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Supporting Information
Indium Salts-Catalyzed O and S-Glycosylation of Bromo Sugar with Benzyl Glycolate: An Unprecedented Hydrogenolysis
Sunena Chandra, Ram N. Yadav, Armando Paniagua, and Bimal K. Banik*
Department of Chemistry, The University of Texas – Pan American, 1201 W. University Drive, Edinburg, TX 78541, USA. Email: [email protected]
List of Contents
1. General Method………………………………………………………………………...S2
2. General Procedures for the Synthesis of Compounds 3a-f and 4a-f………………...S2
3. NMR Data…………………………………………………………………………….....S3
4. NMR Spectras (1H, 13C)………………………………………………………….…….S6
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General Methods
Melting points were determined in a Fisher Scientific electrochemical Mel-Temp* manual melting point apparatus (Model 1001) equipped with a 300°C thermometer. FT-IR spectra were recorded on a Bruker Alpha modular Platinum-ATR FT-IR spectrometer with OPUS software, using the samples directly (neat) without making pellets. 1H-NMR (600 MHz) and 13C-NMR (150 MHz) spectra were obtained at room temperature with Bruker superconducting UltrashieldTM Plus 600 MHz NMR spectrometer with central field 14.09 Tesla, coil inductance 89.1 Henry and magnetic energy 1127.2 kJ using CDCl3 as solvent. Acetobromo-α-D-glucose, galactose, mannose, and benzyl glycolate (reagent grade, 98%) purchased from Sigma-Aldrich Corporation was used. All other chemicals were purchased from Sigma-Aldrich Corporation (analytical grade). Throughout the project the solvents were purchased from Fisher-Scientific. Deionized water was used for the preparation of all aqueous solutions.
General Experimental Procedures (3a-f)
To the stirred suspension of peracetylated bromo sugar (1 equivalent) and indium trichloride (10-15 mol%) in anhydrous dichloromethane (2 mL) at room temperature, benzyl glycolate or benzyl thioglycolate (1.5 equivalent) was added under argon atmosphere. The reaction was stirred 5-10 hours at room temperature. After the completion of the reaction, as monitored by thin layer chromatography the reaction was diluted with dichloromethane and quenched with 10% aqueous acidic acid solution (1 mL). The organic layer washed with water and brine, the solvent was evaporated under reduced pressure and the crude product was purified by flash column chromatography on silica gel (30% ethyl acetate/ hexanes). The corresponding β-carboxymethyl glucosides (β-CMGL) were afforded in good yield with high anomeric selectivity.
General Experimental Procedures (4a-f)
The benzyl glycolate or thiobenzyl glycolate (1.5 equivalent) was added to the stirred suspension of peracetobromo-α-D-glucose, mannose, galactose (1 equivalent) and indium tribromide (10-15 mol%) in anhydrous dichloromethane (2 mL) at room temperature for an hour. The progress of reaction was monitored with thin layer chromatography. After the completion of the reaction, the reaction mixture was diluted with water and quenched with 10% aqueous acidic acid solution (1 mL). The organic layer washed with water and brine, the solvent was evaporated under reduced pressure and the crude product was purified by flash column chromatography on silica gel (90% ethyl acetate/ hexanes). The corresponding β-carboxymethyl glucosides (β-CMGL) were afforded in good yield with high anomeric selectivity.
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NMR Data
(2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-(2-(benzyloxy)-2-oxoethoxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (3a): 1H-NMR (600 MHz, CDCl3) δ 1.99 (3H, s), 2.00 (3H, s), 2.01 (3H, s), 2.04 (3H, s), 3.67 (1H, ddd, J=2.4, 4.7, 10.2 Hz), 3.98-3.96 (1H, m), 4.23 (1H, dd, J=4.7, 12.4 Hz), 4.26 (1H, brs), 4.66 (1H, d, J=8.0 Hz), 5.08-5.01 (1H, m), 5.16 (1H, brs), 5.22 (1H, t, J=9.5 Hz), 5.28 (1H, s), 7.37-7.28 (5H, m). 13C-NMR (150 MHz, CDCl3) δ 20.97 (CH3), 21.15 (CH3), 22.60 (CH3),
22.94 (CH3), 60.32 (CH), 61.73 (CH2), 64.97 (CH2), 66.73 (CH2), 68.10 (CH), 71.75 (CH), 71.90 (CH), 72.50 (CH), 100.05 (CH), 128.26 (2CH), 128.39 (CH), 135.19 (CH), 168.96 (C), 169.37 (CO), 169.54 (CO), 170.11 (CO), 170.56 (CO), 171.07 (CO).1
(2R,3S,4S,5R,6R)-2-(acetoxymethyl)-6-(2-(benzyloxy)-2-oxoethoxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (3b): 1H-NMR (600 MHz, CDCl3) δ 1.98 (3H, s), 2.03 (3H, s), 2.04 (3H, s), 2.14
(3H, s), 4.13 (1H, ddd, J=6.6, 15.1, 20.2 Hz), 4.34 (2H, brs), 4.64 (1H, d, J=8.0 Hz), 5.04 (1H, dd, J=3.4, 10.4 Hz), 5.18 (2H, brs), 5.26-5.23 (3H, m), 5.39 (1H, d, J=3.3 Hz), 7.38-7.37 (5H, m). 13C-NMR (150 MHz, CDCl3) δ 20.54 (CH3), 20.60 (CH3), 20.62 (CH3), 20.70 (CH3), 61.59 (CH2), 64.79
(CH2), 66.44 (CH), 66.76 (CH2), 68.75 (CH), 70.64 (CH), 70.82 (CH), 100.51 (CH), 128.43 (CH), 128.49 (CH), 128.56 (CH), 128.65 (CH), 135.19 (C), 169.03 (CO), 169.81 (CO), 170.05 (CO), 170.17 (CO), 170.33 (CO).
