Synthesis of 5-C-Methylated D-Mannose, D-Galactose,

L-Gulose and L-Altrose, and their Structural Elucidation

by NMR Spectroscopy

Christoph Köllmann, Peter G. Jones and Daniel B. Werz*

Supporting Information

Table of Contents

1. General Information S2
2. Spectroscopic Data S3
2.1 Data for Compounds of the D-Mannose Series S3
2.2 Data for Compounds of the L-Gulose series S13
2.3 Data for Compounds of the L-Altrose series S21
2.4 Data for Compounds of the D-Galactose series S32
2.5 Data for Compounds of the Isopropylidene protected series S41
2.6 Data for Compounds of the D-Glucose series S50
2.7 Data for Compounds of the L-Idose series S59
2.8 Data for 5-C-Monodeuterated Compounds S65
3. X-ray Structure Determinations S68
4. Literature S69

S1
1. General Information
All solvents were purchased as synthetic grade solvents and stored over molecular sieves. All
reactions were carried out in oven-dried glassware, septum-capped and under atmospheric
pressure of argon. Commercially available compounds were used without further purification
unless otherwise stated. Proton (1H) and carbon (13C) NMR spectra were recorded on a Bruker
Avance III 400, a Bruker Avance III HD500 and a Bruker Avance II 600 spectrometer using the
signals from tetramethylsilane as internal references for 1H and 13C chemical shifts,
respectively. Abbreviations for multiplicities were used as following s = singlet, d = doublet, t
= triplet, q = quartet, hept = septet, m = multiplet. ESI-HRMS mass spectrometry was carried
out on a FTICR instrument and IR spectra were received from an ATR spectrometer. Optical
rotations were measured on a common polarimeter at 20 °C.

S2
2. Spectroscopic Data
Compounds 1, 10, 19 and 25a were analogously prepared to procedures reported by Poláková,
Fernández and Sennari.

Compound 1[1,2]

Compound 10[2]

Compound 19[3]

Compound 25a[2]

2.1 D-Mannose Series

Compound 2

DMSO (1.58 mL, 22.2 mmol, 5.0 eq.) was added dropwise to a mixture of oxalyl chloride (0.76 mL,
8.88 mmol, 2.0 eq.) in dry dichloromethane (44 mL) at -78 °C. After the addition was completed, the
reaction mixture was stirred for 15 min before a solution of alcohol 1 (2.4 g, 4.44 mmol, 1.0 eq.) in
dichloromethane (44 mL) was added. The reaction mixture was stirred at equal temperature for 0.5 h
and NEt3 (4.92 mL, 35.5 mmol, 8.0 eq.) was added. The mixture was warmed to room temperature and
diluted with dichloromethane (40 mL) and saturated NaHCO3 solution (40 mL). The aqueous layer was
extracted with dichloromethane (3x 40 mL) and the combined organic phases were washed with
saturated NaCl solution (40 mL). The organic phase was dried over Na2SO4, filtered and evaporated to
dryness.
The crude aldehyde was dissolved in acetonitrile (44 mL) and potassium carbonate (3.68 g, 26.6 mmol,
6.0 eq.) and isobutyric anhydride (4.55 mL, 26.6 mmol, 6.0 eq.) were added. The reaction mixture was
refluxed for 3 h and finally the reaction terminated by the addition of ethyl acetate (40 mL) and water
(40 mL). The aqueous layer was extracted with ethyl acetate (3x 40 mL) and the combined organic
phases were dried over Na2SO4, filtered and evaporated to dryness. Purification by column

S3
chromatography (neutralized SiO2, pentane/ethyl acetate, 10:1) afforded the enol ester as a
diastereomeric mixture of E/Z (1:24) (1.87 g, 3.07 mmol, 69% yield) as a yellow oil.
Z-Isomer
1H NMR (500 MHz, C6D6) δ (ppm) 7.57 (d, J = 1.4 Hz, 1H), 7.40 – 7.24 (m, 10H), 7.19 – 6.99 (m,
10H), 5.31 (d, J = 4.0 Hz, 1H), 5.12 (d, J = 11.4 Hz, 1H), 4.61 (s, 2H), 4.57 (d, J = 11.4 Hz, 2H), 4.54
(d, J = 11.9 Hz, 1H), 4.47 (d, J = 11.6 Hz, 1H), 4.47 (dd, J = 7.7, 0.8 Hz, 1H), 4.43 (d, J = 12.0 Hz,
1H), 4.12 (dd, J = 7.7, 3.0 Hz, 1H), 4.02 (dd, J = 4.0, 2.9 Hz, 1H), 2.41 (hept, J = 7.0 Hz, 1H), 1.03
(d, J = 7.0 Hz, 3H), 1.02 (d, J = 7.0 Hz, 3H).
13C NMR (76 MHz, C D ) δ (ppm) 173.2, 139.1, 139.1, 138.6, 137.8, 136.9, 128.7, 128.6, 128.6,
6 6
128.6, 128.2, 128.0, 127.9, 123.5, 100.3, 79.2, 76.8, 75.4, 73.7, 73.2, 73.1, 70.3, 34.2, 18.9,
18.8.
HR-MS (ESI): m/z calcd for C38H40O7Na+: 631.26662 found 631.26697.
IR (ATR): 𝑣̃ (cm-1) = 3088, 3063, 3031, 2975, 2932, 2875, 1746, 1603, 1588, 1496, 1454, 1357,
1286, 1241, 1205, 1145.
[α]20
D = 36.4° (c = 0.33, CHCl3).

Figure S1. 1H NMR (500 MHz, C6D6) spectrum of compound 2.

S4
Figure S2. 13C NMR (76 MHz, C6D6) spectrum of compound 2.

Compound 3

Before use, enol ester 2 was azeotropically destilled with toluene (3x 10 mL) and dried for 0.5 h at high
vacuum. To a solution of enol ester (4.72 g, 7.76 mmol, 1.0 eq.) in 1,2-dichloroethane (78 mL) was
added molecular sieve 4 Å and diiodomethane (6.25 mL, 77.6 mmol, 10.0 eq.). The suspension was
stirred at room temperature for 0.5 h and finally a solution of diethylzinc (1 M in hexane, 38.8 mL,
38.8 mmol, 5.0 eq.) was added dropwise. The reaction mixture was heated to 50 °C and stirred for 3 d.
After full consumption of starting material the reaction mixture was diluted with dichloromethane
(70 mL), filtered and quenched with saturated Na2CO3 solution (50 mL). The aqueous layer was
extracted with dichloromethane (3x 70 mL), the combined organic phases dried over Na2SO4 and
evaporated to dryness. Purification by column chromatography (neutralized SiO2, pentane/ethyl
acetate, 10:1) afforded a non-separable mixture of diastereomeric spirocyclopropanated
monosaccharides (2.7 g, 4.34 mmol, 56% yield) as a yellow oil.

Compound 4

Potassium carbonate (5.47 g, 39.6 mmol, 10.0 eq.) was added to a solution of the diastereomeric
mixture of 3 (2.47 g, 3.96 mmol, 1.0 eq.) in a mixture of methanol/water 15:1 (40 mL). The suspension

S5
was stirred for 16 h at room temperature. The reaction mixture was diluted with ethyl acetate (200 mL)
and terminated with water (100 mL). The aqueous layer was extracted with ethyl acetate (3x 100 mL).
The combined organic layers were washed with brine (100 mL), dried over Na2SO4, filtrated and
concentrated to dryness. Purification by column chromatography (neutralized SiO2, pentane/ethyl
acetate, 10:1) afforded both aldehydes 4 (1.39 g, 2.52 mmol, 64% yield) and 7 (0.29 g, 0.54 mmol, 13%
yield) as colorless oils.
1
H NMR (400 MHz, C6D6) δ (ppm) 9.60 (s, 1H), 7.38 – 7.04 (m, 20H), 5.54 – 5.51 (m, 1H), 5.02 (d, J =
11.8 Hz, 1H), 4.79 (d, J = 12.0 Hz, 1H), 4.58 (d, J = 11.8 Hz, 1H), 4.50 (d, J = 12.2 Hz, 1H), 4.49 (d, J = 12.2
Hz, 1H),4.43 (d, J = 12.2 Hz, 1H), 4.19 (s, 2H), 3.91 – 3.86 (m, 2H), 3.80 (d, J = 4.4 Hz, 1H), 1.34 (s, 3H).
13
C NMR (101 MHz, C6D6) δ (ppm) 199.5, 139.4, 138.6, 138.4, 138.2, 128.6, 128.6, 128.6, 128.5, 128.3,
128.2, 128.2, 128.0, 127.9, 127.8, 127.6, 98.6, 82.9, 76.9, 76.1, 75.3, 73.9, 73.5, 72.8, 71.1, 19.1.
HR-MS (ESI): m/z calcd for C35H36O6Na+: 575.24041; found: 575.24058.
IR (ATR): 𝑣̃ (cm-1) = 3088, 3063, 3030, 3007, 2981, 2928, 2870, 2815, 2708, 1952, 1877, 1812, 1728,
1605, 1587, 1496, 1453, 1394, 1362, 1330, 1309, 1249, 1206, 1154, 1090, 1025.
[α]20
D = 52.3° (c = 1.54, CHCl3).

Figure S3. 1H NMR (400 MHz, C6D6) spectrum of compound 4.

S6
Figure S4. 13C NMR (101 MHz, C6D6) spectrum of compound 4.

Compound 5

To a solution of aldehyde 4 (0.95 g, 1.72 mmol, 1.0 eq.) in methanol (17 mL) was added sodium
tetrahydridoborate (0.11 g, 2.91 mmol, 1.7 eq.) at 0 °C and the reaction mixture was stirred for 3 h.
After full consumption of starting material the solvent was removed in vacuum and the residue purified
by flash column chromatography (SiO2, pentane/ethyl acetate, 3:1). Purification afforded the alcohol
5 (0.83 g, 1.51 mmol, 88%) as colorless solid.
1
H NMR (300 MHz, C6D6) δ (ppm) 7.35 – 7.03 (m, 20H), 5.07 (d, J = 11.4 Hz, 1H), 4.99 (d, J = 1.9 Hz, 1H),
4.76 (d, J = 10.3 Hz, 1H), 4.71 (d, J = 11.5 Hz, 1H), 4.69 (d, J = 12.3 Hz, 1H), 4.67 (d, J = 12.4 Hz, 1H), 4.52
– 4.46 (m, 2H), 4.40 (d, J = 11.8 Hz, 1H), 4.29 (d, J = 12.1 Hz, 1H), 4.25 (dd, J = 10.3, 2.8 Hz, 1H), 3.90
(dd, J = 2.8, 1.9 Hz, 1H), 3.65 (t, J = 11.0 Hz, 1H), 3.55 (dd, J = 11.4, 2.1 Hz, 1H), 2.27 (dd, J = 10.8, 2.6
Hz, 1H), 1.42 (s, 3H).
13
C NMR (151 MHz, C6D6) δ (ppm) 139.7, 139.3, 139.0, 138.0, 128.7, 128.6, 128.5, 128.5, 128.3, 128.1,
128.0, 127.9, 127.8, 127.7, 127.6, 127.5, 99.4, 80.7, 77.6, 76.8, 75.9, 75.7, 73.2, 72.5, 69.4, 68.3, 19.2.
HR-MS (ESI): m/z calcd for C35H38O6Na+: 577.25606; found: 577.25605.
IR (ATR): 𝑣̃ (cm-1) = 3564, 3477, 3088, 3063, 3030, 3005, 2981, 2911, 2868, 1496, 1453, 1398, 1367,
1332, 1245.
[α]20
D = 53.3° (c = 0.42, CHCl3).

