Module K
Alkynes: Electrophilic Additions
Based on Bruice’s Organic Chemistry: Chapter 7
Learning Outcomes: At the end of this module, you will learn:
1. What is the structure of alkynes that account for their physical and chemical properties?
2. Which addition reactions of alkynes are direct mechanistic extensions of those of alkenes?
3. How to reduce alkynes to cis-alkenes, trans-alkenes, and alkanes?
4. How to convert alkynes to keto compounds via hydration?
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Review
Structure of Alkynes
Carbon-carbon triple bond is constructed from an sp orbital on
each C to form a bond, and unhybridized px and py orbitals
forming 2 bonds
The triple bond is shorter and stronger than single or double bonds:
breaking a bond in acetylene (HC≡CH) requires 318 kJ/mol energy,
whereas ethylene (H2C=CH2) requires 268 kJ/mol
sp
sp
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Review
Electronic Structure of Alkynes
The C sp–hybridization form bonds of 180º
180o
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Physical Properties of Alkynes
Alkynes with more -electrons also have greater van der
Waals interactions
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Review
Naming Alkynes
Number chain containing triple bond to give the smallest number to the triple
bond; give lowest numbers possible to other substituents
An enyne has a double bond and triple bond
Select as the parent chain that which contains both double and triple bonds
A compound with two or three triple bonds is a diyne or triyne
6-methylhepta-1,4-diyne
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Alkynes as substituents
Alkynes as substituents are called alkynyl
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But-1-enyl But-1-ynyl
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Terminology
Symmetrical Unsymmetrical Unsymmetrical
alkyne alkyne alkyne
Substituents stabilize alkynes,
just like for alkenes
Internal alkynes more stable
than terminal alkynes birth control
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Module K
Alkynes: Electrophilic Additions
Based on Bruice’s Organic Chemistry: Chapter 7
Learning Outcomes: At the end of this module, you will learn:
1. What is the structure of alkynes that account for their physical and chemical properties?
2. Which addition reactions of alkynes are direct mechanistic extensions of those of alkenes?
3. How to reduce alkynes to cis-alkenes, trans-alkenes, and alkanes?
4. How to convert alkynes to keto compounds via hydration?
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Alkynes (and Alkenes)
Both are unsaturated molecules, having bonds
Therefore, they undergo similar reactions
Major differences?
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Reactions of Alkynes
Alkynes react by addition to electrophiles—similar
electrophiles that also add to alkenes
Addition of HX
Addition of X2
Addition of H2
Addition of H2O
Acid-catalyzed hydration
Oxymercuration
Hydroboration-oxidation
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Additions to Alkynes
Electron-rich bonds undergo electrophilic additions
Each alkyne has two bonds
Additions can occur twice
Each addition could have issues of regioselectivity and
stereoselectivity
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Reactions of Alkynes: Addition of HX
Addition reactions of alkynes like those of alkenes
Markovnikov addition occurs
Limit to
~ 1 equiv
95% yield
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Reactions of Alkynes: Addition of HX
Addition reactions of alkynes like those of alkenes
Markovnikov addition occurs
Intermediate alkene can react further with more reagent
Markovnikov addition occurs again
geminal dibromide
gem- dibromide
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Mechanism of Addition of HX
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More About Carbocations
Protonation of alkynes generate vinylic carbocations
Secondary vinylic carbocations are about as stable as primary
alkyl carbocations– due to positive charge on sp-C
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More About Carbocations
Protonation of alkynes generate “vinylic carbocations”
Primary vinylic carbocations too unstable
Some unstable vinylic carbocations may be -complexes
Evidence: also (although not always) anti addition
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Stability and Reactivity of Alkynes
Alkynes are less stable
than alkenes, but also
less reactive in
electrophilic additions
Stability refers to
thermodynamics (Gº);
reactivity refers to
kinetics (G‡)
Alkyne < stable than
alkene; but vinyl cation-
like TS is <<< stable than
alkyl cation-like TS
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Addition of HX to Alkynes
Stereochemistry: anti Stereochemistry: not selective
Alkynes can add
one or two
Faster Slower moles of HX
Each addition is
Markovnikov
The second
addition is
slower because
X X
the chloroalkene
is less electron
rich
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Addition of X2 to Alkynes
X2 undergoes anti addition to alkynes
Addition of one or two moles of X2
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Reactions of Alkynes: Addition of X2
First addition is anti, gives trans dihaloalkene as intermediate
Two equivalents of X2 gives tetrahaloalkane as product
Br
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EXERCISE 1
Suggest synthetic routes to the following chloroalkanes,
using any alkyne as starting materials. More than one step
may be needed.
Cl Cl
Cl Cl Cl Cl
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Module K
Alkynes: Electrophilic Additions
Based on Bruice’s Organic Chemistry: Chapter 7
Learning Outcomes: At the end of this module, you will learn:
1. What is the structure of alkynes that account for their physical and chemical properties?
2. Which addition reactions of alkynes are direct mechanistic extensions of those of alkenes?
3. How to reduce alkynes to cis-alkenes, trans-alkenes, and alkanes?
4. How to convert alkynes to keto compounds via hydration?
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Reduction of Alkynes
cannot stop here
Reactive catalysts: Pt, or Pd on carbon
Same catalysts for reduction of alkenes to alkanes
Cannot stop at addition of 1 equivalent of hydrogen
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Reduction of Alkynes
It is possible to add only 1 equivalent of H2 to make alkenes
This partial hydrogenation requires different catalysts
Cis-alkene
Syn addition
because H, H adds from
the catalyst surface
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Reduction of Alkynes to cis-Alkenes
Selecting the right catalyst determines the reduction
outcome, not the amount of H2 used
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Reduction of Alkynes to cis-Alkenes
Reduction using Lindlar catalyst produces a cis-alkene,
and double bonds are not reduced
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Reduction of Alkynes to trans-Alkenes
Reduction of alkynes to make trans-alkenes
is done by a “dissolving metal reduction”
reaction, using Na or Li in liquid ammonia
Anhydrous NH3 is a liquid below -33 ºC
Alkali metals dissolve in liquid ammonia and
function as reducing agents (giving away
electrons)
Alkenes are not reduced
ANTI addition
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Reduction of Alkynes to trans-Alkenes
The dissolving metal reduction has a different stereochemical
outcome, because it proceeds by a completely different
mechanism
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Reduction of Alkynes to trans-Alkenes
Mechanism: completely different!