(2R,4S,5S,6R)-2-(acetoxymethyl)-6-(2-(benzyloxy)-2-oxoethoxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (3c): 1H-NMR (600 MHz, CDCl3) δ 1.99 (3H, s), 2.04 (3H, s), 2.08 (3H, s), 2.15
(3H, s), 4.04 (1H, dd, J=2.3, 12.3 Hz), 4.17-4.13 (1H, m), 4.19 (1H, brs), 4.22 (1H, brs), 4.26-4.23 (2H, m), 4.30 (1H, brs), 4.32 (1H, brs), 4.95 (1H, d, J=1.3 Hz), 5.19 (1H, d, J=2.7 Hz), 5.41-5.37 (1H, m), 7.38-7.32 (5H, m).
13C-NMR (150 MHz, CDCl3) δ 20.62 (CH3), 20.65 (CH3), 20.68 (CH3), 20.79 (CH3), 62.26 (OCH2), 64.71 (OCH2), 66.17 (CH), 67.29 (OCH2), 69.05 (CH), 69.19 (CH), 69.22 (CH), 97.99 (OCH), 128.50 (2CH), 128.57 (2CH), 128.67 (CH), 135.11 (C), 168.87 (CO), 169.67 (CO), 169.75 (CO), 169.76 (CO), 170.56 (CO).2
(2R,4S,5R,6S)-2-(acetoxymethyl)-6-((2-(benzyloxy)-2-oxoethyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate (3d): 1H-NMR (600 MHz, CDCl3) δ 2.01 (3H, s), 2.02 (3H, s), 2.03 (3H, s), 2.04
(3H, s), 3.34 (1H, d, J=8.5 Hz), 3.52 (1H, d, J=8.2 Hz), 3.68 (1H, ddd, J=2.2, 7.9, 10.1 Hz), 4.10 (1H, dd, J=1.5, 2.3 Hz), 4.21 (1H, dd, J=4.8, 4.7 Hz), 4.65 (1H, d, J=10.1 Hz), 5.09-5.02 (2H, m), 5.21-5.15 (3H, m), 7.38-7.32 (5H, m). 13C-NMR (150 MHz, CDCl3) δ 20.53 (CH3), 20.56 (CH3),
20.59 (CH3), 20.65 (CH3), 31.16 (CH2), 61.18 (CH2), 67.23 (CH2), 68.14 (CH), 69.18 (CH), 73.71 (CH), 75.99 (CH), 82.28 (CH), 128.32 (2CH), 128.51 (2CH), 128.65 (CH), 135.40 (C), 169.20 (CO), 169.34 (CO), 169.39 (CO), 170.07 (CO), 170.57 (CO). IR: 1737 cm-1 (C=O).
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(2R,3S,4S,5R,6S)-2-(acetoxymethyl)-6-((2-(benzyloxy)-2-oxoethyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate (3e): 1H-NMR (600 MHz, CDCl3) δ 1.97 (3H, s), 2.02 (3H, s), 2.08 (3H, s),
2.16 (3H, s), 3.27 (2H, brs), 4.19 (1H, ddd, J=6.6, 11.3, 18.2 Hz), 4.55 (1H, d, J=6.9 Hz), 5.01 (1H, dd, J=3.4, 10.4 Hz), 5.19 (2H, brs), 5.29-5.22 (2H, m), 5.40 (1H, d, J=2.6 Hz), 5.85 (1H, d, J=5.7 Hz), 7.40-7.28 (5H, m). 13C-NMR (150 MHz, CDCl3) δ 20.55 (CH3), 20.65 (CH3), 20.67 (CH3), 20.79
(CH3), 31.00 (CH2), 61.33 (CH2), 66.46 (CH), 68.88 (CH), 70.73 (CH2), 82.12 (CH), 99.82 (CH), 127.88 (CH), 128.10 (CH), 128.45 (CH), 128.48 (CH), 128.63 (CH), 136.73 (C), 169.39 (CO), 170.11 (CO), 170.26 (CO), 170.37 (2CO). IR: 1741 cm-1 (C=O).
