressure, wide liquid range, higher ionic conductivity and excellent
In a similar study, the Knoevenagel condensation of benzalde- solubility [147–150]. Xia and colleagues took an interesting
hyde with ethyl cyanoacetate at room temperature was reported, approach in their study by describing the synthesis of a series of
in the presence of as-synthesized and aluminum-enriched HAP as imidazole-based ionic liquid with various alkyl-chain lengths
catalysts [146]. The latter exhibited significantly enhanced cat- grafted on c-Fe2O3, encapsulated in a hydroxyapatite [151]. These
alytic activity which was ascribed to an increased surface area basic magnetic nanoparticles were used as efficient and recyclable
and the presence of HPO24 species. The presence of HPO24 species heterogeneous catalysts for Knoevenagel condensation between
can lead to the formation of Al+3–O2 acid–base pair sites by the various aldehydes and malononitrile, and were put under mild
interaction between Al of AlPO4 with the OH group of HPO24 . conditions in an aqueous environment. XRD, XPS, and TEM mea-
Ionic liquids recently emerged as a promising media for homo- surements confirmed the presence of 1–3 nm c-Fe2O3 particles in
geneous catalysis as well as catalysts. These new compounds have the HAP matrix. This heterogeneous catalyst showed higher cat-
alytic activity than the carrier HAP-c-Fe2O3 and the homogeneous
Table 6 basic ionic liquid [Bmim]OH (Bmim = 1-n-butyl-3-
Synthesis of alkenes via Knoevenagel condensation catalyzed by HAP [144]. methylimidazolium). The high catalytic activity was attributed to
the cooperation between the base sites generated by HAP frame-
work and supported basic ionic liquids; activity decreased gradu-
ally in the sequence of CH3 > C4H9 > C8H17 > C16H33. This decrease
in activity could be ascribed to the low accessibility to the basic
Entry Solvent Time (h) Yield (%)
centers with an increase in steric hindrance, as well as a lower
loading of basic centers (Scheme 5).
1 No solvent 15 24
2 H2O 10 83
The catalyst recovery was quantified by simple magnetic
3 BTEAC 3 87 decantation using a permanent magnet. The catalyst was reused
4 H2O/BTEAC 3 96 several times and remained consistent even after the fourth cycle.

Table 7
Synthesis of alkenes via Knoevenagel condensation catalyzed by HAP [144].

Entry Solvent Time (h) Yield (%)

1 No solvent 30 20
2 H2O 30 22
3 BTEAC 20 37
Scheme 5. Knoevenagel reaction catalyzed byionic liquids functionalized HAP-c-
4 H2O/BTEAC 20 64
Fe2O3 [151].
56 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

Table 10
Knoevenagel reaction facilitated by ionic liquids functionalized HAP-c-Fe2O3 [152].

Entry R1 R2 T (°C) Time (h) Yield (%)

1 CN (CO)OEt 50 3 88
2 (CO)OEt (CO)OEt 50 8 50
3 (CO)Me (CO)Me 80 9 91
4 (CO)Me (CO)OEt 80 10 86

Similarly, Xia and colleagues also reported the synthesis and cat- Table 11
alytic activity of the HAP-encapsulated c-Fe2O3 nanoparticles func- Knoevenagel reaction catalyzed by apatite phosphates containing heterovalent
tionalized with diethyl aliphatic amine basic ionic liquids [152]; cations [154].
good to high yields were obtained in the condensation of various
aldehydes with malononitrile in water at 30 °C (Table 10). Impor-
tantly, this catalyst was found to be superior to homogeneous basic
ionic liquids and the basic ionic liquid-modified polystyrene resin.
This excellent catalytic activity was attributed to the cooperativity
Entry Catalyst Solvent Time (h) Yield (%)
between the base sites generated by framework HAP and the sup-
ported basic ionic liquids. In addition, the results revealed that cat- 1 NaLaCa3(PO4)3OH Neat 30 29
2 NaLaCa3(PO4)3OH H2O 30 42
alyst could be recovered and recycled by simple magnetic
3 LaSr3(PO4)3OH Neat 30 22
decantation, and it could be reused for more than four consecutive 4 LaSr3(PO4)3OH H2O 15 41
trials without significant loss of catalytic activity.
Benhida and colleagues reported the use of porous calcium HAP
as recoverable heterogeneous catalyst [153] using MW irradiation.
The catalyst calcined at 300 °C provided good yields in Knoeve-
nagel condensation for a range of aldehydes that incorporated
electron-donating and electron withdrawing substituents, with
malonitrile and ethyl cyanoacetate (Scheme 6). This catalyst exhib-
ited superior catalytic properties compared to the catalysts cal-
cined at 100, 800 °C and KF/Al2O3 a presumably influenced by
the specific surface area and the chemical nature of the solid sur-
face; catalyst could be recovered by simple filtration and reused
for at least ten reaction cycles without loss of activity.
Scheme 7. Solvent-free Knoevenagel reaction catalyzed by cobalt HAP [155].
HAP analogues of the formula NaLaCa3(PO4)3OH and
NaLaSr3(PO4) have been synthesized to evaluate catalytic activity
in the Knoevenagel condensation (Table 11) [154] which were Jonnalagadda and colleagues reported the use of cobalt HAP as
found to be stable but less active. The addition of water led to catalyst, under solvent-free conditions (Scheme 7) [155] which
the activation of these catalysts and the enhanced catalytic activ- provided products in high yields and with facilitated recovery
ity. An increase in OH sites ions on the surface may have been and reuse. However, deactivation was observed possibly due to
the cause of enhanced catalytic acitvity. Unfortunately, recycling the loss of catalyst during recovery and the poisoning of active
experiments were not reported in this study and a more diverse sites on the surface of catalyst via interaction with other products.
array of substrates is necessary to determine the further scope of
these catalysts. 4.2.2. Claisen-Schmidt reaction
The preparation of chalcones is of interest in organic chemistry
due to its wide presence in many bioactive natural products [156–
159] as they are important intermediates in the biosynthesis of fla-
vonoids and flavones, which are present in the soy beans and soy
derived products [160–162]. Claisen-Schmidt condensation is a
useful method for the generation of chalcones from arylaldehydes
and acetophenones, using various homogeneous catalysts. How-
ever in recent years, many heterogeneous catalysts have been used
to promote this reaction [163–166]. The research group of Sebti
reported an efficient and convenient route to the heterogeneous
synthesis of several chalcones using NaNO3/HAP [167]. The cata-
Scheme 6. Knoevenagel condensation using HAP under microwave heating [153]. lyst was prepared by adding HAP to an aqueous solution of sodium
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 57

Table 12 be a highly efficient catalyst for Michael addition of mercaptans

Claisen-Schmidt condensation catalyzed by modified HAP [167]. and chalcone derivatives (Scheme 9) [179] in ethanol and metha-
nol were the best solvents among those surveyed. Zahouily and
colleagues indicated that the reaction occurred at the surface since
the dimensions of the tunnels of the catalyst were not large
enough, and therefore inaccessible to reactants. The acidic charac-
ter of HAP probably induced the polarization of the C@O bond, and
Entry Catalyst Time (h) Yield (%) the basic sites probably helped enhance the thiolnucleophilicity.
Consequently, the S–C bond formation accelerated and the final
1 HAP 12 7
2 NaNO3/HAP 6 92 product was obtained after protonation of the resulting enolate.
3 NaNO3/HAP/BTEAC 2 95 This catalyst exhibited a higher efficiency compared to natural
phosphate, synthetic diphosphate, Na2CaP2O7 and fluoroapatite;
it showed slightly lower efficiency than potassium fluoride doped
nitrate, followed by stirring and calcination at 900 °C. The XRD with natural phosphate. Moreover, the catalyst was quantitatively
analysis showed the apparition of news phases; one phase recovered by simple filtration, calcined at 500 °C and reused for
observed was probably NaCaPO4. The best results were obtained seven cycles with an almost consistent activity.
with NaNO3/HAP = 1/2 and used methanol as a solvent. The addi- The same research group reported that HAP modified by sodium
tion of benzyltriethylammonium chloride was beneficial for the nitrate, which was found to be effective for selective hydration of
reaction yield (Table 12). It is noteworthy that catalytic activity nitriles, can also be applied to Michael-type addition of aliphatic
decreased progressively when the recovered catalyst was dried at and aromatic amines with a,b-unsaturated carbonyl compounds
150 °C. at room temperature [180]. In this study, the NaHAP was more
The same group described the synthesis of chalcones deriva- active for the reactions in methanol than HAP alone although
tives via Claisen-Schmidt using the HAP under MW irradiation authors did not explain the cause of the difference in reactivity
(Scheme 8) [168]. The solvent had a pronounced effect in these (Table 13). The catalyst was recycled, washed with dichloro-
reactions, of which water proved to be the best solvent; DMF, methane, and calcined at 900 °C.
methanol and ethanol produced moderate yields. According to The b-amino carbonyl compounds synthesized by HAP-
the study, the water acted as a co-catalyst at a specific volume, modified sodium nitrate were successfully used as a direct precur-
however, the increase in its quantity led to a decrease in the cat- sor for synthesized b-amino acids (Scheme 10). For example, the
alytic activity of the HAP which may be due to the formation of a 1,3-diphenyl-3-(phenylamino)propan-1-one was synthesized by a
water-film on the active surface of the catalyst, affecting its reaction of aniline with 1,3-diphenyl-2-propenone, which then
hydrophobicity. The study did not explain the precise role of the was converted to oxime in the presence of NaHAP with an excel-
activation of recovered catalyst via calcination at various tempera- lent yield. The latter was subjected to the reaction induced by thio-
tures with regard to the activity of the catalysts. nyl chloride and chemoselective Beckmann rearrangement to
provide the N-phenylamino-3-phenyl-3-(phenylamino)propan-1-
one. This produced the 3-phenyl-3-(phenylamino)-propanoic acid
4.2.3. Michael addition
after esterification reaction, followed by hydrolysis.
Michael addition is one of the most useful methods for the for-
A similar study reported the preparation of zinc bromide sup-
mation of carbon–carbon bonds in organic chemistry under mild
ported on HAP, and its application as an efficient heterogeneous
conditions [169–171]. Various heterogeneous catalysts have been
catalyst to promote the synthesis of 3-substituted indoles from
developed [172–175] to replace soluble strong bases that are tradi-
Michael addition to indoles to a,b-unsaturated ketones (Table 14)
tionally used for this reaction, which can then lead to side reactions
[181]; the substitution of the indole nucleus occurred exclusively
like auto-oxidation or retro-Michael type decompositions [175–
at the 3-position without the formation of N-alkylation products.
178]. HAP prepared by the co-precipitation method was found to

Scheme 8. Synthesis of chalcones using HAP under microwave irradiation [168].