S7
Figure S5. 1H NMR (300 MHz, C6D6) spectrum of compound 5.

Figure S6. 13C NMR (151 MHz, C6D6) spectrum of compound 5.

S8
Compound 6

Under an argon atmosphere, alcohol 5 (77.0 mg, 0.14 mmol, 1.0 eq.) was dissolved in a mixture of
ethanol, dichloromethane and ethyl acetate (3:1:1, 2.5 mL). Palladium on charcoal (10 wt.% on
activated carbon, 30.0 mg, 0.03 mmol, 0.2 eq.) was added and the argon atmosphere exchanged by a
hydrogen atmosphere. The suspension was stirred at room temperature for 5 h and the reaction
mixture finally filtered through Celite® 545. The Celite® plug was rinsed with methanol (3x 5 mL) and
evaporation of the solvent afforded the fully deprotected monosaccharide 6 (26.0 mg, 0.13 mmol, 96%
yield) as a colorless foam.
For the mixture following data were observed:
HR-MS (ESI): m/z calcd for C7H14O6Na+: 217.06826; found: 217.06834.
IR (ATR): 𝑣̃ (cm-1) = 3320, 2981, 2934, 1646, 1413, 1381, 1252, 1180, 1139, 1022.
[α]20
D = 12.7° (c = 0.96, MeOH).

𝜶-Me-Manp

1
H NMR (600 MHz, D2O) δ (ppm) 5.19 (d, J = 2.4 Hz, 1H), 4.08 (dd, J = 9.7, 3.4 Hz, 1H), 3.93 (dd, J = 3.3,
2.4 Hz, 1H), 3.90 (d, J = 9.7 Hz, 1H), 3.62 (d, J = 12.0 Hz, 1H), 3.52 (d, J = 12.0 Hz, 1H), 1.28 (s, 3H).
13
C NMR (151 MHz, D2O) δ (ppm) 97.7, 82.4, 73.9, 70.8, 70.1, 69.5, 21.4.

𝜷-Me-Manp

1
H NMR (600 MHz, D2O) δ (ppm) 5.07 (d, J = 1.3 Hz, 1H), 3.94 (dd, J = 3.3, 1.3 Hz, 1H), 3.86 (dd, J = 10.3,
3.3 Hz, 1H), 3.78 (d, J = 10.3 Hz, 1H), 3.61 (d, J = 12.0 Hz, 1H), 3.56 (d, J = 12.0 Hz, 1H).
13
C NMR (151 MHz, D2O) δ (ppm) 92.3, 80.0, 74.4, 72.7, 70.3, 69.5, 16.0.

S9
Figure S7. 1H NMR (600 MHz, D2O) spectrum of compound 6.

Figure S8. 13C NMR (151 MHz, D2O) spectrum of compound 6.

S10
Figure S9. Partial NOESY (600 MHz, D2O) of 𝛼-Me-Manp.

Figure S10. Partial NOESY (600 MHz, D2O) of 𝛽-Me-Manp.

S11
Figure S11. Partial NOESY (600 MHz, D2O) of 𝛽-Me-Manp.

Figure S12. Proton-coupled 13C NMR (126 MHz, D2O) spectrum of compound 6.

S12
2.2 L-Gulose Series
Compound 7

For procedure, see compound 4.

1
H NMR (400 MHz, C6D6): δ (ppm) 10.20 (s, 1H), 7.35 – 7.00 (m, 20H), 5.01 (d, J = 3.0 Hz, 1H), 4.76 (d, J
= 11.4 Hz, 1H), 4.72 (d, J = 11.8 Hz, 1H), 4.55 (s, 2H), 4.43 (d, J = 11.4 Hz, 1H), 4.40 – 4.32 (m, 2H), 4.27
(d, J = 11.9 Hz, 1H), 4.26 (dd, J = 9.1, 3.0 Hz, 1H), 4.13 (d, J = 9.2 Hz, 1H), 3.83 (t, J = 3.0 Hz, 1H), 1.53 (s,
3H).
13
C NMR (101 MHz, C6D6): δ (ppm) 200.6, 138.9, 138.8, 138.7, 137.6, 128.7, 128.6, 128.5, 128.4, 127.9,
127.9, 98.0, 80.6, 79.8, 77.4, 75.8, 75.8, 73.2, 72.5, 70.2, 21.4.
HR-MS (ESI): m/z calcd for C35H36O6Na+: 575.24041; found: 575.24034.
IR (ATR): 𝑣̃ (cm-1) 3088, 3063, 3031, 3005, 2988, 2920, 2868, 1728, 1496, 1453, 1393, 1365.
[α]20
D = 37.3° (c = 0.86, CHCl3).

Figure S13. 1H NMR (400 MHz, C6D6) spectrum of compound 7.

S13
Figure S14. 13C NMR (101 MHz, C6D6) spectrum of compound 7.

Compound 8

To a solution of aldehyde 7 (0.29 g, 0.52 mmol, 1.0 eq.) in methanol (50 mL) was added sodium
tetrahydridoborate (0.03 g, 0.88 mmol, 1.7 eq.) at 0 °C and the reaction mixture was stirred for 3 h.
After full consumption of starting material the solvent was removed in vacuum and the residue purified
by flash column chromatography (SiO2, pentane/ethyl acetate, 3:1) afforded alcohol 8 (0.29 g,
0.52 mmol, quant) as a colorless solid.

1
H NMR (500 MHz, CDCl3) δ (ppm) 7.36 – 7.22 (m, 20H), 4.91 (d, J = 11.2 Hz, 1H), 4.89 (d, J = 2.7 Hz,
1H), 4.77 (d, J = 12.1 Hz, 1H), 4.68 (s, 2H), 4.67 – 4.57 (m, 3H), 4.47 (d, J = 12.1 Hz, 1H), 4.16 (dd, J = 9.3,
3.0 Hz, 1H), 3.96 (dd, J = 11.5, 3.5 Hz, 1H), 3.95 (d, J = 9.3 Hz, 1H), 3.75 (t, J = 2.8 Hz, 1H), 3.60 (dd, J =
11.5, 8.8 Hz, 1H), 2.78 (dd, J = 9.0, 4.0 Hz, 1H), 1.42 (s, 3H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 138.4, 138.2, 138.1, 137.2, 128.5, 128.5, 128.4, 128.4, 127.9, 127.9,
127.8, 127.7, 127.7, 127.7, 127.6, 98.1, 82.1, 79.0, 76.6, 75.9, 75.4, 72.8, 72.5, 70.3, 67.4, 23.8.
HR-MS (ESI): m/z calcd for C35H38O6Na+: 577.25606; found: 577.25610.
IR (ATR): 𝑣̃ (cm-1) = 3468, 3087, 3063, 3030, 2920, 1953, 1877, 1811, 1734, 1606, 1587, 1496, 1453,
1369, 1303, 1246, 1208, 1114, 1059, 1041, 1025.
[α]20
D = 35.3° (c = 0.47, CHCl3).

S14
Figure S15. 1H NMR (500 MHz, CHCl3) spectrum of compound 8.

Figure S16. 13C NMR (126 MHz, CHCl3) spectrum of compound 8.

S15
Compound 9

Under an argon atmosphere, alcohol 8 (49.6 mg, 0.09 mmol, 1.0 eq.) was dissolved in a mixture of
ethanol, dichloromethane and ethyl acetate (3:1:1, 1.6 mL). Palladium on charcoal (10 wt.% on
activated carbon, 19.0 mg, 0.02 mmol, 0.2 eq.) was added and the argon atmosphere exchanged by a
hydrogen atmosphere. The suspension was stirred at room temperature for 7 h and the reaction
mixture finally filtered through Celite® 545. The Celite® plug was rinsed with methanol (3x 5 mL) and
evaporation of the solvent afforded the fully deprotected monosaccharide 9 (17.2 mg, 0.09 mmol,
quant) as a colorless foam.
For the mixture following data were observed:
HR-MS (ESI): m/z calcd for C7H14O6Na+: 217.06826; found: 217.06830.
IR (ATR): 𝑣̃ (cm-1) = 3348, 3257, 2991, 2948, 1406, 1375, 1341, 1282, 1186, 1148, 1131, 1088, 1038.
[α]20
D = 4.0° (c = 0.49, MeOH).

𝜶-Me-Gulp

1
H NMR (500 MHz, D2O) δ (ppm) 5.14 (d, J = 3.6 Hz, 1H), 4.10 (dd, J = 8.5, 3.4 Hz, 1H), 3.88 – 3.86 (m,
1H), 3.84 (d, J = 11.8 Hz, 1H), 3.81 (d, J = 8.5 Hz, 1H), 3.64 (d, J = 11.7 Hz, 1H), 1.37 (s, 3H).
13
C NMR (126 MHz, D2O) δ (ppm) 96.1, 82.1, 75.7, 73.4, 70.9, 67.8, 24.6.

𝜷-Me-Gulp

1
H NMR (500 MHz, D2O) δ (ppm) 5.10 (d, J = 1.2 Hz, 1H), 3.95 (dd, J = 3.4, 1.3 Hz, 1H), 3.93 (d, J = 12.6
Hz, 1H), 3.87 (dd, J = 10.5, 3.4 Hz, 1H), 3.69 (d, J = 10.4 Hz, 1H), 3.58 (d, J = 12.5 Hz, 1H), 1.32 (s, 4H).
13
C NMR (126 MHz, D2O) δ (ppm) 92.1, 80.0, 75.9, 74.3, 72.2, 62.3, 24.9.

𝜷-Me-Gulf

1
H NMR (500 MHz, D2O) δ (ppm) 5.33 (d, J = 5.5 Hz, 1H), 4.42 (dd, J = 4.4, 3.0 Hz, 1H), 4.16 (d, J = 2.9
Hz, 1H), 4.06 (dd, J = 5.5, 4.4 Hz, 1H), 3.54 (d, J = 11.9 Hz, 1H), 3.50 (d, J = 11.4 Hz, 1H), 1.32 (s, 3H).
13
C NMR (126 MHz, D2O) δ (ppm) 103.7, 82.5, 80.6, 77.0, 75.3, 68.9, 22.6.