2-(2R,3R,4S,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-yl)oxy)acetic acid (4a) : m.p. 130-132°C. 1H-NMR (600 MHz, CDCl3) δ 2.03 (3H, s), 2.05 (3H, s), 2.09 (3H, s), 2.11 (3H, s), 3.75 (1H, ddd, J=2.4, 7.6, 10.0 Hz), 4.17 (1H, dd, J=2.3, 12.3 Hz), 4.28 (1H, dd, J=4.8, 12.4 Hz), 4.35 (1H, brs), 4.68 (1H, d, J=7.9 Hz) 4.74 (1H, d, J=1.9 Hz), 5.13-5.05 (1H, m), 5.28-5.23 (1H, m).13C-NMR (150
MHz, CDCl3) δ 20.55 (CH3), 20.65 (CH3), 20.67 (CH3), 20.69 (CH3), 61.72 (CH2), 65.26 (CH2), 68.24 (CH), 70.99 (CH), 72.13 (CH), 72.38 (CH), 72.52 (CH), 10.37 (CH), 169.42 (CO), 169.70 (CO), 170.20 (CO), 170.71 (CO), 171.83 (CO). IR: 1738, 1725 cm-1 (C=O).3
2-(2R,3R,4S,5S,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-yl)oxyacetic acid (4b): 1H-NMR (600 MHz, CDCl3) δ 1.99 (3H, s), 2.06 (3H, s), 2.09 (3H, s), 2.16 (3H, s), 4.72 (1H, ddd, J=4.7, 7.2, 11.2 Hz), 4.35 (1H, brs), 4.63 (1H, d, J=7.9 Hz), 5.06 (1H, dd, J=3.4, 10.4 Hz), 5.26-5.24 (1H, m), 5.40 (1H, d, J=3.4 Hz).13C-NMR (150 MHz, CDCl3) δ 20.53 (CH3), 20.60 (CH3), 20.63 (CH3),
20.74 (CH3), 60.48 (CH), 61.25 (CH), 61.61 (CH2), 63.90 (CH), 64.04 (CH), 64.84 (CH2), 67.11 (CH), 100.70 (OCH), 169.92 (CO), 170.15 (CO), 170.25 (CO), 170.53 (CO), 172.80 (CO).
2-(3S,4S,5R,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-yl)oxy) acetic acid (4c): 1H-NMR (600 MHz, CDCl3) δ 1.93 (3H, s), 1.98 (3H, s), 2.04 (3H, s), 2.09 (3H, s), 4.09-4.02 (2H, m), 4.27-4.16 (2H, m), 4.89 (1H, dd, J=1.1, 9.1 Hz), 5.31-5.08 (4H, m).13C-NMR (150 MHz, CDCl3) δ 20.67 (CH3), 20.70
(CH3), 20.76 (CH3), 20.81 (CH3), 62.39 (OCH2), 64.12 (OCH2), 65.94 (CH), 68.87 (CH), 69.10 (CH), 69.18 (CH), 169.77 (CO), 169.90 (CO), 169.95 (CO), 170.73 (CO), 172.71 (CO).2
2-(3R,4S,5R,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-yl)thio-acetic acid (4d): m.p. 70-72°C. 1H-NMR (600 MHz, CDCl3) δ 2.02 (3H, s), 2.04 (3H, s), 2.07 (3H, s), 2.10 (3H, s), 3.32 (1H, d, J=15.3 Hz), 3.55 (1H, d, J=15.4 Hz), 3.76 (1H, ddd, J=2.5, 7.6, 10.1 Hz), 4.09 (1H, dd, J=2.1, 12.5 Hz), 4.28-4.16 (2H, m),
4.68 (1H, d, J=10.1 Hz), 5.13-5.05 (1H, m), 5.78 (1H, d, J=5.9 Hz).13C-NMR (150 MHz, CDCl3) δ 20.55 (CH3), 20.57 (CH3), 20.61 (CH3), 20.73 (CH3), 31.09 (SCH2), 61.87 (OCH2), 68.19 (CH), 69.62 (CH), 73.66 (CH), 76.01 (CH), 82.32 (OCH), 169.46 (CO), 169.58 (CO), 170.23 (CO), 170.07 (CO), 173.74 (CO). IR: 1740, 1718, 1686 cm-1 (C=O).4
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2-(3R,4S,5S,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-yl)thio-acetic acid (4e): 1H-NMR (600 MHz, CDCl3) δ 1.99 (3H, s), 2.04 (3H, s), 2.07 (3H, s), 2.16 (3H, s), 3.34 (1H, d, J=15.2 Hz), 3.61 (1H, d, J=15.1 Hz), 4.13-3.98 (1H, m), 4.65 (1H, d, J=9.4 Hz), 5.08 (1H, d, J=8.1 Hz), 5.30-5.25 (1H, m), 5.43 (1H,
brs).13C-NMR (150 MHz, CDCl3) δ 20.54 (CH3), 20.59 (CH3), 20.64 (CH3), 20.70 (CH3), 31.10 (SCH2), 61.32 (OCH2), 65.84 (CH), 66.90 (CH), 71.68 (CH), 74.70 (CH), 82.80 (OCH), 169.76 (CO), 170.07 (CO), 170.29 (CO), 170.61 (CO), 174.68 (CO). IR: 1738 cm-1 (C=O).5
NMR Spectra ( 1 H, 13 C)
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