Scheme 9. Michael reaction using HAP as catalyst [179].

58 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

Table 13
Formation of carbon-nitrogen bond using of HAP and NaHAP catalysts [180].

Entry R1 R2 Catalyst Time (h) Yield (%)

1 H C6H5 HAP 24 30
2 H C6H5 NaHAP 1.5 99
3 Cl C6H5 HAP 24 80
4 Cl C6H5 NaHAP 6 96
5 OMe C6H5 HAP 24 2
6 OMe C6H5 NaHAP 4 96
7 Me C6H5 HAP 24 78
8 Me C6H5 NaHAP 6 90
9 H 4-MeOC6H5 HAP 24 42
10 H 4-MeOC6H5 NaHAP 1 98
11 Cl 4-MeOC6H5 HAP 24 44
12 Cl 4-MeOC6H5 NaHAP 8 70
13 OMe 4-MeOC6H5 HAP 24 20
14 OMe 4-MeOC6H5 NaHAP 7 92
15 H C6H5CH2 HAP 48 62
16 H C6H5CH2 NaHAP 5 94
17 Cl C6H5CH2 HAP 48 85
18 Cl C6H5CH2 NaHAP 5 92

Scheme 10. Synthesis of b-amino acid using modified HAP as catalyst [180].

Unfortunately, the study did not report any information regarding NMR studies of the reaction products showed that part of the deu-
leaching or mechanisms. terium atoms had been transferred from the partially deuterated
Gruselle and co-workers reported that the calcium hydroxyap- apatite to the methylene group, which is adjacent to the ketone
atite with different compositions and various specific surface areas function of the 3-oxo-butyl chain of the final product (Scheme 11).
was highly active in the Michael reaction of ethyl 2- These results confirmed that the hydroxyl ions located on the sur-
oxocyclopentanecarboxylate with 3-buten-2-one, in the absence face of the apatites were responsible for the basicity and acted as a
of solvents [182]; products were obtained with 90% conversion at basic catalyst that led to a carbanion by abstraction of an acidic
65 °C, regardless of different stoichiometries and specific surface proton.
areas. Using deuterium-labeling experiments to explain the origin The use of the Michael reaction was extended to calcium HAP
of the basicity of this catalyst, the authors proposed a mechanism with Ca/P = 1.61. The reaction of ethyl 2-oxocyclopentane-
based on the basic properties of the calcium HAP surfaces. The carboxylate, methyl 2-oxocyclopentanecarboxylate, ethyl
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 59

Table 14
ZnHAP-catalyzed Michael addition of indoles to electron-deficient olefins [181].

Entry R1 R2 R3 Time (h) Yield (%)

1 CH3 CH3 H 4 98
2 H CH3 H 4 89
3 C6H5 CH3 H 20 98
4 H C6H5 C6H5 24 70
5 CH3 C6H5 C6H5 24 95
6 C6H5 CH3 C6H5 24 21

Scheme 11. Proposed mechanism for the deuterium transfer from the apatite surface to the final product [182].

Scheme 12. Michael carbon-carbon bond formation using HAP as catalyst [182].

2-oxocyclohexanecarboxylate, methyl 1-oxoindan-2-carboxylate extended to include various sets of donors and acceptors
and ethyl 3-oxo-3-phenylpropanoate with 3-buten-2-one pro- (Scheme 13).
duced good to excellent yields (Scheme 12). Importantly, this The calcium vanadate apatite was also tested as a catalyst in
heterogeneous catalyst was readily recovered by filtration, subse- Michael addition of ethyl 2-oxocyclopentanecarboxylate with
quently washed with ethanol or dichloromethane, then was reused 3-buten-2-one where a 99% yield of the targeted ethyl
several times without marked loss of catalytic activity. 2-oxo-1-(3-oxocyclohexyl)cyclopentanecarboxylate compound
Kaneda and colleagues described the use of calcium vanadate was consistently obtained during four consecutive cycles (Table 15)
apatite (VAP), in which a [PO4]3 group of HAP was substituted [184]. There was no observable leaching of any vanadium in the
by [VO4]3 ; for a Michael reaction of 2-oxo-cyclopentane car- aqueous phase that was discerned. To check the heterogeneity of
boxylic acid ethyl ester with 2-cyclohexen-1-one as a model reac- this system, the catalyst was separated by a simple filtration from
tion [183]. The catalytic activity was attributed to a [VO3OH]2 the reaction mixture with 55% conversion; the reaction was con-
moiety which ensued from partial dissolution of the apatite in tinued for an additional 1 h. The conversion remained almost
water and the calcination process was necessary to achieve cat- unchanged, which clearly demonstrated that vanadium did not
alytic activity. It is interesting to note that orthovanadate and leach as confirmed by ICP analysis and the absence of vanadium
pyrovanadate derivatives that contained isolated VO4 tetrahedra in the filtrate.
such as Na3VO4, K3VO4, and Mg2V2O7 were found less effective Electropositive properties and the coordination ability of lan-
compared to calcined calcium vanadate apatite; procedure was thanide ions have been exploited by HAP-bound lanthanum cata-
60 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

Scheme 13. Aqueous Michael reaction catalyzed by calcium vanadate apatite [183].

Table 15 This approach was extended to an asymmetric version of

Recycling experiments of VAP-catalyzed aqueous Michael reaction [184]. Michael reaction where in the heterogenized La3+ species and (R,
R)-tartaric acid on HAP were used. The supported catalyst was suc-
cessfully tested in the addition of cyclic acetoacetates to methyl
vinyl ketone in toluene, affording the respective product a 99%
yield and 30% ee (Table 17). Unfortunately, the catalytic system
proved to be less enantioselective than LaFAP.

4.3. Oxidation reactions

Entry Cycle Conversion (%) Yield (%)
1 First cycle 99 99 Selective oxidation reactions constitute industrial core tech-
2 Second cycle 99 99 nologies for converting bulk chemicals to useful products of a
3 Third cycle 99 99 higher oxidation state and recently many heterogenous catalyst
4 Fourth cycle 99 99 systems have been developed for selective oxidation catalysis
[187,188].

Table 16 4.3.1. Oxidation of alcohols

Michael catalyzed by various modified HAPs [185]. The selective oxidation reactions of alcohols are undeniably
part of the key reactions of organic synthesis; they allow the syn-
thesis of carbonyl compounds which are very useful for the synthe-
sis of important pharmaceutical intermediates [189,190]. A
considerable effort has been devoted to develop efficient heteroge-
neous catalysts to replace the classical oxidation methods employ-
ing stoichiometric permanganate, dichromate or nitrogen oxides in
oxidations carried out with nitric acid. Among the developed cat-
Entry Catalyst Solvent Yield (%)
alytic materials, supported ruthenium (Ru) and Pd catalysts are
transition metals that offer excellent opportunities for aerobic oxi-
1 LaHAP Neat >99
dation of alcohols.
2 ScHAP Neat 90
3 YHAP Neat 67 Despite the remarkable efforts since 1967, and in contrast to
4 LaFAP Neat 41 Suzuki reactions, there are relatively few examples of heteroge-
5 LaHAP H2O >99 neous Pd-catalyzed aerobic oxidation of alcohols [191]. Among
6 LaHAP C6H5CH3 58
the catalysts developed, the Pd on activated carbon [192], Pd on
7 LaHAP CH3CN 35
8 LaHAP CH2Cl2 30 hydrotalcite [193], Pd on simple oxides such as titania [194], and
9 LaHAP C6H12 21 Pd/polymeric materials [195] are most reliable. However, these
10 LaHAP THF 9 systems suffer from a number of drawbacks namely moderate cat-
11 LaHAP DMF Trace alytic activity and a limited scope of substrates. An important con-
tribution in the development of heterogeneous Pd catalysts for
selective oxidation of alcohols was described by Kaneda and col-
lyst prepared via a cation-exchange method in the Michael addi- leagues in 2002 and 2004 [121,196] wherein HAP-supported Pd
tion reaction of 2-oxocyclopentanecarboxylate with methyl vinyl nanoclusters PdHAP-0 were shown to be efficient not only for Heck
ketone under aqueous or solvent-free conditions. The main find- and Suzuki reactions, but were also useful for aerobic oxidation of
ings were that the LaHAP catalyst was more active compared to alcohols. Using 0.2–0.6 mol% Pd catalyst and molecular oxygen as
ScHAP, YHAP, YbHAP and LaFAP (Table 16) [185,186]. Among the oxidant, a wide variety of alcohols (including bearing heteroatoms
solvents surveyed, neat and aqueous conditions provided higher substrates) were oxidized in trifluorotoluene at 90 °C, in water at
yields than those using organic solvents. It is worth noting that this 110 °C or under solvent-free conditions (Scheme 14). This method-
methodology could be extended to other 1,3-dicarbonyl com- ology could be extended to a larger-scale study of the oxidation of
pounds and enones. Due to its heterogeneous character, the cata- 1-phenylethanol under solvent-free conditions at 160 °C. Impor-
lyst was reused during three cycles under solvent-free conditions. tantly, TEM analysis revealed that during reaction Pd(2+) was
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 61

Table 17
Asymmetric Michael reaction catalyzed by calcium lanthanide apatite [186].