Involves radicals, and single electron movement
NH2
radical anion
Notice the use of different arrows to show
electron or electron pair movement
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Reduction of Alkynes to trans-Alkenes
Mechanism: completely different!
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Summary on Alkyne Additions (I)
How to control additions to occur once or twice?
Addition of HX, X2/CCl4: control by the amount of reagent
Addition of H2: control by catalyst and reaction
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EXERCISE 2
Suggest synthetic routes to the following molecules, using
any alkyne as starting materials. More than one step may
be needed.
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Module K
Alkynes: Electrophilic Additions
Based on Bruice’s Organic Chemistry: Chapter 7
Learning Outcomes: At the end of this module, you will learn:
1. What is the structure of alkynes that account for their physical and chemical properties?
2. Which addition reactions of alkynes are direct mechanistic extensions of those of alkenes?
3. How to reduce alkynes to cis-alkenes, trans-alkenes, and alkanes?
4. How to convert alkynes to keto compounds via hydration?
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Hydration of Alkynes
Acid-catalyzed addition of water
KETONE
But these products
(called ENOLS) are not isolated!
An enol is formed but it is quickly converted to the more
stable ketone form
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Hydration of Alkynes
Terminal alkynes are less reactive towards protonation,
so oxymercuration is used
Alkynes undergo oxymercuration to add water according
to Markovnikov’s rule
C4H9C CH
HO H
C4H9 H
C C
HO H
ENOL
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Hydration of Alkynes
Addition of H-OH as in alkenes
Mercury (II) catalyzes Markovnikov addition
Hydroboration-oxidation gives anti-Markovnikov product
2-hexanone
KETONE
ISOMERIZATION
H2C C hexanal
ALDEHYDE
C4H9 H
ENOLS are not isolated
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Keto-enol Tautomerism
An isomerization where constitutional isomers rapidly interconvert
is called a tautomerization; the isomers are called tautomers
One important instance of tautomerism is the keto-enol
We observe the keto form (ketone or aldehyde) as product because it
is usually the more stable form compared to the enol
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Keto-enol Tautomerism
The isomerization is a change of the
-bond position and proton location
Keto-enol Tautomerization Mechanism under acid-catalyzed conditions:
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Keto Enol Tautomerization
Mechanism under acid-catalyzed conditions:
Mechanism under base-catalyzed conditions:
enolate 39
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EXERCISE 3
Draw the alkyne precursors that were hydrated to give the
following enols. Convert them to the keto tautomers. Draw the
mechanism of tautomerization under acidic and basic conditions.
HO
OH
OH
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Mercury(II)-Catalyzed Hydration of Alkynes
tautomerization
tautomerization
Water adds to the unsymmetrical mercurinium ion
Demercuration occurs in the reaction (no additional reagent needed)
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Comparison of Oxymercurations
Alkene oxymercuration-demercuration
Typically uses Hg(OAc)2
Requires the addition of NaBH4 to induce demercuration
Hg(OAc)2 HgOAc NaBH4
H2O OH OH
Terminal alkyne oxymercuration
Typically uses more electrophilic HgSO4 because alkynes are less reactive
Demercuration occurs in situ; separate step not required
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Hydroboration-oxidation of Alkynes
Overall anti-Markovnikov addition of water to alkyne
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Synthetically Useful Hydrations
an aldehyde
a methyl ketone
For terminal alkynes, anti-Markovnikov and Markovnikov
hydrations generate different major products selectively
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Synthetically Useful Hydrations
mixture of products — not useful
For internal alkynes, there is no Markovnikov regioselectivity
Only the hydration of symmetrical alkynes result in single
product and not a mixture
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EXERCISE 4
Draw the mechanism to account for the product.
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Summary on Alkyne Additions (II)
How to control additions to occur once or twice for alkynes?
Addition of HX, X2: control by the amount of reagent
Addition of H2: control by catalyst and method
Addition of H2O or X2 / H2O: does not add twice due to rapid
conversion of enol to keto compound
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EXERCISE 5:
Can these compounds be obtained as major products starting
from alkynes? If so, suggest the reagents and conditions.
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Summary of Alkyne Addition Reactions
Similarities between the reactivities of alkenes and alkynes in
electrophilic additions
Similar reaction mechanisms
Beware of issues of double addition
Addition of HX, X2/CCl4
Syn addition of H2 by partial hydrogenation, anti addition by
dissolving metal reduction, full reduction using reactive catalysts
Addition of water (acid-catalyzed hydration, X2/H2O,
oxymercuration, hydroboration-oxidation) generate enols that
tautomerize to keto compounds
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Module K
Alkynes: Electrophilic Additions
Based on Bruice’s Organic Chemistry: Chapter 7
Check that you have achieved these learning outcomes, and can give
examples to explain and answer each of these questions:
1. What is the structure of alkynes that account for their physical and chemical properties?
2. Which addition reactions of alkynes are direct mechanistic extensions of those of alkenes?
3. How to reduce alkynes to cis-alkenes, trans-alkenes, and alkanes?
4. How to convert alkynes to keto compounds via hydration?
Copyright © 2018-2023 HKU