S16
Figure S17. 1H NMR (500 MHz, H2O) spectrum of compound 9.

Figure S18. 13C NMR (500 MHz, H2O) spectrum of compound 9.

S17
Figure S19. Partial NOESY (500 MHz, D2O) of compound 𝛼-Me-Gulp.

Figure S20. Partial NOESY (500 MHz, D2O) of compound 𝛼-Me-Gulp.

S18
Figure S21. Partial NOESY (500 MHz, D2O) of compound 𝛽-Me-Gulp.

Figure S22. Partial NOESY (500 MHz, D2O) of compound 𝛽-Me-Gulf.

S19
Figure S23. Proton-coupled 13C NMR (126 MHz, D2O) spectrum of compound 9.

S20
2.3 L-Altrose Series
Compound 11

DMSO (3.84 mL, 54.1 mmol, 5.0 eq.) was added dropwise to a mixture of oxalyl chloride (1.86 mL,
21.6 mmol, 2.0 eq.) in dry dichloromethane (110 mL) at -78 °C. After the addition was completed, the
reaction mixture was stirred for 15 min before a solution of alcohol 10 (5.85 g, 10.8 mmol, 1.0 eq.) in
dichloromethane (110 mL) was added. The reaction mixture was stirred at equal temperature for 0.5 h
and NEt3 (12.0 mL, 86.6 mmol, 8.0 eq.) was added. The mixture was warmed to room temperature and
diluted with dichloromethane (100 mL) and saturated NaHCO3 solution (100 mL). The aqueous layer
was extracted with dichloromethane (3x 100 mL) and the combined organic phases were washed with
saturated NaCl solution (100 mL). The organic phase was dried over Na2SO4, filtered and evaporated
to dryness.
The crude aldehyde was dissolved in acetonitrile (110 mL) and potassium carbonate (8.97 g,
64.9 mmol, 6.0 eq.) and isobutyric anhydride (10.8 mL, 64.9 mmol, 6.0 eq.) were added. The reaction
mixture was refluxed for 3 h and finally the reaction terminated by the addition of ethyl acetate
(100 mL) and water (100 mL). The aqueous layer was extracted with ethyl acetate (3x 100 mL) and the
combined organic phases were dried over Na2SO4, filtered and evaporated to dryness. Purification by
column chromatography (neutralized SiO2, pentane/ethyl acetate, 10:1) afforded the enol ester 11 as
a diastereomeric mixture of E/Z (1:7) (5.96 g, 9.79 mmol, 91% yield) as a colorless solid.
Z-Isomer
1
H NMR (500 MHz, CDCl3) δ (ppm)7.43 – 7.26 (m, 20H), 6.75 (s, 1H), 5.04 (d, J = 12.0 Hz, 1H), 4.87 (d, J
= 10.9 Hz, 1H), 4.81 (d, J = 10.9 Hz, 1H), 4.78 (d, J = 12.7 Hz, 1H), 4.76 (d, J = 11.9 Hz, 1H), 4.63 (d, J =
7.1 Hz, 1H), 4.58 (s, 2H), 4.42 (d, J = 12.7 Hz, 1H), 4.07 (dd, J = 9.5, 7.1 Hz, 1H), 3.89 (d, J = 3.4 Hz, 1H),
3.52 (dd, J = 9.5, 3.4 Hz, 1H), 2.72 (hept, J = 7.0 Hz, 1H), 1.27 (d, J = 7.0 Hz, 3H), 1.26 (d, J = 7.0 Hz, 3H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 173.7, 138.6, 138.0, 137.6, 137.0, 133.5, 128.4, 128.3, 128.2, 128.2,
128.1, 128.0, 127.9, 127.7, 127.7, 127.6, 127.5, 123.8, 102.9, 78.9, 78.6, 75.2, 72.1, 71.2, 70.9, 69.2,
33.9, 18.8, 18.7.
HR-MS (ESI): m/z calcd for C38H40O7Na+: 631.26662; found: 631.26681.
IR (ATR): 𝑣̃ (cm-1) = 3115, 3088, 3063, 3032, 2977, 2931, 2878, 1955, 1876, 1751, 1604, 1496, 1453,
1390, 1360, 1310, 1288, 1240, 1196, 1142, 1091, 1047, 1022.
[α]20
D = -56.2° (c = 0.43, CHCl3).

S21
Figure S24. 1H NMR (500 MHz, CDCl3) spectrum of the diastereomeric mixture of compound 11.

Figure S25. 13C NMR (126 MHz, CDCl3) spectrum of the diastereomeric mixture of compound 11.

S22
Compound 12

Before use, enol ester 11 was azeotropically destilled with toluene (3x 10 mL) and dried for 0.5 h at
high vacuum. To a solution of enol ester (5.63 g, 9.26 mmol, 1.0 eq.) in 1,2-dichloroethane (90 mL) was
added molecular sieve 4 Å and diiodomethane (7.46 mL, 92.6 mmol, 10.0 eq.). The suspension was
stirred at room temperature for 0.5 h and finally a solution of diethylzinc (1 M in hexane, 46.0 mL,
46.0 mmol, 5.0 eq.) was added dropwise. The reaction mixture was heated to 50 °C and stirred for 3 d.
After full consumption of starting material the reaction mixture was diluted with dichloromethane
(100 mL), filtered and quenched with saturated Na2CO3 solution (100 mL). The aqueous layer was
extracted with dichloromethane (3x 100 mL), the combined organic phases were dried over Na2SO4
and evaporated to dryness. Purification by column chromatography (neutralized SiO2, pentane/ethyl
acetate, 10:1) afforded a non-separable mixture of diastereomeric spirocyclopropanated
monosaccharides 12 (2.89 g, 4.64 mmol, 50% yield) as a yellow oil.

Compound 13

Potassium carbonate (0.36 g, 2.57 mmol, 1.0 eq.) was added to a solution of the diastereomeric
mixture of 12 (1.60 g, 2.57 mmol, 1.0 eq.) in a mixture of methanol/dichloromethane/water 16:2:1
(100 mL). The suspension was stirred for 3 h at 0 °C. After the addition of ethyl acetate (50 mL) and
water (50 mL), the aqueous layer was extracted with ethyl acetate (3x 20 mL). The combined organic
layers were washed with brine (20 mL), dried over Na2SO4, filtrated and concentrated to dryness.
Purification by column chromatography (neutralized SiO2, pentane/ethyl acetate, 3:1) afforded both
spirocyclopropanols 13 (0.71 g, 1.28 mmol, 50% yield) as a colorless solid and 16 (0.15 g, 0.27 mmol,
11% yield) as a colorless oil.
1
H NMR (600 MHz, C6D6) δ (ppm) 7.41 – 7.32 (m, 8H), 7.20 – 7.04 (m, 12H), 5.03 (d, J = 11.3 Hz, 1H),
4.97 (d, J = 12.2 Hz, 1H), 4.83 – 4.77 (m, 2H), 4.72 (dd, J = 12.2, 4.3 Hz, 2H), 4.66 – 4.61 (m, 2H), 4.56
(d, J = 12.0 Hz, 1H), 4.31 (dd, J = 9.5, 7.7 Hz, 1H), 3.63 (dd, J = 9.5, 3.3 Hz, 1H), 2.72 (d, J = 3.3 Hz, 1H),
2.66 (dd, J = 7.4, 4.1 Hz, 1H), 1.30 (s, 1H), 0.90 (dd, J = 7.4, 4.2 Hz, 1H), 0.61 (t, J = 7.4 Hz, 1H).
13
C NMR (151 MHz, C6D6) δ (ppm) 139.9, 139.5, 139.5, 138.6, 128.6, 128.6, 128.5, 128.4, 128.3, 128.3,
127.8, 127.7, 127.7, 127.5, 102.7, 81.1, 79.5, 77.5, 75.2, 72.8, 72.3, 71.1, 58.0, 51.8, 19.1.
HR-MS (ESI): m/z calcd for C35H36O6Na+: 575.24041; found: 575.24057.
IR (ATR): 𝑣̃ (cm-1) = 3483, 3378, 3063, 3028, 2918, 2873, 1495, 1452, 1354, 1259, 1203, 1173, 1095,
1025.
[α]20
D = -59.8° (c = 1.34, CHCl3).

S23
Figure S26. 1H NMR (600 MHz, C6D6) spectrum of compound 13.

Figure S27. 13C NMR (151 MHz, C6D6) spectrum of compound 13.

S24
Figure S28. Partial NOESY (600 MHz, C6D6) of compound 13.

Compound 13a

Potassium carbonate (99.5 mg, 0.72 mmol, 10.0 eq.) was added to a solution of cyclopropanol 13
(39.7 g, 0.07 mmol, 1.0 eq.) in a mixture of methanol/water 15:1 (4 mL). The suspension was stirred
for 16 h at room temperature. After the addition of ethyl acetate (10 mL) and water (10 mL), the
aqueous layer was extracted with ethyl acetate (3x 10 mL). The combined organic layers were washed
with brine (10 mL), dried over Na2SO4, filtrated and concentrated to dryness. Purification by column
chromatography (neutralized SiO2, pentane/ethyl acetate, 3:1) afforded aldehyde 13a (39.6 mg,
0.07 mmol, quant) as a colorless oil.
1
H NMR (600 MHz, CDCl3) δ (ppm) 9.53 (s, 1H), 7.43 – 7.23 (m, 20H), 5.01 (d, J = 11.9 Hz, 1H), 4.99 (d,
J = 11.2 Hz, 1H), 4.87 (d, J = 10.8 Hz, 1H), 4.76 (d, J = 11.8 Hz, 1H), 4.73 (d, J = 10.9 Hz, 1H), 4.71 (d, J =
12.0 Hz, 1H), 4.69 (d, J = 11.8 Hz, 1H), 4.63 (d, J = 11.4 Hz, 1H), 4.60 (d, J = 7.7 Hz, 1H), 4.00 (d, J = 2.8
Hz, 1H), 3.89 (dd, J = 9.7, 7.7 Hz, 1H), 3.47 (dd, J = 9.7, 2.8 Hz, 1H), 1.25 (s, 3H).
13
C NMR (151 MHz, CDCl3) δ (ppm) 203.0, 138.5, 138.3, 138.0, 137.2, 128.4, 128.4, 128.2, 128.1, 128.1,
127.9, 127.7, 127.7, 127.7, 127.5, 100.8, 82.4, 79.8, 78.4, 75.4, 75.0, 74.9, 73.4, 71.1, 18.9.
HR-MS (ESI): m/z calcd for C35H36O6Na+: 575.24041; found: 575.24062.
IR (ATR): 𝑣̃ (cm-1) = 3088, 3063, 3030, 2927, 2867, 2797, 2694, 1730, 1605, 1587, 1496, 1454, 1395,
1363, 1313, 1209, 1074, 1039.
[α]20
D = -59.6° (c = 1.13, CHCl3).