Entry Catalyst Yield (%) ee (%)

1 LaFAP 97 60
2 LaHAP >99 30

Scheme 15. Proposed reaction pathway for the oxidation of alcohols on the surface
of Pd(0) nanoclusters [196].

which is efficient for Suzuki couplings, could also perform the

Scheme 14. Oxidation of various alcohols catalyzed by PdHAP-0 using molecular
oxygen [196].
selective aerobic oxidation of benzyl alcohols to corresponding
aldehydes, using water as the solvent under atmospheric air
(Table 18) [123]. The reusability of this catalyst was examined in
reduced to Pd(0) by the reactant alcohol and the active catalytic the oxidation of benzyl alcohol, and the results of the study
species were apatite-supported Pd nanoparticles, with an average showed that the catalyst could be recycled at least five times with
diameter of 4 nm. Pd leaching from this heterogeneous catalyst only a slight loss of activity (from 95 to 86% yield after five cycles);
was evaluated in the oxidation of 1-phenylethanol which clearly leaching studies were not reported for this system.
demonstrated that no leaching of Pd in active form occurred. The Studies have shown that a variety of low valent Ru species sup-
catalyst was recovered by centrifugation, followed by filtration, ported on solid matrices such as zeolites [199], alumina [200], sil-
and was reused three times without any loss of catalytic activity icotungstate [201], and hydrotalcite [202] catalyze the oxidation of
when another equivalent of the1-phenylethanol and trifluoro- alcohols with negligible Ru leaching. However, these catalysts dis-
toluene was added. play strong shape selectivity due to uniform pore size, but their
The probable reaction mechanism was initiated by oxidative activity is moderate compared with some platinum and Pd-based
addition of OAH alcohol bond by the unsaturated Pd(0) species catalysts. Monomeric Ru species were immobilized on the surface
located at the edge to afford a Pd-alcoholate species. The latter of HAP by an equimolar substitution of Ca(2+) ions with Ru(3+)
underwent a b-hydride elimination that produced the carbonyl [203]. This heterogeneous catalyst gave efficient conversions of
compounds and a hydrido-palladium species, which reacted with primary, secondary and functionalized alcohols using molecular
molecular oxygen to regenerate the Pd(0) species. This reaction oxygen but required high catalyst loading (Scheme 16).
closed the catalytic cycle as well as the formation of O2 and H2O Kaneda and colleagues indicated conclusively that the active
(Scheme 15). species are monomeric Ru cation surrounded by four oxygen and
Conducting oxidation reactions in aqueous media can be advan- chlorine which contrasts with the findings of Opre and colleagues
tageous, particularly for large-scale industrial applications. Some for a similar catalyst [204]. The reusability of RuHAP catalyst was
of the benefits of an aqueous media include the ease of purification, assessed in the oxidation of benzyl alcohol with up to three consec-
environmental friendliness and use of water as a reaction medium utive cycles with consistent activity; the amount of Ru content in
[197,198]. Paul and colleagues demonstrated that he Pd(0)HAP the filtrate was below the detection limit of 10 ppb and the negli-
62 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

Table 18 LRu Cl
Oxidation of benzyl alcohols in presence of Pd(0)HAP as catalyst [123]. H OH
L= Phosphate ligand

R1 R2

HCl
1
Entry R Yield (%)
1 H 95 H O RuL
2 4-MeO 96
O
3 4-Me 92 β-elimination
R1 R2
4 4-Cl 91 H 2O + 1/2 O 2
5 4-F 93 R1 R2
6 4-NO2 90
7 3-NO2 87

H 2O 2
LRu H

H OH
O2
R1 R2
LRu OOH

Scheme 17. Plausible reaction pathway for the oxidation of alcohols using RuHAP
[203].

Scheme 16. Oxidation of various alcohols over RuHAP [203].

giving benzaldehyde in 93% yield; the turnover number based on
Ru approached 930 after 24 h. Baiker and colleagues reported the
gible leaching was attributed to the strong coordinations of Ru in effect of organic modification on the catalytic properties of RuHAP
the apatite framework. The oxidation was initiated by a ligand in the oxidation of aromatic and aliphatic alcohols using molecular
exchange between the alcohol and the chlorine moiety of RuHAP. oxygen as the sole source of oxidant [207]. This new strategy
In the second step, the Ru-alcoholate underwentb-hydride elimi- involved the modification of the host HAP and added polar organic
nation that produced the carbonyl compound and a hydrido- compounds that were able to form strong hydrogen bonds with the
ruthenium species. The latter reoxidized by molecular oxygen to OH and phosphate functions of HAP. The incorporation of Ru was
afford the Ru–OOH species, which underwent a ligand exchange not affected by the ion-exchange but by an adsorption process con-
with alcohol to regenerate the Ru-alcoholate species together with trolled by the polar organic compounds; organic modification
the formation of O2 and H2O (Scheme 17). tripled the catalytic activity of RuHAP due to higher intrinsic activ-
In an independent study, the same group described a very orig- ity of Ru species and coordination in organically modified HAP.
inal approach based on the synthesis of recoverable RuHAP- Interestingly, during the oxidation process, the modifiers leach
encapsulated superparamagnetic nanoparticles catalyst (RuHAP- out and thus do not disturb the catalytic oxidation of alcohols. To
c-Fe2O3) by the simultaneous crystallization of HAP and c-Fe2O3, check for leaching, the organically modified RuHAP was removed
under basic conditions [205]. The ion exchange capabilities of the at 60% conversion by simple filtration; the filtrate reacted under
external HAP surface were utilized to substitute calcium with Ru. the reaction conditions. The above treatment of the filtrate did
The physicochemical characterization revealed that the c-Fe2O3 not provide any yield. It clearly demonstrated that there was not
nanoparticles were uniformly dispersed on the HAP matrix and any leaching of ruthenium in active form. The reusability of this
had an average size of 8 nm. The catalyst provided a very efficient heterogeneous catalyst was also tested. After complete conversion
system for aerobic oxidation of a variety of benzylic, allylic, alipha- of benzyl alcohol, an equimolar amount of 4-methylbenzyl alcohol
tic, aliphatic and heterocyclic alcohols at room temperature in tri- was added to the reaction mixture and the reaction was com-
fluorotoluene or toluene in the absence of any additives pleted. The same procedure was repeated with the opposite
(Scheme 18). sequence of alcohol addition. The results indicated that the average
Importantly, this system was found equally active in the oxida- reaction rates in the oxidation of benzyl alcohol were almost iden-
tion of a series of sterically bulky alcohols. For example, 3,5- tical, independent of the order of the addition of the two sub-
dibenzyloxybenzyl alcohol, cholestanol and hexadec-7-yn-1-ol strates. In a subsequent study, the catalytic activity of RuHAP
were successfully converted quantitatively into the corresponding could be improved by the incorporation of various promoter ions
carbonyl compounds, under relatively mild conditions. The catalyst into the HAP lattice [207]. After incorporation of Ru, the thermal
could be separated from the reaction mixture by an external mag- treatments of the catalysts were critical due to the dehydration
net, avoiding the usual filtration or centrifugation process and was and irreversible restructuring of the active species Ru(OH)2+ and
recycled several times without any detectable deactivation and nor its surroundings. On the basis of various methods of characteriza-
leaching of the catalyst to the organic layer. The Ru species on the tion, it was thought that the active site consisted of Ru(OH)2+2 sur-
RuHAP-c-Fe2O3 surface is a monomeric Ru(OH)2+ 2 surrounded by rounded by four oxygen atoms. The RuCoHAP and RuPbHAP that
four phosphate ligands, an observation which contrasts with a pre- dried at moderate temperature gave satisfactory yield and showed
vious report by Opre and colleagues on RuHAP [206]. According to selectivity in oxidation of benzyl alcohol in the presence of molec-
the authors, the lowering of the Ru content and incorporation of c- ular oxygen. It is interesting to note that catalysts that were pre-
Fe2O3 nanoparticles might play an important role on the local envi- pared with a short contact time were more active than those
ronment of the active Ru species. 1-phenylethanol was oxidized prepared with a longer contact time. This finding is due to the min-
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 63

Scheme 18. RuHAP-c-Fe2O3-catalyzed oxidation of alcohols [205].

Scheme 19. Oxidation of alcohols over RuCoHAP [207].

imization of restructuring via dissolution-redeposition. The scope catalyst that entailed impregnating sheet composites with RuHAP
of the RuCoHAP catalyst, prepared by reaction of CoHAP and aque- powder; this technique showed a superior performance compared
ous RuCl3 solution at room temperature for 10 min, was studied in to RuHAP beads in oxidation of benzyl alcohol and benzaldehyde in
the oxidation of various alcohols (Scheme 19). Under optimized a batch reaction process. Using this heterogeneous catalyst, the
conditions that involve 1.7 mol% of the ruthenium catalyst, toluene oxidation of benzyl alcohol in a continuous system and a fixed-
as the solvent and molecular oxygen as oxidant, the benzylic and bed reactor were also examined; RuHAP sheets showed more
cycloaliphatic alcohols were successfully transformed selectively oxidative efficiency compared to the powder catalyst as the porous
to the corresponding carbonyl compounds. However, the oxidation sheet structure improves the mass transfer within the sheet.
of primary and secondary aliphatic alcohols required high catalyst Although not relevant to the present section, the racemization of
loading compared to aromatic alcohols; no leaching of Ru from the chirally secondary alcohols by employing immobilized Ru on
catalyst occurred under the reaction conditions. HAP has been demonstrated [210]; both a-benzylic and aliphatic
The exact mechanism of the RuCoHAP catalyzed alcohol oxida- alcohols were racemized at 80 °C in toluene in a substrate to cata-
tion reaction is unknown and is generally supposed to take place lyst ratio of 33.
through the hydridometal pathway (Scheme 20) [208]. The first
step of the mechanism involves the formation of a Ru-alcoholate 4.3.2. Oxidations of silanols
species, which undergoes a-hydride elimination to produce the Silanol compounds have attracted worldwide attention in the
carbonyl compound, followed by a hydrido-ruthenium species synthesis of silicon-based polymeric materials as well as organics
which are then reoxidized by molecular oxygen to complete the [211–214]. These silanol compounds are mostly used as valuable
catalytic cycle (Scheme 20). nucleophilic partners in transition-metal catalyzed carbon–carbon
Fukahori and colleagues reported the selective oxidation of ben- cross-coupling reactions [215–217], and in organocatalysts
zyl alcohol [209] using a papermaking technique to make a RuHAP for activating carbonyl compounds [218–220]. Typically these
64 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

H Although RuHAP was an effective catalyst for this process, its

R1
cost was a drawback. Fortunately, AgHAP prepared by similar
HO
HO OH strategy is significantly less expensive and was found to be more
R2
active than the Ru catalyst in water (Table 19) [228]. However,
Run+ Step 1
the silver (Ag) catalyst was effective only for aromatic silanes
Step 3
H 2O which could interact strongly with Ag nanoparticles thus conclud-
1/2 O 2 ing the existence of cooperative action between Ag nanoparticles
and HAP. The increasing concentration of nucleophiles OH from
H
water activated on the AgHAP surface promotes formation of sila-
R2 nols by suppressing condensation to disiloxane; the biphasic nat-
HO O
HO H ure of the organosilane/H2O system reduces the effective
Run+ R1 concentration of water in the organosilane phase [229].
Run+
Kaneda and colleagues reported successful use of gold (Au)
nanoparticles embedded in hydroxyapatite (AuHAP) in the cat-
alytic oxidation of silanes to silanols using water as an oxidant
Step 2 [230]; catalyst was synthesized by treatment of HAP, with an aque-
ous solution of HAuCl4. TEM measurements revealed that the aver-
O age size of the gold nanoparticles was 3.0 nm. Using 0.83 mol% of
catalyst and under organic-solvent-free conditions, various silanes
R1 R2 with different structures were converted selectively into the corre-
Scheme 20. Mechanism of alcohol oxidation over RuCoHAP [208].
sponding silanols in high yield (Scheme 22) with the exception of
triphenylsilane presumably due to strong steric hindrance
(Scheme 23). The catalyst offered a number of advantages, namely
compounds are prepared by hydrolysis of the corresponding of excellent stability, easy separation from the reaction mixture by
chlorosilanes, or from siloxanes and hydrosilanes via nucleophilic filtration, use of water as a clean oxidant, and reusability over sev-
substitution and oxidation [221–225]. However, the catalytic oxi- eral times without loss of activity and selectivity. Another advan-
dation of hydrosilanes using water as oxidant, and under neutral tage is that AuHAP catalysts can offer the possibility of the
conditions is an attractive route for clean and economic synthesis oxidation of a wide range of silanes, including various aliphatic
of silanols in comparison to other preparations [226]. The RuHAP silanes.
catalyst system, which was found to be effective for aerobic oxida-
tion of alcohols, can also be applied to oxidation of silanes [227]. 4.3.3. Epoxidation reaction
Ethyl acetate, (EtAc) acetonitrile and dimethylformamide were Epoxidation of olefin is a widely used transformation in the
the best solvents among those that were surveyed, and the use organic synthesis of fine chemicals [231,232]. It is an oxygen-
of typical heterogeneous catalysts such as Ru/carbon, RuO2 and transfer reaction for which hydrogen peroxide and its derivatives
Ru/Al2O3 etc. was less effective than RuHAP. A variety of silanes, are particularly well suited. A large number of epoxidation pro-
including aliphatic silanes, were successfully converted to corre- cesses have been developed in the recent years using homoge-
sponding silanols in good yields, by employing 5 mol% of catalyst neous and heterogeneous catalysts [233–237]. An effective and
in the presence of ethyl acetate as a solvent at 80 °C (Scheme 21). environmentally friendly protocol for the epoxidation of olefins
Recycling studies showed that the catalyst could be reused at least and a,b-unsaturated ketones using HAP as catalyst, has been devel-
five times with consistent activity. These leach-proof catalysts oped [238] via a sonochemical route and was deployed for a wide
leave no remnants of metal in the end products, an especially range of olefins and olefinic ketones using hydrogen peroxide
important feature since metal contamination is highly regulated under relatively mild reaction conditions. Acetonitrile and acetone
in the industry. were found to be the best solvents and no reaction was observed in
other solvents studied. The cyclic and linear olefins such as
cyclopentene, cyclohexene, substituted cyclohexenes, cyclooctene,
norbornene, 1-hexene, 2-hexene, 1-octene, and 2-octene afforded
the corresponding epoxides as sole products in good to excellent
yields. However, the epoxidation of cyclooctadiene gave a mixture
of mono and diepoxides. It is interesting to note that the epoxida-
tion of styrene led to styrene oxide in poor yield, with the forma-
tion of a small quantity of phenyl acetaldehyde. The epoxidation
of stilbene also gave poor yield, but its yields were greatly
improved by conducting the reaction in a mixture of acetonitrile
and acetone. This could be attributed to the enhancement of solu-
bility of stilbene in acetonitrile-acetone mixture when compared
to that in acetonitrile. A variety ofa,b-unsaturated ketones were
efficiently converted to the corresponding epoxides, but it was
found that the presence of a substituent at the olefinic carbon
inhibited the reaction, perhaps, due to the steric hindrance of the
substituent. The catalyst could easily be separated from the reac-
tion mixture by simple filtration and reused at least four times in
the epoxidation of cyclohexene, with no apparent deactivation
(Table 20).
Parvulescu and colleagues reported the epoxidation of cyclo-
hexene and indene using peroxotungstic species complexed
Scheme 21. RuHAP-catalyzed oxidation of silanes [227]. with phosphate groups at the surface of HAP in the presence of
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 65

Table 19
Oxidation of silanes by in water with Ag/HAP or Ru/HAP catalysts [228].

Entry Catalyst Solvent Time (h) Yield (%) TON Reused time
1 Ag/HAP (3 mol%) H2O 0.25 99 33 5
2 Ru/HAP (5 mol%) EtAc 3 99 20 5

of accessible OH groups and by the strength of the ensuing bond.

The epoxidation of cyclohexene and indene occurred with varying
TOFs and selectivities; cyclohexene led to rather high TOF values,
but the maximum selectivity to epoxide was 30%. Leached tung-
sten resulted in acidic species that catalyzed the hydrolysis of
epoxide to diols. In the case of the recycled catalysts, for which
the leaching was much reduced, the hydrolysis of epoxides to diols
could be associated with the properties of the remaining free OH
groups on HAP. In the second run, after the weakly bonded tung-
sten leached out, both the TOF and selectivity to epoxide increased.
A new magnetically recyclable and efficient nanocomposite cat-
alyst for the epoxidation of olefins was reported using molybde-
num oxide nanoparticles supported on HAP encapsulated c-Fe2O3
nanocrystallites [240]. The catalytic system comprising tert-butyl
hydroperoxide as oxidant and chloroform as the solvent, in the
presence of 20 wt% MoOx/HAP-c-Fe2O3 showed good activity for
the epoxidation of cyclohexene; cyclic and linear alkenes were all
converted into the corresponding epoxides with excellent conver-
sions and epoxide selectivities. The successful recycling tests are an
advantage of this methodology, since the recovered catalyst was
Scheme 22. Oxidation of silanes over AuHAP catalyst in water [230].
reused six times with a consistent activity; ICP analysis of the
filtrate confirmed that the metal content was negligible
(Mo < 5 lg/L, Fe < 3 lg/L). The epoxidation of styrene catalyzed
by Auclusters supported on HAP has been reported [241]. This
heterogeneous catalytic system was prepared by dispersion of
Au25(SG)18 (SG = glutathione ligand), followed by calcination to
remove the SG ligand, and was able to oxidize styrene with 100%
conversion and 92% selectivity in the presence of tert-
butylhydroperoxide (TBHP) as an oxidant at 80 °C. The
morphology-dependant catalyst prepared from the Au25(SG)18 pre-
cursor exhibited higher selectivity to styrene oxide than the same
Scheme 23. Oxidation of triphenylsilane using AuHAP catalyst [230].
catalyst prepared from HAuCl4 by adsorption technique, despite a
similar conversion and size of the supported Au nanoparticles. In
addition, recyclability and high selectivity make this catalyst a
Table 20
Reusability of HAP catalyst in the epoxidation of cyclohexene [238]. promising system for the selective epoxidation of alkenes. In
another study, Jin and colleagues showed that the very small col-
loidal clusters of Au, Au25, Au38, and Au144, capped with
phenylethanethiolate, (e.g., Au25(SC2H4Ph)18), was supported on
HAP and SiO2 for application in catalysis; oxidation of styrene in
the presence of TBHP or oxygen as the main oxidant, in toluene
as the solvent occurred at 80 °C. With TBHP as the oxidant, the cat-
Entry Cycle Yield (%)
alytic activity was almost independent of the size of the cluster but
1 1 65 when O2 was used as the oxidant, a distinct size effect was
2 2 66
observed for (Au) nanocatalyst in selective oxidation of styrene,
3 3 64
4 4 64 the order of catalytic activity being: Au25 > Au38 > Au144. After
calcination, the Au nanocatalysts were still active. However, aggre-
gation of gold was observed which might contrast the expected
benefit of decapping the catalytic centers. Using O2 as the sole oxi-
hydrogen peroxide [239]. In this study, the approach was to neu- dant, the uncalcined Aun(SR)m catalysts achieved higher activity
tralize the basic OH groups of HAP with tungstic acid or a complex than the calcined Aun(SR)m catalysts. This is due to cluster sinter-
of tungstic acid with Aliquat 336; bonding of WO3 and/or WO(O2)2 ing in calcination and the larger ensuing particles cannot effec-
units to the surface of phosphates generated the phosphotungstic tively activate O2. Using Au25/HAP capped catalyst at 80 °C in
species. However, anchoring on HAP was limited by the number toluene under similar reaction conditions, TBHP was more effective
66 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