S25
Figure S29. 1H NMR (600 MHz, CDCl3) spectrum of compound 13a.

Figure S30. 13C NMR (151 MHz, CDCl3) spectrum of compound 13a.

S26
Compound 14

To a solution of aldehyde 13a (0.3 g, 0.54 mmol, 1.0 eq.) in methanol (15 mL) was added sodium
tetrahydridoborate (34.6 mg, 0.91 mmol, 1.7 eq.) at 0 °C and the reaction mixture stirred for 2 h. After
full consumption of starting material the solvent was removed in vacuum and the residue purified by
flash column chromatography (SiO2, pentane/ethyl acetate, 3:1). Purification afforded alcohol 14
(0.27 g, 0.49 mmol, 91% yield) as colorless solid.
1
H NMR (600 MHz, CDCl3) δ (ppm) 7.40 – 7.18 (m, 20H), 4.90 (d, J = 12.1, 1H), 4.85 (d, J = 3.3 Hz, 1H),
4.73 (d, J = 11.7 Hz, 1H), 4.68 (d, J = 12.0 Hz, 1H), 4.66 – 4.59 (m, 2H), 4.57 (d, J = 11.6 Hz, 1H), 4.55 (d,
J = 11.5 Hz, 1H), 4.52 (d, J = 12.1 Hz, 1H), 3.89 (dd, J = 5.9, 3.6 Hz, 1H), 3.87 (d, J = 3.3 Hz, 1H), 3.84 (dd,
J = 5.7, 3.1 Hz, 1H), 3.55 (dd, J = 11.3, 7.7 Hz, 1H), 3.39 (dd, J = 11.3, 5.0 Hz, 1H), 1.81 (dd, J = 7.7, 5.0
Hz, 1H), 1.44 (s, 3H).
13
C NMR (151 MHz, CDCl3) δ (ppm) 138.6, 138.5, 138.1, 137.8, 128.4, 128.3, 128.2, 128.0, 127.8, 127.7,
127.7, 127.6, 127.5, 127.5, 127.4, 99.1, 77.8, 77.4, 76.1, 74.4, 73.2, 72.6, 69.7, 67.2, 19.8.
HR-MS (ESI): m/z calcd for C35H38O6Na+: 577.25606 found: 577.25603.
IR (ATR): 𝑣̃ (cm-1) = 3442, 3088, 3062, 3033, 2930, 2883, 1606, 1587, 1497, 1453, 1367, 1312, 1279,
1209, 1088, 1043.
[α]20
D = -40.7° (c = 0.28, CHCl3).

Figure S31. 1H NMR (600 MHz, CDCl3) spectrum of compound 14.

S27
Figure S32. 13C NMR (151 MHz, CDCl3) spectrum of compound 14.

Compound 15

Under an argon atmosphere, alcohol 14 (0.17 g, 0.31 mmol, 1.0 eq.) was dissolved in a mixture of
ethanol, dichloromethane and ethyl acetate (3:1:1, 15 mL). Palladium on charcoal (10 wt.% on
activated carbon, 66 mg, 0.06 mmol, 0.2 eq.) was added and the argon atmosphere exchanged by a
hydrogen atmosphere. The suspension was stirred at room temperature for 3.5 h and the reaction
mixture finally filtered through Celite® 545. The Celite® plug was rinsed with methanol (3x 5 mL) and
evaporation of the solvent afforded the fully deprotected monosaccharide 15 (60.0mg, 0.31 mmol,
quant) as a colorless foam.
Alternative preparation from compound 23
Alcohol 23 (11.0 mg, 40.1 µmol) was emulsified in water (1 mL) and concentrated hydrochloric acid
(0.1 ml) was added dropwise. The raction mixture was stirred for 1 d. After full consumption of starting
material the reaction mixture was diluted with water (10 mL) and aluminium oxide (basic, Brockmann
I) was added until neutralization was achieved. The suspension was filtered through Celite® 545 and
evaporated to dryness. The residue was extracted with methanol (3x 5 mL) and evaporation of the
solvent afforded compound 15 (6.2 mg, 31.9 µmol, 80% yield).
For the mixture following data were observed:
HR-MS (ESI): m/z calcd for C7H14O6Na+: 217.06826; found: 217.06827.
IR (ATR): 𝑣̃ (cm-1) = 3299, 2928, 1735, 1651, 1411, 1375, 1263, 1213, 1121, 1016.
[α]20
D = -5.0° (c = 0.72, MeOH).

S28
𝜶-Me-Altp
1
H NMR (500 MHz, D2O) δ (ppm) 5.27 (d, J = 4.7 Hz, 1H), 4.27 (t, J = 7.5 Hz, 1H), 4.07 (dd, J = 7.6, 4.8
Hz, 1H), 3.76 (d, J = 7.5 Hz, 1H), 3.57 – 3.54 (m, 2H), 1.23 (s, 3H).
13
C NMR (126 MHz, D2O) δ (ppm) 97.3, 86.6, 79.4, 76.1, 75.8, 68.6, 22.5.

𝜷-Me-Altp

1
H NMR (500 MHz, D2O) δ (ppm) 4.82 (d, 1H), 3.86 (dd, J = 10.2, 3.6 Hz, 1H), 3.80 (d, J = 12.2 Hz, 1H),
3.75 (d, J = 3.9 Hz, 2H), 3.56 (d, J = 12.8 Hz, 3H), 3.49 (dd, J = 10.2, 8.0 Hz, 1H), 1.28 (s, 3H).
13
C NMR (126 MHz, D2O) δ (ppm) 95.4, 81.8, 74.6, 73.8, 73.2, 64.8, 22.8.

𝜷-Me-Altf
1
H NMR (500 MHz, D2O) δ (ppm) 5.22 (d, J = 3.1 Hz, 1H), 4.18 (dd, J = 6.4, 4.4 Hz, 1H), 4.01 (dd, J = 4.4,
3.1 Hz, 1H), 3.99 (d, J = 6.4 Hz, 1H), 3.58 – 3.57 (m, 2H), 1.23 (s, 3H).
13
C NMR (126 MHz, D2O) δ (ppm) 103.5, 88.3, 84.4, 78.0, 75.8, 68.8, 22.4.

Figure S33. Partial NOESY (500 MHz, D2O) of compound 𝛼-MeAltp.

S29
Figure S34. Partial NOESY (600 MHz, D2O) of compound 𝛽-Me-Altp.

Figure S35. Partial NOESY (500 MHz, D2O) of compound 𝛽-Me-Altf.

S30
Figure S36. Proton-coupled 13C NMR (126 MHz, D2O) spectrum of compound 15.

S31
2.4 D-Galactose Series

Compound 16

For the procedure, see compound 13.

1
H NMR (300 MHz, CD3CN) δ (ppm) 7.46 – 7.18 (m, 20H), 4.86 (d, J = 10.2 Hz, 1H), 4.82 (d, J = 9.4 Hz,
1H), 4.79 (d, J = 11.6 Hz, 1H), 4.73 (d, J = 11.2 Hz, 1H), 4.64 (d, J = 12.1 Hz, 1H), 4.63 (d, J = 11.7 Hz, 1H),
4.59 (d, J = 11.8 Hz, 1H), 4.56 (d, J = 11.7 Hz, 1H),.4.51 (d, J = 7.5 Hz, 1H), 3.75 (dd, J = 9.5, 7.4 Hz, 1H),
3.65 (dd, J = 9.5, 3.1 Hz, 1H), 3.44 (t, J = 6.4 Hz, 1H), 3.20 (d, J = 3.1 Hz, 1H), 0.66 – 0.55 (m, 2H).
13
C NMR (75 MHz, CD3CN) δ (ppm) 140.2, 140.0, 139.8, 138.9, 129.4, 129.3, 129.2, 129.2, 129.1, 128.9,
128.8, 128.7, 128.5, 103.7, 80.6, 77.5, 75.6, 72.4, 72.1, 71.6, 57.9, 53.7, 16.4.
HR-MS (ESI): m/z calcd for C35H36O6Na+: 575.24041; found: 575.24059.
IR (ATR) 𝑣̃ (cm-1) = 3488, 3088, 3062, 3032, 2922, 2885, 2857, 1877, 1818, 1735, 1661, 1633, 1604,
1586, 1497, 1454, 1427, 1362, 1309, 1258, 1241, 1227, 1211, 1156, 1105, 1056, 1027.
[α]20
D = -10.6° (c = 0.42, CHCl3).

Figure S37. 1H NMR (300 MHz, CD3CN) spectrum of compound 16.

S32
Figure S38. 1H NMR (76 MHz, CD3CN) spectrum of compound 16.

Figure S39. Partial NOESY (600 MHz, CD3CN) of compound 16.

S33
Figure S40. Partial NOESY (600 MHz, CD3CN) of compound 16.

Compound 16a

Potassium carbonate (10.0 mg, 74.0 µmol, 10.0 eq.) was added to a solution of cyclopropanol 16
(4.1 mg, 7.42 µmol, 1.0 eq.) in a mixture of methanol/water 15:1 (1 mL). The suspension was stirred
for 16 h at room temperature. After the addition of ethyl acetate (10 mL) and water (10 mL), the
aqueous layer was extracted with ethyl acetate (3x 10 mL). The combined organic layers were washed
with brine (10 mL), dried over Na2SO4, filtrated and concentrated to dryness. Purification by column
chromatography (neutralized SiO2, pentane/ethyl acetate, 3:1) afforded aldehyde 16a (3.2 mg,
5.79 µmol, 78% yield) as colorless oil.

1
H NMR (500 MHz, CDCl3) δ (ppm) 9.70 (s, 1H), 7.40 – 7.20 (m, 20H), 4.96 (d, J = 12.0 Hz, 1H), 4.86 (d,
J = 11.0 Hz, 1H), 4.83 (d, J = 11.0 Hz, 1H), 4.81 (d, J = 6.8 Hz, 1H), 4.77 (d, J = 11.8 Hz, 1H), 4.72 (d, J =
11.0 Hz, 1H), 4.68 – 4.63 (m, 2H), 4.44 (d, J = 11.0 Hz, 1H), 3.98 (dd, J = 8.8, 6.8 Hz, 1H), 3.86 (d, J = 2.7
Hz, 1H), 3.77 (dd, J = 8.8, 2.7 Hz, 1H), 1.23 (s, 3H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 203.7, 138.3, 138.1, 137.8, 137.4, 128.4, 128.4, 128.3, 128.2, 128.2,
128.0, 127.8, 127.7, 127.7, 127.7, 127.6, 99.1, 81.0, 79.5, 79.0, 78.0, 74.8, 74.5, 73.2, 70.8, 18.1.
HR-MS (ESI): m/z calcd for C35H36O6Na+: 575.24041; found: 575.24035.
IR (ATR) 𝑣̃ (cm-1) = 3088, 3063, 3031, 2869, 2360, 1953, 1879, 1811, 1738, 1605, 1496, 1453, 1362,
1210, 1092, 1041.
[α]20
D = -35.4° (c = 0.95, CHCl3).