than O2, while TBHP as initiator and O2 as the main oxidant exhib- (0.1  x  3.7 wt% Cr), prepared by cation-exchange method
ited an intermediate conversion. More importantly, in the case of between HAP and chromium(III) nitrate [252]. According to the
TBHP and (O2 + TBHP), the oxidation of styrene led to benzalde- authors, several isolated chromium species were identified after
hyde with high selectivity (100%) and 80% selectivity with sole calcinations, mainly being Cr2+, Cr+6 and Cr3+. The latter is prepon-
O2 as oxidant; acetophenone and styrene oxide were formed only derant at a much higher loading and located on the apatite surface
as minor reaction products. The catalytic activity of the thiolate- as isolated Cr3+–O–Ca2+ or Cr3+–O–Cr3+, whereas the Cr6+ is prepon-
capped cluster was surprising, considering the expected poisoning derant at low loading as monochromates; Cr6+ species might be
effect of sulfur compounds [242]. In brief, the selective oxidation of allowed only to initiate the cracking of propane since they were
styrene catalyzed by Au25(SCH2CH2Ph)18 nanoclusters, using three reduced by the reaction mixture. It has been proposed that the
different oxidation systems, involves the activation of oxygen on Cr3+ present in Cr3+–O–Ca2+ was the most active species because
small Au clusters and the role of peroxidic species; these gold it favors the release of the neighboring lattice oxygen, leaving
nanocatalysts can be readily recovered without any precautions either an oxygen vacancy or a Cr2+ species. The Cr3+–O–Cr3+ species
and reused several times with only a slight loss of activity. were considered less active because they were less basic than Cr3+–
O–Ca2+. The basicity of the HAP allowed abstraction of the proton
4.3.4. Oxidative dehydrogenation of ethane and propane from propane and the oxygen lability was favored by the presence
To date, steam cracking, fluid-catalytic-cracking and catalytic Cr3+. However, the decrease in the basicity induced by the fixation
dehydrogenation processes are the main methods to produce ole- of Cr3+ counterbalanced the positive effect of chromium on oxygen
fins, the oxidative dehydrogenation being an attractive alternative reactivity, which limited its performance.
for the efficient production of olefins with salient advantages that The same research group reported the synthesis of Fe3+-loaded
include: reduced cost, lower green house gas emissions, low HAP (FeHAP) and its catalytic activity toward propane oxidative
energy consumption and the low deposition of carbon during the dehydrogenation [253]; the characterization of FeHAP revealed
process [243,244]. In addition, this reaction is exothermic, avoiding the presence of Fe3+ species in distorted octahedral and lower coor-
the thermodynamic constraints of non-oxidative routes by forming dination site forms. The catalyst exhibited good propene selectivity
water as a byproduct. Extensive works on this topic have been (34–90%) but with low conversion. Importantly, the maximum
reported [245–247] and the yield of alkenes obtained by oxidative propene yield of 6.2% was obtained at low Fe content with the for-
dehydrogenation on most catalysts is limited by alkene combus- mation of carbon oxides and ethylene. The Fe3+–O–Ca2+ species
tion to CO and CO2. The effects of the addition of tetra- identified at low Fe content led to the maximum propene yield
chloromethane (TCM) into the feed-stream of the oxidative (6.2%) at 550 °C with the formation of carbon oxides and ethylene.
dehydrogenation of propane have been thoroughly investigated This may be due to low Fe content, which allowed avoidance of the
by Sugiyama and colleagues; strontium and barium supported on decrease in the basicity and maintained it for the hydrogen
HAP, with and without treatment with Cu2+ and Pb2+ have been abstraction from the propane.
used [248]. In the absence of TCM, the system SrHAP was signifi- On a side note, vanadium pentoxide, with loadings varying from
cantly more efficient than BaHAP. For both the SrHAP and BaHAP, 2.5 to 15 wt%, supported on HAP via wet impregnation techniques
the selectivity to propylene decreased with increasing time-on- have been used in oxidative dehydrogenation ofn-octane [254].
stream when the TCM was added. The introduction of lead by The XRD and IR characterizations revealed that the vanadium exhi-
ion-exchange, with calcium in the HAP, resulted in the decrease bits two types of phases, the vanadium pentoxide at lower loadings
in the yield of propylene, independently of the addition of TCM and pyrovanadate phase for weight loadings in excess of 10%. The
in the reaction mixture. In the presence of TCM, the incorporation electron microscopy measurements revealed that the vanadium
of copper in the HAP structures dramatically improved the conver- species were highly dispersed on the HAP. Importantly, the tem-
sion of propane and the selectivity to propylene 16 and 80%, perature programmed reduction showed that total acidity of the
respectively; the activities remained constant during 6 h on- catalysts increased as the vanadium loading increased. The vana-
stream. The understanding of the origin of this improvement still dium pentoxide exhibited high selectivity towards octenes and
remains an open question with a popular belief that the TCM con- low selectivity towards aromatics. The pyrovanadate phase also
tributed to the reduction of Cu2+ to metallic Cu. produced octenes as a major product, but the selectivity towards
HAP partially substituted with vanadate, Ca10(PO4)6- aromatics was improved compared to the other catalysts. Moder-
x(VO4)x(OH)2 where V/P = 0, 0.025, 0.05 and 0.10 (atomic ratio), ate to high selectivity towards carbon oxides were obtained with
have been used in oxidative dehydrogenation of propane to propy- all the catalysts since vanadium pentoxide also favors the forma-
lene [249]; the incorporation of vanadate in a molar ratio of V/ tion of oxygenates. C2–C7 is the favorable cyclization mode for
P = 0.05 increased the conversion of propane to 7.6–17.2% and the formation of aromatics, and aromatics selectivity increased
the selectivity from 3.5 to 52.4%, values being close to those with both vanadium content and temperature.
obtained by magnesium pyrovanadate, which is one of the most
active catalysts for the oxidative dehydrogenation [250]. It is evi- 4.4. Photocatalytic reactions
dent that the lattice oxygen in the vanadate plays an important
role in this improvement. The preparation of HAP-titania composites (HAP/TiO2) has
In order to identify the active site on HAPs for oxidation of alka- attracted considerable interest with several methods developed
nes, the oxidative dehydrogenation of propane using strontium for their preparation to improve the photocatalytic activities
HAP and incorporated cobalt cation and H-D exchange behaviors [255]. Anmin and colleagues reported the synthesis of HAP/TiO2
of OH groups in those catalysts with D2O have been studied via hydrothermal treatment of HAP powders with colloidal Ti
[251]. Interestingly, based on 1H and 31P MAS NMR studies, the (OH)4 solutions [256]. TEM characterizations concluded that TiO2
active oxygen species formed by abstraction of hydrogen of OH granules were deposed on HAP as anatase crystals with a particle
groups in the HAP was enhanced on the Co2+ rich catalysts. These size distribution in the range of 3–5 nm. The photocatalytic activity
species contributed directly to the hydrogen abstraction from pro- of this hydroxyapatite-titania composite was evaluated in the
pane, which allowed improvement of catalytic activity of the cata- decomposition of methylene blue wherein this nano-composite
lysts in propane dehydrogenation. was more effective than that of HAP and undoped TiO2. The syn-
Ziyad and colleagues reported the oxidative dehydrogenation of thesis and the characterization of such photocatalysts with differ-
propane using the chromium-loaded HAP catalysts Cr(x)/HAP ent titanium concentrations at varying hydrothermal temperatures
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 67

have been reported [257]. The study indicated that at higher pair and the large BET specific surface area of hydroxyapatite mod-
hydrothermal temperature synthesis, the increasing titanium sub- ified by Ag-TiO2.
stitution led to an increase in the crystallinity of HAP/TiO2 with Pd-TiO2-HAP nanoparticles with 3 wt% of Pd and 25 wt% of TiO2
adsorption capacities being in the range of UV–vis spectra. Photo- were successfully synthesized by an impregnation method [265].
catalytic activity efficiency in the decomposition of methylene blue The catalytic performance of this catalyst was evaluated in the
significantly increased with the Ti/(Ca + Ti) mole ratio concluding photocatalytic oxidation of potassium cyanide into carbon dioxide
that the photocatalytic properties of this composite may be related and nitrogen gases under visible light irradiation; the catalyst dis-
with the particle size, crystalline quality, morphology, and specific played significantly higher photocatalytic activity as compared to
surface area. Hu and Zhong have reported similar observations in Pd-TiO2, undoped TiO2, and P25 powders. This was due to the
the photocatalytic degradation of formaldehyde and acetaldehyde absorption of radiation in the visible light region, the small recom-
using Ti4+-substituted HAP [258]. bination rate of the electron-hole pair, and the high surface area.
Colloidal calcium HAP doped with Ti(IV) ions in different atomic The photocatalytic degradation of cyanide followed first-order
ratios, Ti/(Ca + Ti) = XTi, by a co-precipitation method has been kinetics. Recycling experiments confirmed the relative stability of
reported in which H3PO4 was added to the solution containing Ca the catalyst. Recently, Vaimakis and colleagues reported the syn-
(NO3)2 and Ti(SO4)2 [259]. For charge balance in the HAP lattice, thesis of HAP/TiO2 nanocomposites and its photocatalytic applica-
the added Ti(IV) may exist in the HAP crystals as divalent cations tions in the oxidation of nitrogen monoxide [266]. The morphology
such as [Ti(OH)2]2+ and [TiHPO4]2+. The photocatalytic activities was dependent upon the volume ratio between HAP and TiO2 in
of this modified HAP were examined in the decomposition reac- the initial solution. At a low HAP/TiO2 ratio, an aggregate of spher-
tions of acetaldehyde and albumin; modified HAP particles were ical particles were observed, while the decrease in the TiO2 amount
active while the HAP particles were completely inactive towards resulted in formation of needle and lath like particles. The compos-
the decomposition of both the materials. ite with the highest amount of TiO2 in the initial solution (VHA/
A study used the Quartz crystal microbalance technique to VTiO2 = 1, volume ration) demonstrated higher OH production
investigate the adsorption and degradation behavior of bilirubin capability than pure TiO2. The HAP/TiO2 composite exhibited dif-
on HAP-modified titania coatings [260,261]. Interestingly, the ferent activities for each part of the NO?NO2?NO3 photocatalytic
authors noted that the adsorption and the photocatalytic degrada- process. Even still, the composites exhibited increased NO?NO2
tion of bilirubin under UV irradiation was closely related to the oxidation in comparison to the pure TiO2; their activity in the
amount of HAP deposited on titania coatings, and the most degra- NO2?NO3 oxidation was extremely low, especially for the samples
dation efficiency of bilirubin was found when the percentage of with volume ratio more than 1. The behavior of the HAP/TiO2 com-
HAP was 0.7 wt%; the degradation-rate constant of bilirubin on posites was attributed to the presence of residual acidic groups
HAP (0.7 wt%)-titania coatings were (1.18 ± 0.12)  10 3 s 1, which was due to the HAP precipitation procedure.
which is higher than that on other titania coatings. Wei and colleagues reported the synthesis and photocatalytic
Nanometer-sized TiO2 island structures on the lamellate activity of HAP modified by nitrogen-doped TiO2 catalyst [267].
hydroxyapatite nanocrystals were prepared via a two-step emul- This new photocatalyst was evaluated in the decomposition of gas-
sion process [262]. After preparation of platy HAP nanocrystals eous acetone under visible light irradiation; 10%-HAP-N-TiO2 was
with a particle size distribution in the range of 70–200 nm by superior to that of the commercial Degussa P25 counterpart. The
heat-treatment at 1078 K, the HAP nanocrystals were then enhanced catalytic activity was attributed to the synergistic effect
immersed in NaH2PO4 solution to generate the formation of hydro- of HAP that adsorbed the chemical compound and the TiO2 photo-
xyl group on its surface. In the second step, the titanium tetraiso- catalyst that generated oxygen reactive species, which diffused and
propoxide reacted with the hydroxyl group of HAP surface to form reacted with the molecules located on the HAP. The doped nitrogen
TiO2 nanoparticles on the surface of HAP nanocrystals. The ensuing species played a key role in narrowing the band gap and made the
HAP nanocrystals loaded with TiO2 nanoparticles showed the high composite active under visible-light irradiation.
photocatalytic activity compared to the commercial TiO2 catalyst A HAP/TiO2 thin film was deposited on glass using a radio fre-
in the photodegradation of benzaldehyde. quency magnetron sputtering process [268] which showed that
The synthesis of TiO2/hydroxyapatite composite photocatalyst the decomposition of formaldehyde gas on such film showed a
with a novel morphology was accomplished from commercially higher decomposition rate than either the TiO2 or the HAP film
available a-tri-calcium phosphate and TiO2 powders, using a pro- alone.
cess based on the liquid immiscibility effect, followed by precalci- The recovery and reuse of expensive catalysts after catalytic
nation and hydrothermal treatment [263]; a blue shift of the reactions are important factors to consider for sustainable process-
absorption edge of 16 nm was observed upon hybridization of ing. Although nanocatalysts are highly active, they are not easy to
TiO2 and HAP. Microstructure analysis revealed that the granule isolate from the reaction mixture, which hampers overall process
contained rod-shaped HAP crystals with a surface adorned by sustainability. However, due to its magnetic properties, the use
nanosized TiO2 particles. Importantly, the active anatase surface of magnetic nanoparticles as a support seems to be a promising
was retained effectively in the composite granules, and they oper- option to overcome this separation problem [269,270]. In this con-
ated as three-dimensional, highly porous, size-controllable small text, Liu and coworkers prepared Fe3O4/HAP nanoparticles by
reactors. Compared with that of bulk TiO2, in the photodegradation homogeneous precipitation method and used it as photocatalyst
of methylene blue, the photocatalytic reaction rate greatly in the photodegradation of diazinon [271]. XRD and TEM measure-
increased when using this composite granule. ments revealed that the obtained nanoparticles were composed of
The preparation of modified Ag-TiO2 powders using the wet Fe3O4 and HAP, and these particles were almost spherical with an
chemical strategy has been documented wherein the modified average particle size of 25 nm in diameter. The effect of calcination
Ag-TiO2 powders photocatalytically decompose gaseous acetone temperature on photocatalytic activity of Fe3O4/HAP nanoparticles
under visible-light illumination [264]. The modified Ag-TiO2-HAP was investigated, and the results showed that the catalyst that cal-
powders showed higher catalytic activity and photochemical sta- cined at 400 °C possessed photocatalytic activity in comparison
bility compared to Ag-TiO2, undoped TiO2 and P25 powders. These with that calcined at other temperatures.
improvements could be attributed to strong absorption in the A similar study involved the development of a novel Pd/HAP/
visible-light region, low recombination rate of the electron–hole Fe3O4 for photocatalytic degradation of azo dyes [272]. This
68 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

catalyst showed high catalytic activity and good stability without

any visible light irradiation or application of adulterant; the cat-
alytic activity being significantly enhanced under acidic conditions.
A reaction mechanism involving the reaction of Pd/HAP/Fe3O4 with
dissolved oxygen, with the assistance of acid to form a Pd
hydroperoxide that oxidizes azo dyes under HAP catalysis, was
proposed. Interestingly, the concentrations of dyes changed expo-
nentially with time and high rate constants were obtained for the
degradation of these dyes. The pseudo-first-order equation was Scheme 24. Three-component coupling over CuHAP catalyst [279].
shown to fit degradation kinetics in most cases. Due to the mag-
netic properties of nano-Fe3O4, this catalyst was separated from uids [280]. This recoverable catalyst could be reused four times
the reaction mixture by an external magnet, thus avoiding the without any significant decrease in its catalytic activity, and there
usual filtration or centrifugation process. was not any detection of leaching of copper species from the sup-
In a report by Nishikawa and Omamiuda, the photocatalytic port upon atomic adsorption spectroscopy of the reaction mixture.
decomposition of methyl mercaptane over HAP under UV irradia- Mahajan and colleagues used antimony chloride doped on HAP
tion was investigated [273]. From the results of electron spin res- (SbCl3-HAP) as a Lewis solid acids catalyst for the one-pot stereos-
onance studies, the researchers concluded that the radical elective synthesis of trans-pyrano[3,2-c]quinolones from anilines,
species formed under UV irradiation was a superoxide anion radi- benzaldehydes and 3,4-dihydro-2H-pyran (Scheme 25) [281]; sig-
cal species. It was also reported that the photocatalytic activity of nificant and notable feature being the formation of a single trans
HAP treated at 200 °C was different from that of HAP after treat- isomer in contrast to SbCl3 and SbCl3-Al2O3, which led to the for-
ment at 1150 °C for decomposition of methyl mercaptane. The mation of both cis and trans.
photocatalytic activity of HAP was attributed to the production The catalyst was quantitatively recovered from the reaction,
of sufficient amounts of superoxide anion radical species under and its reusability was explored with 4-tolualdehyde, o-toluidine
UV irradiation. In this study, it was shown that the photocatalytic and 3,4-dihydro-2H-pyranas a model reaction. The catalyst was
activity of the HAP sample used for dimethyl sulfide was not satis- easily recycled up to ten cycles without significant any loss in
factory under UV irradiation, which indicated that the oxidation of activity. However, the leaching study was not reported for this
dimethyl sulfide is more difficult than that of methyl mercaptane. system.
The photocatalytic decomposition of dimethyl sulfide under Sun and colleagues reported on one-pot synthesis of a-
UV irradiation using two types of HAP with Ca/P molar ratios aminophosphonate via chlorinated benzyl alcohol and aniline with
(Ca/P = 1.67, HAP-1) and (Ca/P = 1.67, HAP-2) [274] showed that dimethyl phosphite under solvent-free conditions, using Au sup-
the HAP-2 was more active than HAP-1 and b-tricalcium phos- ported on HAP (AuHAP) [282]. The reaction proceeded smoothly
phate in the conversion of dimethyl sulfide, which led to stoichio- at 100 °C under atmospheric pressure to furnish product in a good
metrical carbon dioxide, sulfur dioxide and water. This high 86% yield (Scheme 26).
photocatalytic activity could not be due to the surface area of Interestingly, a one-pot synthesis of naphthopyrans has been
HAP alone, but must be due to the crystallinity toward the a-axis developed by Solhy research group via a three-component cou-
of HAP crystal. pling from b-naphthol and aldehydes, with malononitrile, using
The HAP modified Pt-ZnO nanoparticles were synthesized using HAP and sodium-modified HAP in aqueous media [283]; sodium
a template-ultrasonic assisted method [275]. TEM measurements nitrate was used to impregnate to create the sodium-modified
for the ensuing Pt/ZnO/HAP particles were located on the surface HAP (SMH) which was superior to HAP alone (Table 21). The
HAP nanorod with an average diameter of 9 nm. The photocatalytic SMH catalyst was readily recovered by filtration, followed by calci-
activities of these nanoparticles were evaluated in the photocat- nation at 450 °C. The recycling of the catalyst had been briefly
alytic oxidation decomposition of benzene under a visible-light examined in the reaction of malononitrile with b-naphthol and
irradiation; Pt/ZnO/HAP was found to be significantly higher than benzaldehyde. The results showed that the catalyst could be recy-
that of ZnO, P25 and Pt-ZnO. This was attributed to strong absorp- cled at least five times without any loss of activity.
tion in the visible-light region, a low recombination rate of
the electron-hole pair, and the large BET specific surface area of 4.5.2. Alkylation reactions
Pt/ZnO/HAP. Acylation of aromatic compounds is a powerful and widely used
method for the production of fine chemicals [284]. The classic
4.5. Othermiscellaneous reactions methodology for Friedel-Crafts acylation uses stoichiometric
amounts of Lewis acids or strong mineral acids as catalysts, and
4.5.1. Multicomponent reactions results in a substantial amount of waste and corrosion problems
Multicomponent reactions are generally reactions whereby [285]. One of the best ways to overcome these problems is the
more than two starting materials react in a sequential manner to use of solid acids such as zeolites, clays, Nafion-H, and heteropoly
give highly selective products that essentially retain the atoms of acids [286–289]. Sebti and colleagues explored these options and
the starting material [276–278]; relatively few examples of HAP- successfully used HAP alone or activated with metal halides in
supported catalysts exist in multicomponent reactions. Choudary the Friedel-Crafts alkylation of benzene, toluene and p-xylene by
reported that use of HAP-supported copper catalyst (CuHAP) could benzyl chloride (Scheme 27) [290]; HAP alone can catalyze the
catalyze the formation of propargylamines via the coupling of alde- selective alkylation to monoalkyl-compounds thus confirming
hydes, amines, and alkynes without any co-catalyst or additive the acid character of the material. The obtained products of
[279], acetonitrile being the best solvent with optimum ratio of monoalkylation mostly consist of: benzene benzylation (68%
aldehyde, amine and alkyne 1:1.2:1.3. Among the catalysts monoalkyl, 32% dialkyl); toluene benzylation (88% monoalkyl,
screened, there activity order was CuHAP > Cu(OAc)2 > RuHAP > 12% dialkyl); p-xylene benzylation (87% monoalkyl, 13% dialkyl).
Cu > FeHAP for reactions that accommodated various aldehydes It is noteworthy that the reactivity of the aromatic nucleus
with a variety of terminal alkynes and amines possessing a wide increases with the number of electron donor groups. To improve
range of functional groups (Scheme 24); they were found to be the acid catalytic activity of HAP, authors impregnated the phos-
more rapid compared to earlier reported case using again ionic liq- phate with metal halides such as ZnCl2, NiCl2 and CuCl2 and these
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 69

Scheme 25. SbCl3-HAP-catalyzed stereoselective one-pot synthesis of pyrano[3,2-c]quinolones [281].