S34
Figure S41. 1H NMR (500 MHz, CDCl3) spectrum of compound 16a.

Figure S42. 13C NMR (126 MHz, CDCl3) spectrum of compound 16a.

S35
Compound 17

To a solution of aldehyde 16a (9.5 mg, 17.2 µmol, 1.0 eq.) in methanol (1 mL) was added sodium
tetrahydridoborate (1.1 mg, 0.03 mmol, 1.7 eq.) at 0 °C and the reaction mixture was stirred for 3 h.
After full consumption of starting material the solvent was removed in vacuum and the residue purified
by flash column chromatography (SiO2, pentane/ethyl acetate, 3:1). Purification afforded alcohol 17
(9.5 mg, 17.1 µmol, quant) as a colorless solid.

1
H NMR (600 MHz, CDCl3) δ (ppm) 7.38 – 7.26 (m, 20H), 4.94 (d, J = 11.6 Hz, 1H), 4.89 (d, J = 10.8 Hz,
1H), 4.88 (d, J = 12.1 Hz, 1H), 4.82 (d, J = 11.7 Hz, 1H), 4.74 (d, J = 10.8 Hz, 1H), 4.73 (d, J = 7.3 Hz, 1H),
4.71 (d, J = 11.8 Hz, 1H), 4.61 (d, J = 11.7 Hz, 2H), 3.93 (dd, J = 9.2, 7.4 Hz, 1H), 3.85 (dd, J = 9.2, 2.8 Hz,
1H), 3.61 (d, J = 2.7 Hz, 1H), 3.58 (d, J = 6.6 Hz, 2H), 1.58 (t, J = 6.6 Hz, 1H), 1.17 (s, 3H).
13
C NMR (151 MHz, CDCl3) δ (ppm) 138.5, 138.4, 138.2, 137.7, 128.5, 128.5, 128.4, 128.3, 128.3, 128.2,
128.2, 128.0, 127.9, 127.7, 127.7, 127.7, 127.6, 99.2, 79.9, 79.5, 77.4, 75.0, 74.4, 73.4, 70.8, 67.5, 18.8.
HR-MS (ESI): m/z calcd for C35H38O6Na+: 577.25606; found: 577.25614.
IR (ATR): 𝑣̃ (cm-1) = 3585, 3472, 3088, 3063, 3030, 2877, 1951, 1877, 1811, 1604, 1587, 1496, 1454,
1363, 1209, 1092, 1062, 1026.
[α]20
D = -46.1° (c = 0.96, CHCl3)

Figure S43. 1H NMR (600 MHz, CDCl3) spectrum of compound 17.

S36
Figure S44. 13C NMR (151 MHz, CDCl3) spectrum of compound 17.

Compound 18

Under an argon atmosphere, alcohol 17 (8.9 mg, 16.0 µmol, 1.0 eq.) was dissolved in a mixture of
ethanol, dichloromethane and ethyl acetate (3:1:1, 1 mL). Palladium on charcoal (10 wt.% on activated
carbon, 3.5 mg, 3.3 µmol, 0.2 eq.) was added and the argon atmosphere exchanged by a hydrogen
atmosphere. The suspension was stirred at room temperature for 3.5 h and the reaction mixture finally
filtered through Celite® 545. The Celite® plug was rinsed with methanol (3x 1 mL) and evaporation of
the solvent afforded the fully deprotected monosaccharide 18 (3.1 mg, 16.0 µmol, quant) as a colorless
foam.
For the mixture following data were observed:
HR-MS (ESI): m/z calcd for C7H14O6Na+: 217.06826; found: 217.06827.
IR (ATR): 𝑣̃ (cm-1) = 3299, 2928, 1651, 1411, 1375, 1263, 1213, 1121, 1016.
[α]20
D = -7.7 (c = 0.33, MeOH).

𝜶-Me-Galp

1
H NMR (500 MHz, D2O) δ (ppm) 5.27 (d, J = 4.7 Hz, 1H), 4.25 (t, J = 7.4 Hz, 1H), 4.09 (dd, J = 7.6, 4.7
Hz, 1H), 3.82 (d, J = 7.1 Hz, 1H), 3.56 (d, J = 11.5 Hz, 1H), 3.52 (d, J = 11.6 Hz, 1H), 1.22 (s, 3H).
13
C NMR (126 MHz, D2O) δ (ppm) 97.4, 86.2, 79.6, 76.3, 75.5, 69.2, 21.2.

𝜷-Me-Galp

1
H NMR (500 MHz, D2O) δ 4.82 (d, J = 8.1 Hz, 1H), 3.95 (dd, J = 10.1, 3.4 Hz, 1H), 3.80 (d, J = 3.4 Hz,
1H), 3.58 (d, J = 11.2 Hz, 1H), 3.50 (dd, J = 10.1, 8.0 Hz, 1H), 1.32 (s, 2H).

S37
13
C NMR (126 MHz, D2O) δ 95.5, 80.3, 75.3, 74.4, 73.2, 68.8, 19.8.

𝜷-Me-Galf

1
H NMR (500 MHz, D2O) δ (ppm) 5.21 (d, J = 3.2 Hz, 1H), 4.17 (dd, J = 6.5, 4.6 Hz, 1H), 4.00 (dd, J = 4.7,
3.4 Hz, 2H), 4.00 (d, J = 6.4 Hz, 1H), 3.57 (d, J = 11.5 Hz, 1H), 3.53 (d, J = 11.4 Hz, 1H), 1.22 (s, 3H).
13
C NMR (126 MHz, D2O) δ (ppm) 103.5, 87.5, 84.5, 78.2, 75.7, 69.2, 21.6.

Figure S45. Partial NOESY (500 MHz, D2O) of compound 𝛼-Me-Galp.

S38
Figure S46. Partial NOESY (500 MHz, D2O) of compound 𝛽-Me-Galp.

Figure S47. Partial NOESY (600 MHz, D2O) of compound 𝛽-Me-Galf.

S39
Figure S48. Partial NOESY (500 MHz, D2O) of compound 𝛽-Me-Galf.

Figure 49. Proton-coupled 13C NMR (126 MHz, D2O) spectrum of compound 18.

S40
2.5 Isopropylidene Protected Series
Compound 20

DMSO (20.5 mL, 0.29 mol, 5.0 eq.) was added dropwise to a mixture of oxalyl chloride (9.9 mL,
0.12 mol, 2.0 eq.) in dry dichloromethane (200 mL) at -78 °C. After full addition the reaction mixture
was stirred for 15 min before a solution of alcohol 19 (15.0 g, 0.06mol, 1.0 eq.) in dichloromethane
(200 mL) was added. The reaction mixture was stirred at equal temperature for 0.5 h and NEt3
(64.0 mL, 0.46 mol, 8.0 eq.) was added. The mixture was warmed to room temperature and diluted
with dichloromethane (100 mL) and saturated NaHCO3 solution (100 mL). The aqueous layer was
extracted with dichloromethane (3x 100 mL) and the combined organic phases were washed with
saturated NaCl solution (100 mL). The organic phase was dried over Na2SO4, filtered and evaporated
to dryness.
The crude aldehyde was dissolved in acetonitrile (200 mL) and potassium carbonate (48.1 g, 0.35 mol,
6.0 eq.) and isobutyric anhydride (58.0 mL, 0.35 mol, 6.0 eq.) were added. The reaction mixture was
refluxed for 3 h and finally the reaction terminated by the addition of ethyl acetate (100 mL) and water
(100 mL). The aqueous layer was extracted with ethyl acetate (3x 100 mL) and the combined organic
phases were dried over Na2SO4, filtered and evaporated to dryness. Purification by column
chromatography (SiO2, pentane/ethyl acetate, 5:1) and crystallization from diethyl ether afforded a
non-separable mixture of the E/Z diastereomers (1:26) of 20 (15.5 g, 47.2 mmol, 81% yield) as a
colorless solid.
Z Isomer

1
H NMR (500 MHz, CDCl3) δ (ppm) 7.04 (s, 1H), 5.66 (d, J = 3.7 Hz, 1H), 4.62 (dd, J = 7.5, 2.3 Hz, 1H),
4.51 (d, J = 7.5 Hz, 1H), 4.30 (dd, J = 3.7, 2.2 Hz, 1H), 2.70 (hept, J = 7.0 Hz, 1H), 1.48 (s, 3H), 1.39 (s,
3H), 1.37 (s, 3H), 1.35 (s, 3H), 1.22 (d, J = 7.0 Hz, 3H), 1.20 (d, J = 7.0 Hz, 3H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 173.6, 133.4, 123.1, 110.4, 109.8, 97.1, 73.1, 70.4, 70.2, 33.7, 26.7,
26.3, 25.6, 24.3, 18.9, 18.6.
HR-MS (ESI): m/z calcd for C16H24O7Na+: 351.14142; found: 351.14146.
IR (ATR): 𝑣̃(cm-1) = 3090, 2988, 2940, 2915, 2878, 1749, 1465, 1384, 1323, 1294, 1251, 1204, 1145,
1086, 1061.
[α]20
D = -157.3° (c = 1.07, CHCl3).

S41
Figure S50. 1H NMR (500 MHz, CDCl3) spectrum of the diastereomeric mixture of compound 20.

Figure S51. 13C NMR (126 MHz, CDCl3) spectrum of the diastereomeric mixture of compound 20.