Scheme 26. Three components route toa-aminophosphonates using Au/HAP catalyst [282].

Table 21
ZnHAP-catalyzed Michael addition of indoles to electron-deficient olefins [283].

Entry R1 Catalyst Time (h) Yield (%)

1 H HAP 6 74
2 H SMH 3 95
3 4-Me HAP 6 71
4 4-Me SMH 3 79
5 4-OMe HAP 6 61
6 4-OMe SMH 3 72
7 4-Cl HAP 6 75
8 4-Cl SMH 3 96
9 3-NO2 HAP 87 6
10 3-NO2 SMH 93 2
11 4-NO2 HAP 82 6
12 4-NO2 SMH 2 92

dialkyl that varied between 95/5 and 87/13; for benzene, the ratio
varied between 83/17 and 68/32. The para-substituted product
was the major compound (about 63% para/37% ortho) in the alky-
lation of toluene. Unfortunately, recycling experiments were not
reported for these systems.
It is worth noting – even if it is out of the main scope of the pre-
sent review, that the fluorapatite (FAP) alone or impregnated by
transition metal halides easily catalyzed the Friedel-Crafts alkyla-
tion [291]; fluorapatite was found to be less acidic than HAP.
Among many halides such as ZnCl2, ZnBr2, CuCl2, CuBr2 and NiCl2
Scheme 27. Friedel-Crafts alkylation of benzene over different Lewis acid sup-
doped on FAP, the best results were obtained with ZnCl2/FAP and
ported on HAP [290]. ZnBr2/FAP; catalysts were recycled through simple filtration and
drying methods, although leaching of metal of the catalyst to the
organic layer caused progressive deactivation.
three catalytic systems showed good catalytic activity and high Masuyama and colleagues developed a Pd-exchanged HAP and
selectivity to produce monoalkylation in the Friedel-Crafts alkyla- explored its catalytic properties in allylic alkylation [292]. Using
tion; ZnCl2/HAP being much more effective than the catalysts 1 mol% of catalyst in aqueous medium, and 0.01 mmol of PPh3 in
NiCl2/HAP and CuCl2/HAP. The selectivity towards monoalkylation water at 50 °C, this catalyst system gave satisfactory yields of
was greater with toluene and p-xylene, with a ratio of monoalkyl/ monoallylated product in the reaction of allyl methyl carbonate
70 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

with active methylene compounds such as diethyl malonate, 2-et

hoxycarbonylcyclopentanone, 2-ethoxycarbonylcyclohexanone
and 2,2-dimethyl-1,3-dioxane-4,6-dione under mild reaction con-
ditions (Scheme 28). The reusability was tested in allylic alkylation
of allyl methyl carbonate with diethyl malonate, in the presence of
PPh3 which reduced Pd(II) to active Pd(0) in situ; catalyst could be
reused ten times without losing activity presumably via the coor- Scheme 30. Selective hydration of nitriles over HAP as catalyst [300].
dination of phosphate moieties to Pd.
Synthesis and the catalytic activity of heterogeneous HAP
impregnated with zinc bromide have been explored for Friedel-
Crafts acylation of anisole (Scheme 29) [293]. The high catalytic
efficiency of ZnBr2/HAP displayed high selectivity and could be
reused at least five times without obvious activity loss.

4.5.3. Hydration of nitriles

The catalytic hydration of nitriles to the corresponding amides Scheme 31. Hydration of nitriles to amides using AgHAP as catalyst [301].
is an efficient and economical route to useful amides from an
industrial point of view. Amides are found in numerous natural
products and are also widely used in the organic synthesis for bearing electron-withdrawing groups were significantly more
lubricants, detergent additives, drug stabilizers, and functional reactive than that of the bearing-electron donating groups.
polymers [294–297]. This catalytic hydration is usually performed HAP-supported Ag (AgHAP) nanoparticles have been described
using a strong acid or a base [298,299]. However, under these con- as an efficient and recyclable catalytic system for the selective
ditions various by-products, notably carboxylic acids which are hydration of nitriles [301]; catalyst was prepared by treating HAP
formed by over hydrolysis of amides, and generation of salts after with AgNO3 followed by reduction with KBH4, the average size of
neutralization of the catalysts. These harsh conditions can be cir- metal particles in AgHAP being 7.6 nm (Scheme 31). The limita-
cumvented using heterogeneous catalysts instead. Hydration of tions of the system were found to be aliphatic nitriles, which were
nitriles using sodium nitrate impregnated HAP has been reported not converted to corresponding amides even at 180 °C. Nonethe-
[300] wherein a variety of benzonitriles derivatives including less, it is significant that this methodology could extend to various
heteroaromatic nitriles such as 3-cyanopyridine, 4-cyanopyridine heteroaromatic nitriles giving useful to excellent isolated yields of
and prazinecarbonitrile were smoothly hydrated to corresponding expected amides; the hydration of pyrazinecarbonitrile could be
amides in excellent yield (Scheme 30). However, the substituents maintained at 99% after four recycling steps, using 3 mol% of
catalyst.

4.5.4. Transesterification
Transesterification is an important organic reaction that can be
employed to synthesize esters [302] and this organic transforma-
tion reaction is more advantageous than the ester synthesis from
carboxylic acids and alcohols. Transesterification has traditionally
been carried out by the use of strong acids or by soluble bases such
as caustic soda [303–305]. However, traditional homogeneous
transterification poses significant issues related to product separa-
tion which could be addressed by the use of heterogeneous catal-
ysis namely HAP supported zinc chloride [306] exemplified in
the transesterification reaction between methyl benzoate and
butan-1-ol as a model reaction; supported Lewis acid catalyst
exhibited higher catalytic activity than HAP alone. The general pro-
cedure included various aromatic and aliphatic esters with alipha-
tic, cyclic and aromatic alcohols; fairly good to excellent yields of
corresponding esters were obtained under reflux conditions
(Table 22).
The catalyst recovered after filtration was dried at 150 °C, and
then successfully reused in 3 runs with only a 3% reduction in
yield. There was not any reactivity found in a filtration test, and
Scheme 28. Allylic alkylation of allyl methyl carbonate with active methylene no Zinc leaching was detected by atomic absorption spectroscopy.
compounds over PdHAP catalyst [292]. The transesterification of soybean oil with methanol has been
reported using a solid base catalyst, prepared by calcining the mix-
ture of porous HAP and Sr(NO3)2 at 873 K [307]; the activity of the
catalysts showing strong dependency upon the loading amount of
Sr(NO3)2 onto porous HAP. The catalyst of 20 wt% Sr(NO3)2/HAP
showed the highest catalytic activity towards the transesterifica-
tion and the catalytic activity decreased when the loading amount
of Sr(NO3)2 exceeded 20 wt% presumably due to the decrease in
Scheme 29. Friedel-Crafts acylation of anisole catalyzed by ZnBr2/HAP catalyst specific surface area. Importantly, no catalytic activity was dis-
[293]. cerned when the Sr(NO3)2/HAP was non-calcined, which is due to
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 71

Table 22
Transesterification reactions catalyzed by HAP and ZnCl2/HAP [306].

Entry R1 R2 Catalyst Time (h) Yield (%)

1 C6H5 C6H13 HAP 24 60
2 C6H5 C6H13 ZnCl2/HAP 6 92
3 C6H5 C6H5CH2 HAP 24 49
4 C6H5 C6H5CH2 ZnCl2/HAP 6 93
5 C6H5 C6H11 HAP 24 60
6 C6H5 C6H11 ZnCl2/HAP 3 75
7 C6H11 C8H17 HAP 24 57
8 C6H11 C8H17 ZnCl2/HAP 6 93
9 C6H11 C6H5CH2 HAP 24 50
10 C6H11 C6H5CH2 ZnCl2/HAP 6 90
11 C3H7 C8H17 HAP 24 29
12 C3H7 C8H17 ZnCl2/HAP 6 58