S42
Compound 21

Before use, enol ester 20 was azeotropically destilled with toluene (3x 5 mL) and dried for 0.5 h at high
vacuum. To a solution of enol ester 20 (9.5 g, 28.9 mmol, 1.0 eq.) in 1,2-dichloroethane (280 mL) was
added molecular sieve 4 Å and diiodomethane (23.4 mL, 0.29 mol, 10.0 eq.). The suspension was
stirred at room temperature for 0.5 h and finally a solution of diethylzinc (1 M in hexane, 144 mL,
0.15 mol, 5.0 eq.) was added dropwise. The reaction mixture was heated to 50 °C and stirred for 3 d.
After full consumption of starting material the reaction mixture was diluted with dichloromethane
(100 mL), filtered and quenched with saturated Na2CO3 solution (100 mL). The aqueous layer was
extracted with dichloromethane (3x 200 mL), the combined organic phases dried over Na2SO4 and
evaporated to dryness. Purification by column chromatography (SiO2, pentane/ethyl acetate, 15:1)
afforded spirocyclopropanated monosaccharides 21 (2.59 g, 7.57 mmol, 26% yield) as yellow oil.
1
H NMR (500 MHz, CDCl3) δ (ppm) 5.35 (d, J = 3.8 Hz, 1H), 4.62 (dd, J = 6.6, 1.5 Hz, 1H), 4.34 (dd, J =
3.8, 1.7 Hz, 1H), 4.19 (d, J = 6.6 Hz, 1H), 3.96 (dd, J = 7.7, 4.6 Hz, 1H), 2.58 (hept, J = 7.0 Hz, 1H), 1.37 (t,
J = 7.7 Hz, 1H), 1.17 (d, J = 7.0 Hz, 2H), 1.16 (d, J = 7.0 Hz, 4H), 0.95 (dd, J = 7.6, 4.7 Hz, 1H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 177.8, 109.9, 109.2, 96.4, 74.1, 73.4, 71.6, 57.3, 53.6, 33.8, 27.0,
26.3, 25.6, 25.2, 19.0, 18.9, 14.5.
HR-MS (ESI): m/z calcd for C17H26O7Na+: 365.15707; found: 365.15694.
IR (ATR): 𝑣̃ (cm-1) = 2983, 2937, 1743, 1464, 1378, 1348, 1317, 1238, 1211, 1157, 1062, 1016.
[α]20
D = -91.6° (c = 1.03, CHCl3).

Figure S52. 1H NMR (500 MHz, CDCl3) spectrum of compound 21.

S43
Figure S53. 13C NMR (126 MHz, CDCl3) spectrum of compound 21.

Figure S54. Partial NOESY (500 MHz, CDCl3) of compound 21.

S44
Figure S55. Partial NOESY (500 MHz, CDCl3) of compound 21.

Compound 22

Potassium carbonate (2.63 g, 19.0 mmol, 10.0 eq.) was added to a solution of compound 21 (0.65 g,
1.9 mmol, 1.0 eq.) in a mixture of methanol/water 15:1 methanol (16 mL). The suspension was stirred
for 16 h at room temperature. The reaction mixture was diluted with ethyl acetate (100 mL) and water
(50 mL). The aqueous layer was extracted with ethyl acetate (3x 50 mL). The combined organic layers
were washed with brine (50 mL), dried over Na2SO4, filtrated and concentrated to dryness. Purification
by column chromatography (neutralized SiO2, pentane/ethyl acetate, 5:1) afforded both aldehyde 22
(0.36 g, 1.32 mmol, 69% yield) as colorless oil and spirocyclopropanol 24 (50.0 mg, 0.18 mmol, 10%
yield) as colorless solid.
1
H NMR (300 MHz, CDCl3) δ (ppm) 9.63 (s, 1H), 5.60 (d, J = 5.5 Hz, 1H), 4.68 (d, J = 7.6 Hz, 1H), 4.56 (dd,
J = 7.6, 1.7 Hz, 1H), 4.28 (dd, J = 5.5, 1.7 Hz, 1H), 1.47 (d, J = 0.7 Hz, 3H), 1.43 (d, J = 0.9 Hz, 3H), 1.37 (d,
J = 0.7 Hz, 3H), 1.30 (d, J = 0.7 Hz, 3H), 1.28 (s, 3H).
13
C NMR (76 MHz, CDCl3) δ (ppm) 200.5, 108.4, 108.0, 95.6, 79.1, 70.7, 70.1, 70.0, 26.3, 24.4, 24.3,
24.3, 18.8.
HR-MS (ESI): m/z calcd for C13H20O6Na+: 295.11521; found: 295.11539.
IR 𝑣̃ (cm-1) = 2986, 2939, 2910, 2830, 1729, 1458, 1378, 1316, 1292, 1258, 1210, 1167, 1116, 1062.
[α]20
D = -75.6° (c = 0.55, CHCl3).

S45
Figure S56. 1H NMR (300 MHz, CDCl3) spectrum of compound 22.

Figure S57. 13C NMR (76 MHz, CDCl3) spectrum of compound 22.

S46
Compound 23

To a solution of aldehyde 22 (0.29 g, 1.07 mmol, 1.0 eq.) in methanol (3 mL) was added sodium
tetrahydridoborate (68.9 mg, 1.82 mmol, 1.7 eq.) at 0 °C and the reaction mixture stirred for 5 h. After
full consumption of starting material the solvent was removed in vacuum and the residue purified by
flash column chromatography (SiO2, pentane/ethyl acetate, 7:1) affording alcohol 23 (0.29 g,
1.04 mmol, 97%) as colorless oil.
1
H NMR (500 MHz, CDCl3) δ (ppm) 5.55 (d, J = 4.3 Hz, 1H), 4.56 (dd, J = 7.0, 0.8 Hz, 1H), 4.19 (dd, J =
4.3, 0.9 Hz, 1H), 4.10 (d, J = 7.0 Hz, 1H), 3.66 (dd, J = 11.7, 6.5 Hz, 1H), 3.38 (dd, J = 11.8, 7.7 Hz, 1H),
2.46 (dd, J = 7.7, 6.5 Hz, 1H), 1.53 (d, J = 0.7 Hz, 3H), 1.46 (d, J = 0.8 Hz, 3H), 1.36 (d, J = 0.8 Hz, 3H), 1.35
(d, J = 0.8 Hz, 3H), 1.29 (s, 3H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 108.9, 108.2, 94.7, 76.2, 74.2, 73.5, 71.9, 67.0, 26.8, 26.3, 25.1,
24.7, 19.5.
HR-MS (ESI): m/z calcd for C13H22O6Na+: 297.13086; found: 297.13095.
IR 𝑣̃ (cm-1) = 3518, 2987, 2940, 1458, 1378, 1241, 1212, 1163, 1126, 1105, 1046.
[α]20
D = -31.2° (c = 1.57, CHCl3).

Figure S58. 1H NMR (500 MHz, CDCl3) spectrum of compound 23.

S47
Figure S59. 13C NMR (126 MHz, CDCl3) spectrum of compound 23.

Compound 24

For the procedure, see compound 22.

1
H NMR (500 MHz, CDCl3) δ (ppm) 5.64 (d, J = 5.7 Hz, 1H), 4.60 (dd, J = 7.2, 2.3 Hz, 1H), 4.49 (dd, J =
5.8, 2.3 Hz, 1H), 3.94 (dd, J = 2.1, 0.6 Hz, 1H), 3.57 (d, J = 7.3 Hz, 1H), 3.23 (ddd, J = 6.6, 4.0, 2.1 Hz, 1H),
1.60 (d, J = 0.7 Hz, 3H), 1.50 (d, J = 0.7 Hz, 3H), 1.37 (d, J = 0.7 Hz, 3H), 1.36 (d, J = 0.7 Hz, 3H), 1.11 (dd,
J = 7.5, 6.6 Hz, 1H), 0.94 (dd, J = 7.7, 3.9 Hz, 1H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 109.1, 108.5, 96.9, 75.9, 70.7, 70.2, 59.9, 53.1, 26.3, 25.4, 25.2,
24.4, 18.9.
HR-MS (ESI): m/z calcd for C13H20O6Na+: 295.11521; found: 295.11538.
IR 𝑣̃ (cm-1) = 3448, 3093, 2994, 2940, 2907, 1462, 1439, 1379, 1314, 1263, 1214, 1169, 1142, 1099,
1070, 1038.
[α]20
D = -169.2° (c = 0.63, CHCl3).

S48
Figure S60. 1H NMR (500 MHz, CDCl3) spectrum of compound 24.

Figure S61. 13C NMR (126 MHz, CDCl3) spectrum of compound 24.

S49
2.6 D-Glucose Series
Compound 25b

DMSO (2.51 mL, 35.3 mmol, 5.0 eq.) was added dropwise to a mixture of oxalyl chloride (1.21 mL,
14.1 mmol, 2.0 eq.) in dry dichloromethane (71 mL) at -78 °C. After the addition was completed, the
reaction mixture was stirred for 15 min before a solution of alcohol 25a (3.82 g, 7.07 mmol, 1.0 eq.) in
dichloromethane (71 mL) was added. The reaction mixture was stirred at equal temperature for 0.5 h
and NEt3 (7.84 mL, 56.5 mmol, 8.0 eq.) was added. The mixture was warmed to room temperature and
diluted with dichloromethane (70 mL) and saturated NaHCO3 solution (70 mL). The aqueous layer was
extracted with dichloromethane (3x 70 mL) and the combined organic phases were washed with
saturated NaCl solution (70 mL). The organic phase was dried over Na2SO4, filtered and evaporated to
dryness.
The crude aldehyde was dissolved in acetonitrile (70 mL) and potassium carbonate (5.86 g, 42.4 mmol,
6.0 eq.) and isobutyric anhydride (7.25 mL, 42.4 mmol, 6.0 eq.) were added. The reaction mixture was
refluxed for 3 h and finally the reaction terminated by the addition of ethyl acetate (70 mL) and water
(70 mL). The aqueous layer was extracted with ethyl acetate (3x 70 mL) and the combined organic
phases were dried over Na2SO4, filtered and evaporated to dryness. Purification by column
chromatography (neutralized SiO2, pentane/ethyl acetate, 10:1) afforded the enol ester as a
diastereomeric mixture of E/Z (1:3) (2.99 g, 4.91 mmol, 69% yield) as a yellow oil.

Z-isomer
1
H NMR (500 MHz, CDCl3) δ (ppm) 7.40 – 7.25 (m, 20H), 6.97 (d, J = 1.2 Hz, 1H), 5.00 (d, J = 11.8 Hz,
1H), 4.99 (d, J = 6.6 Hz, 1H), 4.80 (d, J = 11.4 Hz, 1H), 4.73 (d, J = 11.8 Hz, 1H), 4.71 (d, J = 11.7 Hz, 1H),
4.67 (s, 2H), 4.66 (d, J = 11.4 Hz, 1H), 4.59 (d, J = 11.6 Hz, 1H), 4.01 (dd, J = 6.4, 1.2 Hz, 1H), 3.72 (dd, J
= 6.9, 6.3 Hz, 1H), 3.62 (t, J = 6.8 Hz, 1H), 2.70 (hept, J = 7.0 Hz, 1H), 1.25 (d, J = 7.0 Hz, 3H), 1.24 (d, J =
7.0 Hz, 3H).
13
C NMR (126 MHz, CDCl3) δ 173.7, 138.1, 138.1, 137.5, 137.0, 134.9, 128.5, 128.4, 128.3, 128.3, 128.0,
128.0, 127.9, 127.9, 121.5, 101.6, 82.0, 81.2, 76.1, 74.1, 73.9, 72.0, 71.0, 33.9, 18.9, 18.8.
HR-MS (ESI): m/z calcd for C38H40O7Na+: 631.26662; found: 631.26707.
IR (ATR): 𝑣̃ (cm-1) = 3088, 3063, 3031, 2975, 2933, 2908, 2875, 1954, 1876, 1748, 1704, 1603, 1496,
1454, 1388, 1360, 1286, 1239, 1206, 1183, 1140, 1066, 1022.