the lack of strong basic sites. The reaction of the solid phase ple filtration after the second run, then another equivalent of the
ion-exchange between Ca5(PO4)3(OH) and SrO was prompted by reactants were added. The reaction was performed and the conver-
decomposition of Sr(NO3)2 at 873 K and led to the formation of sion of glycerol was only 2.1%, indicating that only a very small
Ca5-xSrx(PO4)3(OH) and CaxSr1-xO. The latter was dispersed onto amount of the KF used for the reaction leached into the product
the surface of HAP, which prevented the decomposition and mixture.
recrystallization of the porous HAP, and maintained porous mor-
phology of HAP at 873 K with the active base sites were probably 4.5.5. Hydroformylation reactions
derived from the CaxSr1-xO phase. The catalytic activity of KF/ Hydroformylation, also known as oxo synthesis, is a chemical
HAP prepared by a wet-impregnation method was investigated process that adds a formyl group and a hydrogen atom to an alkene
in the synthesis of glycerol carbonate via transesterification reac- to form an aldehyde. This reaction was accidentally discovered by
tion from glycerol and dimethyl carbonate [308]. SEM characteri- Otto Roelen in 1938 during his investigations into the origin of
zations concluded that KF was well dispersed on the surface of oxygenated products formed in cobalt-catalyzed Fischer-Tropsch
HAP, which was consistent with XRD results. Using dimethyl car- reactions [309]. The hydroformylation reaction represents one of
bonate/glycerol in a molar ratio of 2:1, catalyst/glycerol in a weight the most important synthetic transformations developed in the
ratio of 3% with 50 min reaction time at 78 °C, the conversion of 20th century [310] and is generally catalyzed by soluble rhodium
glycerol and yield of glycerol carbonate reached 99.3% and 99.0%, or cobalt complexes with various ligands, using homogeneous cat-
respectively. Comparing conversions under the same reaction alytic systems because of its high reactivity, selectivity, and turn-
methods, the KF/HAP catalyst was superior to Zr/HAP, Li/HAP, Ce/ over numbers, and milder reaction conditions. Rhodium catalysts
HAP, Li/HAP and typically work under mild conditions (100 °C, 25 bar), giving good
K/HAP (Table 23); the selectivity to the glycerol carbonate being activity and selectivity (80–90%) for the desired linear aldehyde.
higher than 98% of the overall modified HAP catalysts. It is partic- Nonetheless, most commercial plants carrying out this reaction
ularly noteworthy that the catalytic performance of KF/HAP was use cobalt catalysts, which require much harsher conditions (typi-
comparable to the homogenous KF catalyst and better than that cally 200 °C, 100 bar) and give poorer selectivity; this may be due
of K2CO3 and HAP alone. to rhodium catalysts’ decomposition while attempting to distill the
To establish the reusability of the catalyst for glycerol transes- product from them [311]. To overcome these separation problems,
terification, the catalyst was filtered after the first reaction and chemists and engineers have investigated two strategies other
then washed with methanol. It was then dried in an oven at than distillation for recycling of the catalyst. In the first strategy,
383 K before being reused for up to four cycles; a slow decrease the catalyst is anchored to some kind of soluble or insoluble sup-
in conversion of glycerol and an increase in reaction time occurred. port, and the separation is conducted via a filtration technique
To check the heterogeneity of the catalyst, it was separated by sim- often referred to as heterogenizing homogeneous catalysts. The
other strategy involves designing the catalyst so that it is solubi-
lized in a solvent that, under some conditions, is immiscible with
Table 23
the reaction product. These reactions involve two phases and are
Synthesis of glycerol carbonate over different modified HAP catalysts [308].
often referred to as biphasic systems. To date, there are relatively
few examples of HAP-supported catalysts used in hydroformyla-
tion reactions. One study used the apatitictricalcium phosphate
as support for supported aqueous phase hydroformylation of
octene at 80 °C in toluene, using a dinuclear rhodium complex
bearing as tris(m-sulfonatophenyl)phosphine hydrophilic ligands.
Entry Catalyst Time (h) Conversion (%) Yield (%) Kalck and colleagues attributed the high aldehyde yield to the
favorable orientation of the catalytic molecule that arose from
1 HAP 2 5.0 4.5
2 Zr/HAP 2 46.9 46.6
the absorption of some of the tris(m-sulfonatophenyl)phosphine
3 Ce/HAP 2 50.5 49.7 ligands onto the hydrophilic surface of apatite [312].
4 Li/HAP 2 34.1 33.7 Wang and colleagues prepared HAP supported rhodium and
5 La/HAP 2 54.7 54 explored its catalytic prowess in the hydroformylation of 1-
6 K/HAP 2 64.0 62.9
hexene [313]. This catalyst was prepared by treating the HAP with
7 KF/HAP 0.83 99.1 99.0
Rh(CO)2(acetylacetonate) in acetone at room temperature
72 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76

H3C O OH H 3C
CO
O P O
CO CO
Acetone
Rh + Hydroxyapatite r.t
Rh
O CO O O
H 3C O P
H3C

Hydroxyapatite

Scheme 32. Hydroformylation of 1-hexene over HAP supported rhodium [313].

(Scheme 32) and the supported catalyst was characterized by Table 24

infrared and solid state NMR. It was proposed that the proton in Hydrogenolysis of Z-protected amino acids catalyzed by PdHAP [316].
the P–OH group of HAP reacted with the acetylacetonate ligand
to generate acetylacetone, which coordinated with Rh dicarbonyl;
the latter being anchored on the surface via the resulting P–O
group. This supported catalyst exhibited high catalytic activity in
catalyzing hydroformylation of 1-hexene without the need of any
auxiliary ligand and Importantly, was found to be more active than
the unsupported Rh(CO)2(acetylacetonate) homogeneous system. Entry Catalysts (mol%) Yield (%)
The catalyst was recycled by simple filtration and reused, although
1 PdHAP (0.4) 92
there was a slight reduction in the yield. 2 Pd/C (5.0) 68
3 Pd/SiO2 (0.5) 64
4 Pd/Al2O3 (0.5) 60

4.5.6. Hydrogenolysis reactions

The hydrogenolysis reactions have attracted increased interest
due to their potential application in many organic processes such 4.5.7. Hydrogenation reactions
as the conversion of glycerol into commodity chemicals [314]; Hydrogenation is a catalytic process of great importance to the
chemical bond dissociation and simultaneous addition of hydrogen petrochemical and fine chemical industries [318]. This process is
to the ensuing molecular fragments occured. In this context, lately investigated to convert carbon dioxide to methanol and alke-
Kaneda and co-workers examined the efficiency of PdHAP as cata- nes and aromatics into saturated alkanes and cycloalkanes
lyst in hydrogenolysis of C X bonds of various organic halides [319,320]. Several research groups have used the HAP as a support
[315]. Pd(0)HAP catalyst showed good catalytic activity in to design heterogeneous catalysts for hydrogenation reactions
hydrodehalogenation of chlorobenzene to benzene using [321]. Venugopal and co-workers investigated the catalytic activity
0.05 mol% of catalyst and in molecular hydrogen atmosphere. of HAP-supported Ru, Pt, Pd, Ni catalysts also in the hydrogenation
Additionally, PdHAP was able to promote the dehalogenation of of levulinic acid to c-valerolactone using water as the sole reaction
halophenols such as 4-chlorophenol in water under an atmo- medium [322]. Among the evaluated catalysts, the RuHAP exhib-
spheric pressure of molecular hydrogen (Scheme 33); hydrogenol- ited good catalytic activity and selectivity to c-valerolactone
ysis of bromooarenes namely 4-bromochlorobenzene to at70 °C under 0.5 MPa H2 pressure (Scheme 35). Recycling studies
chlorobenzene occurs in high yield (95%). have shown that the Ru/HAP catalyst can be readily recovered and
It is worth noting that the PdHAP was highly effective for the reused up to four times with only a slight loss of activity. The HAP
deprotection of N-benzyloxycarbonyl group from amino acids in supported Ru was found to be an active catalyst for the hydrogena-
the presence of molecular hydrogen and in methanol as solvent tion of quinoline at 150 °C and 5 MPa of hydrogen pressure in
(Table 24) [316]. This catalyst exhibited superior catalytic proper- cyclohexane [323]. The authors believe that this high performance
ties compared to most common catalyst deployed for such reaction of this catalyst is attributed to the cooperation between the hydro-
such as Pd/C, Pd/SiO2, and Pd/Al2O3. The PdHAP catalyst was also xyl groups on support surface and active metal centers. Zah-
efficient in the deprotection of N-benzyloxycarbonyl group poly makıran and co-workers reported the preparation of Ru(0) and
(amido amine) dendrimer functionalized with n-hexyl groups. Rh(0) nanoclusters supported on HAP and their use for the hydro-
In another study, the same research group used this catalyst in genation of aromatics to their corresponding cyclohexane deriva-
the hydrogenolysis reactions of 1,1,1-trichloro-2,2-bis(4-chlorophe tives under mild conditions [324,325]. Bimetallic Ru-Zn catalysts
nyl)ethane (DDT) and its derivatives 1,1-dichloro-2,2-bis(4-chloro supported on HAP was prepared via ion-exchange method and
phenyl)ethene (DDE) and 1,1-dichloro-2,2-bis(4-chlorophenyl)eth used for the partial hydrogenation of benzene to cyclohexene
ane (DDD) using hydrogen under moderate reaction conditions [326]. The hydrogenation reaction was conducted over RuZnHAP
(Scheme 34) [317]. Importantly, this catalyst was found to be more catalyst at the optimized conditions and the catalyst can be recov-
active compared to other catalytic systems such as Pd/Al2O3 and ered and reused at least four times without any loss of catalytic
Pd/C. activity.
Huang and co-workers have shown RhHAP catalyst to be an
effective catalyst for the hydrogenation of nitroarenes and olefins
with under mild conditions [327]. A variety of nitroarenes bearing
various halide functional groups such as fluorine, chlorine, bro-
mine were hydrogenated selectively to the corresponding anilines
over the RhHAP catalyst in the presence of hydrazine as a reducing
agent (Scheme 36). Moreover, olefins were also hydrogenated to
Scheme 33. Hydrogenolysis of 4-chlorphenol over PdHAP [315]. the corresponding alkanes in good yields over the RhHAP. This cat-
 A. Fihri et al. / Coordination Chemistry Reviews 347 (2017) 48–76 73

Scheme 34. Hydrogenolysis of DDT, DDE and DDT using PdHAP catalyst [317].

Ca-deficient composition. In addition, the replacement of Ca2+ sites

in CaHAP by divalent or trivalent cations such as Sr2+, Ba2+, Pd2+,
Ru3+ leads to stable material formation with enhancement of cat-
alytic performances. However, a number of challenges remain
untapped. For instance, the textural properties and the mesoporos-
Scheme 35. Hydrogenation of levulinic acid over RuHAP catalyst [322]. ity of such material are still difficult to control. Another weakness
of HAP is its poor mechanical properties that are not adequate
enough to prevent its success in long-term load bearing applica-
tions. It is also worth noticing that HAP may decompose in an acid
medium, which poses as a significant drawback of the material. For
all aforementioned reasons, the interest on studying the earth-
abundant HAP will continue to be a fast-progressing topic in the
coming years.

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