S50
Figure S62. 1H NMR (500 MHz, CHCl3) spectrum of compound 25b.

Figure S63. 13C NMR (126 MHz, CHCl3) spectrum of compound 25b.

S51
Compound 27

Before use, enol ester 25b was azeotropically destilled with toluene (3x 10 mL) and dried for 0.5 h at
high vacuum. To a solution of enol ester (2.92 g, 4.79 mmol, 1.0 eq.) in 1,2-dichloroethane (48 mL) was
added molecular sieve 4 Å and diiodomethane (3.86 mL, 47.9 mmol, 10.0 eq.). The suspension was
stirred at room temperature for 0.5 h and finally a solution of diethylzinc (1 M in hexane, 24 mL,
24.0 mmol, 5.0 eq.) was added dropwise. The reaction mixture was heated to 50 °C and stirred for 3 d.
After full consumption of starting material the reaction mixture was diluted with dichloromethane
(50 mL), filtered and quenched with saturated Na2CO3 solution (50 mL). The aqueous layer was
extracted with dichloromethane (3x 50 mL), the combined organic phases dried over Na2SO4 and
evaporated to dryness. Purification by column chromatography (neutralized SiO2, pentane/ethyl
acetate, 10:1) afforded a non-separable mixture of diastereomeric spirocyclopropanated
monosaccharides 27 (1.94 g, 3.12 mmol, 65% yield) as a yellow oil.

Compound 25c

Potassium carbonate (1.22 g, 8.8 mmol, 10.0 eq.) was added to a solution of the diastereomeric
mixture of 27 (0.55 g, 0.88 mmol, 1.0 eq.) in a mixture of methanol/water 15:1 (9 mL). The suspension
was stirred for 16 h at room temperature. After the addition of ethyl acetate (20 mL) and water
(20 mL), the aqueous layer was extracted with ethyl acetate (3x 20 mL). The combined organic layers
were washed with brine (20 mL), dried over Na2SO4, filtrated and concentrated to dryness. Purification
by column chromatography (neutralized SiO2, pentane/ethyl acetate, 10:1) afforded both aldehydes
25c (0.21 g, 0.37 mmol, 42% yield) as colorless solid and 26a (0.18 g, 0.33 mmol, 38% yield) as a
colorless oil.
1
H NMR (600 MHz, C6D6) δ (ppm) 9.43 (s, 1H), 7.33 – 7.26 (m, 6H), 7.27 – 7.22 (m, 2H), 7.19 – 7.04 (m,
12H), 4.85 (d, J = 11.5 Hz, 1H), 4.82 (d, J = 6.8 Hz, 1H), 4.78 (d, J = 11.5 Hz, 1H), 4.75 (d, J = 12.0 Hz, 1H),
4.67 (d, J = 11.4 Hz, 1H), 4.64 (d, J = 11.5 Hz, 1H), 4.62 (d, J = 11.0 Hz, 1H), 4.43 (d, J = 11.0 Hz, 1H), 4.38
(d, J = 11.9 Hz, 1H), 3.78 (dd, J = 8.6, 0.7 Hz, 1H), 3.75 (dd, J = 8.6, 7.2 Hz, 1H), 3.63 (t, J = 7.0 Hz, 1H),
1.30 (s, 3H).
13
C NMR (151 MHz, C6D6) δ (ppm) 199.1, 139.1, 139.0, 138.5, 137.9, 128.7, 128.6, 128.6, 128.5, 128.34,
128.3, 128.1, 128.0, 127.9, 127.8, 127.8, 99.4, 82.7, 81.2, 80.8, 77.9, 75.0, 75.0, 74.3, 70.8, 14.6.
HR-MS (ESI): m/z calcd for C35H36O6Na: 575.24041; found: 575.24057.
IR (ATR) 𝑣̃ (cm-1) = 3088, 3063, 3031, 2971, 2923, 2873, 1747, 1605, 1496, 1454, 1358, 1286, 1241,
1205, 1107, 1024.
[α]20
D = -41.2° (c = 0.75, CHCl3).

S52
Figure S64. 1H NMR (600 MHz, C6D6) spectrum of compound 25c.

Figure S65. 13C NMR (600 MHz, C6D6) spectrum of compound 25c.

S53
Compound 25d

To a solution of aldehyde 25c (0.15 g, 0.27 mmol, 1.0 eq.) in methanol (12 mL) was added sodium
tetrahydridoborate (17.5 mg, 0.46 mmol, 1.7 eq.) at 0 °C and the reaction mixture was stirred for 2 h.
After full consumption of starting material the solvent was removed in vacuum and the residue purified
by flash column chromatography (SiO2, pentane/ethyl acetate, 3:1) affording alcohol 25d (0.14 g,
0.25 mmol, 93% yield) as colorless solid.

1
H NMR (500 MHz, CDCl3) δ (ppm) 7.40 – 7.14 (m, 20H), 4.94 (d, J = 10.8 Hz, 1H), 4.90 (d, J = 10.9 Hz,
1H), 4.90 (d, J = 11.3 Hz, 1H), 4.86 (d, J = 11.8 Hz, 1H), 4.78 (d, J = 10.8 Hz, 1H), 4.77 (d, J = 7.9 Hz, 1H),
4.74 (d, J = 10.8 Hz, 1H), 4.66 (d, J = 11.3 Hz, 1H), 4.64 (d, J = 11.8 Hz, 1H), 3.82 – 3.74 (m, 2H), 3.55 –
3.49 (m, 2H), 3.48 – 3.44 (m, 1H), 2.00 (dd, J = 8.7, 5.1 Hz, 1H), 1.17 (s, 3H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 138.6, 138.5, 138.3, 137.3, 128.5, 128.4, 128.4, 128.3, 128.2, 128.1,
128.0, 127.9, 127.7, 127.6, 127.6, 98.5, 83.1, 82.1, 78.3, 76.8, 75.8, 75.3, 75.1, 71.3, 67.4, 15.2.
HR-MS (ESI): m/z calcd for C35H38O6Na+: 577.25606; found: 577.25615.
IR (ATR): 𝑣̃ (cm-1) = 3482, 3088, 3031, 2872, 1951, 1876, 1810, 1605, 1587, 1496, 1454, 1397, 1362,
1242, 1211, 1066.
[α]20
D = -20.2° (c = 0.64, CHCl3).

Figure S66. 1H NMR (500 MHz, CHCl3) spectrum of compound 25d.

S54
Figure S67. 13C NMR (126 MHz, CHCl3) spectrum of compound 25d.

Compound 25

Under an argon atmosphere, alcohol 25d (56.0 mg, 0.10 mmol, 1.0 eq.) was dissolved in a mixture of
ethanol, dichloromethane and ethyl acetate (3:1:1, 3 mL). Palladium on charcoal (10 wt.% on activated
carbon, 21.3 mg, 0.02 mmol, 0.2 eq.) was added and the argon atmosphere exchanged by a hydrogen
atmosphere. The suspension was stirred at room temperature for 6 h and the reaction mixture finally
filtered through Celite® 545. The Celite® plug was rinsed with methanol (3x 5 mL) and evaporation of
the solvent afforded the fully deprotected monosaccharide 25 (19.4 mg, 0.10 mmol, quant) as a
colorless foam.
For the mixture following data were observed:
HR-MS (ESI): m/z calcd for C7H14O6Na+: 217.06826; found: 217.06829.
IR (ATR): 𝑣̃ (cm-1) = 3307, 2983, 2921, 1729, 1649, 1377, 1266, 1212.
[α]20
D = 7.6° (c = 0.35, MeOH).

𝜷-Me-Glcp
1
H NMR (600 MHz, D2O) δ (ppm) 4.81 (d, J = 8.2 Hz, 1H), 3.67 (t, J = 9.6 Hz, 1H), 3.58 (d, J = 12.1 Hz,
1H), 3.57 (d, J = 9.7 Hz, 1H), 3.55 (d, J = 12.0 Hz, 1H), 3.22 (dd, J = 9.5, 8.1 Hz, 1H), 1.18 (s, 3H).
13
C NMR (151 MHz, D2O) δ (ppm) 94.7, 80.2, 77.9, 75.6, 73.6, 69.1, 16.5.

S55
Figure S68. 1H NMR (600 MHz, D2O) spectrum of compound 𝛽-MeGlcp.

Figure S69. 13C NMR (151 MHz, D2O) spectrum of compound 25.

S56
Figure S70. Partial NOESY (600 MHz, D2O) of compound 𝛼-Me-Glcp.

Figure S71. Partial NOESY (600 MHz, D2O) of compound 𝛽-Me-Glcp.

S57
Figure S72. Proton-coupled 13C NMR (126 MHz, D2O) spectrum of compound 25.

S58
2.7 L-Idose Series

Compound 26a

For procedure, see compound 25c.

1
H NMR (300 MHz, CDCl3) δ (ppm) 9.81 (s, 1H), 7.45 – 7.13 (m, 20H), 5.01 (d, J = 7.7 Hz, 1H), 4.98 (d, J
= 11.9 Hz, 1H), 4.97 (d, J = 11.2 Hz, 1H), 4.89 (d, J = 11.0 Hz, 1H), 4.87 (d, J = 10.8 Hz, 1H), 4.78 – 4.64
(m, 4H), 3.65 – 3.54 (m, 2H), 3.48 (td, J = 7.6, 1.7 Hz, 1H), 1.41 (s, 3H).
13
C NMR (75 MHz, CDCl3) δ (ppm) 202.3, 138.4, 137.9, 137.6, 128.6, 128.5, 128.5, 128.4, 128.2, 128.1,
128.0, 127.9, 127.8, 99.2, 84.1, 82.7, 82.5, 80.2, 76.2, 75.8, 74.8, 71.7, 21.2.
HR-MS (ESI): m/z calcd for C35H36O6Na+: 575.24041; found: 575.24060.
IR (ATR): 𝑣̃ (cm-1) = 3087, 3063, 3031, 2876, 1952, 1877, 1810, 1730, 1603, 1588, 1496. 1453, 1362,
1313, 1269, 1209, 1166, 1067, 1025.
[α]20
D = -38.4° (c = 0.29, CHCl3).

Figure S73. 1H NMR (300 MHz, CHCl3) spectrum of compound 26a.

S59
Figure S74. 13C NMR (75 MHz, CHCl3) spectrum of compound 26a.

Compound 26b

To a solution of aldehyde 26a (0.15 g, 0.27 mmol, 1.0 eq.) in methanol (12 mL) was added sodium
tetrahydridoborate (17.4 mg, 0.46 mmol, 1.7 eq.) at 0 °C and the reaction mixture was stirred for 2 h.
After full consumption of starting material the solvent was removed in vacuum and the residue purified
by flash column chromatography (SiO2, pentane/ethyl acetate, 3:1) affording alcohol 26b (0.15 g,
0.27 mmol, quant) as colorless solid.

1
H NMR (500 MHz, CDCl3) δ (ppm) 7.39 – 7.22 (m, 20H), 4.90 (m, 4H), 4.82 (d, J = 7.2 Hz, 1H), 4.74 (d, J
= 10.9 Hz, 1H), 4.69 (d, J = 11.0 Hz, 1H), 4.65 (d, J = 12.0 Hz, 1H), 4.64 (d, J = 11.0 Hz, 1H), 3.90 (t, J = 9.1
Hz, 1H), 3.78 (dd, J = 11.7, 6.0 Hz, 1H), 3.71 (dd, J = 11.7, 6.4 Hz, 1H), 3.58 (d, J = 9.5 Hz, 1H), 3.53 (dd,
J = 8.8, 7.2 Hz, 1H), 2.00 (t, J = 6.0 Hz, 1H), 1.34 (s, 3H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 138.4, 138.2, 137.9, 137.2, 128.5, 128.4, 128.4, 128.4, 128.1, 128.1,
127.9, 127.9, 127.9, 127.8, 127.7, 127.6, 98.4, 85.0, 83.0, 82.1, 76.4, 76.1, 75.4, 74.6, 71.0, 64.4, 23.7.
HR-MS (ESI): m/z calcd for C35H38O6Na+: 577.25606; found: 577.25616.
IR (ATR): 𝑣̃ (cm-1) = 3445, 3088, 3063, 3030, 2889, 1872, 1811, 1606, 1587, 1496, 1453, 1397, 1366,
1210, 1180, 1068, 1024.
[α]20
D = -19.3° (c = 0.54, CHCl3).

S60
Figure S75. 1H NMR (500 MHz, CHCl3) spectrum of compound 26b.

Figure 76. 13C NMR (126 MHz, CHCl3) spectrum of compound 26b.

S61
Compound 26

Under an argon atmosphere, alcohol 26b (63.3 mg, 0.11 mmol, 1.0 eq.) was dissolved in a mixture of
ethanol, dichloromethane and ethyl acetate (3:1:1, 3 mL). Palladium on charcoal (10 wt.% on activated
carbon, 24.3 mg, 0.023 mmol, 0.2 eq.) was added and the argon atmosphere exchanged by a hydrogen
atmosphere. The suspension was stirred at room temperature for 6 h and the reaction mixture finally
filtered through Celite® 545. The Celite® plug was rinsed with methanol (3x 5 mL) and evaporation of
the solvent afforded the fully deprotected monosaccharide 26 (22.1 mg, 0.11 mmol, quant) as a
colorless foam.
For the mixture following data were observed:
HR-MS (ESI): m/z calcd for C7H14O6Na+: 217.06826; found: 217.06827.
IR (ATR): 𝑣̃ (cm-1) = 3295, 2983, 2918, 1647, 1421, 1372, 1272, 1177, 1011.
[α]20
D = 6.7° (c = 0.18, MeOH).

𝜷-Me-Idop
1
H NMR (600 MHz, D2O) δ (ppm) 4.89 (d, J = 8.1 Hz, 1H), 3.92 (d, J = 12.7 Hz, 1H), 3.69 (t, J = 9.7 Hz,
1H), 3.60 (d, J = 12.7 Hz, 1H), 3.45 (d, J = 9.9 Hz, 1H), 3.25 (dd, J = 9.5, 8.1 Hz, 1H), 1.31 (s, 3H).
13
C NMR (151 MHz, D2O) δ (ppm) 94.6, 80.6, 79.3, 78.0, 75.2, 62.6, 25.0.

Figure S77. 1H NMR (600 MHz, D2O) spectrum of compound 26.

S62
Figure S78. 13C NMR (151 MHz, D2O) spectrum of compound 26.

Figure S79. Partial NOESY (600 MHz, D2O) of compound 𝛼-Me-Idop.

S63
Figure S80. Partial NOESY (600 MHz, D2O) of compound 𝛽-Me-Idop.

Figure S81. Proton-coupled 13C NMR (126 MHz, D2O) spectrum of compound 26.

S64
2.8 5-C-Monodeuterated compounds

Compound 29

Potassium carbonate (0.4 g, 2.9 mmol, 10.0 eq.) was added to a solution of the diastereomeric mixture
of 27 (0.16 g, 0.29 mmol, 1.0 eq.) in a mixture of deuterated methanol/deuterated water 15:1 (3 mL).
The suspension was stirred for 16 h at room temperature. After the addition of ethyl acetate (20 mL)
and water (20 mL), the aqueous layer was extracted with ethyl acetate (3x 20 mL). The combined
organic layers were washed with brine (20 mL), dried over Na2SO4, filtrated and concentrated to
dryness. Purification by column chromatography (neutralized SiO2, pentane/ethyl acetate, 10:1)
afforded both aldehydes 29 (0.1 g, 0.18 mmol, 61% yield) as colorless oil and 30 as (54.8 mg, 0.1 mmol,
34% yield) colorless solid.
1
H NMR (500 MHz, CDCl3) δ (ppm) 9.45 (s, 1H), 7.37 – 7.22 (m, 20H), 4.89 (d, J = 11.9 Hz, 1H), 4.85 (d,
J = 7.0 Hz, 1H), 4.83 (d, J = 10.9 Hz, 1H), 4.79 (d, J = 11.0 Hz, 1H), 4.71 (d, J = 10.7 Hz, 2H), 4.67 (d, J =
11.0 Hz, 1H), 4.62 (d, J = 11.9 Hz, 1H), 4.56 (d, J = 10.9 Hz, 1H), 3.79 – 3.74 (m, 2H), 3.54 (ddd, J = 6.9,
6.1, 2.0 Hz, 1H), 1.36 (s, 2H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 199.4, 138.2, 138.0, 137.7, 137.0, 128.5, 128.4, 128.3, 128.1, 128.0,
128.0, 127.8, 127.7, 127.7, 98.8, 82.3, 80.9, 80.3, 77.5, 75.2, 74.8, 74.4, 71.0, 14.0 (t, JC-D = 19.7 Hz).
HR-MS (ESI): m/z calcd for C35H35DO6Na++CH3OH: 608.27290; found: 608.27289.
IR (ATR): 𝑣̃ (cm-1) = 3087, 3063, 3031, 2909, 2872, 1953, 1874, 1810, 1740, 1605, 1588, 1496, 1454,
1397, 1362, 1327, 1279, 1210, 1159, 1068, 1028.
[α]20
D = -42.5° (c = 0.79, CHCl3).

Figure S82. 1H NMR (500 MHz, CHCl3) spectrum of compound 29.

S65
Figure S83. 13C NMR (126 MHz, CHCl3) spectrum of compound 29.

Compound 30
For procedure, see compound 29.

1
H NMR (500 MHz, CDCl3) δ (ppm) 9.81 (s, 1H), 7.44 – 7.38 (m, 2H), 7.37 – 7.23 (m, 18H), 5.01 (d, J =
7.9 Hz, 1H), 4.98 (d, J = 11.8 Hz, 1H), 4.96 (d, J = 11.2 Hz, 1H), 4.91 – 4.85 (m, 2H), 4.75 (d, J = 11.9 Hz,
1H), 4.71 (d, J = 10.8 Hz, 1H), 4.70 (d, J = 11.3 Hz, 1H), 4.67 (d, J = 10.9 Hz, 1H), 3.63 – 3.54 (m, 2H), 3.48
(t, J = 8.0 Hz, 1H), 1.40 (s, 2H).
13
C NMR (126 MHz, CDCl3) δ (ppm) 202.2, 138.2, 138.2, 137.7, 137.4, 128.4, 128.4, 128.3, 128.2, 128.0,
127.9, 127.9, 127.8, 127.8, 127.7, 127.6, 99.0, 83.9, 82.6, 82.3, 80.0, 76.0, 75.7, 74.6, 71.5, 20.8 (t, JC-
D = 19.68 Hz).
HR-MS (ESI): m/z calcd for C35H35DO6Na+: 576.24669; found: 576.24665.
IR (ATR): 𝑣̃ (cm-1) = 3087, 3063, 3031, 2939, 2876, 1951, 1876, 1810, 1731, 1605, 1588, 1496, 1454,
1362, 1313, 1275, 1210, 1152, 1066, 1027, 1004.
[α]20
D = -40.3° (c = 0.93, CHCl3).

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Figure S84. 1H NMR (500 MHz, CHCl3) spectrum of compound 30.

Figure S85. 13C NMR (126 MHz, CHCl3) spectrum of compound 30.

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3. X-ray Structure Determinations

The crystals were mounted in inert oil on glass fibres and transferred to the cold gas stream of the
diffractometer (Oxford Diffraction Nova A using mirror-focussed Cu Kα radiation). Absorption
corrections were implemented on the basis of multi-scans. The structures were refined anisotropically
on F2 using the program SHELXL-97.[4] Hydrogen atoms at C6, C7 and O6 of 24 were refined freely.
Other hydrogens were refined using rigid methyl groups or a riding model starting from calculated
positions.
The absolute configurations were confirmed for both structures on the basis of the anomalous
scattering of the oxygen atoms.
The CIF files have been deposited with the Cambridge Crystallographic Data Centre as supplementary
publications no. CCDC-1812853 (Z-20), -1812854 (24). These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre.

Figure S86. The two independent molecules of compound Z-20 in the crystal. Ellipsoids correspond to
50% probability levels.

Figure S87. The molecule of compound 24 in the crystal. Ellipsoids correspond to 50% probability
levels.
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4. Literature
[1] M. Poláková, M. U. Roslund, F. S. Ekholm, T. Saloranta, R. Leino, Eur. J. Org. Chem. 2009, 870.
[2] C. Fernández, O. Nieto, J. A. Fontenla, E. Rivas, M. L. de Ceballos, A. Fernández-Mayoralas, Org.
Biomol. Chem. 2003, 1, 767.
[3] G. Sennari, T. Hirose, M. Iwatsuki, S. Ōmura, T. Sunazuka, Chem. Commun. 2014, 50, 8715.
[4] a) G. M. Sheldrick, Acta Cryst. 2015, C71, 3-8; b) G. M. Sheldrick, Acta Cryst. 2008, A64, 112-122.

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