Dimethylformamide → 6-O-[tert-Butyl(diphenyl)silyl]-D-glucose

HRID 922352Notes

Reaction equation

HRID 922352 reaction equation
CN(C=O)C.[O:6]=[CH:7][C@@H:8]([C@H:10]([C@@H:12]([C@@H:14]([CH2:16][OH:17])[OH:15])[OH:13])[OH:11])[OH:9].[C:18]([Si:22](Cl)([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([CH3:21])([CH3:20])[CH3:19]>C(OCC)(=O)C>[Si:22]([O:6][CH2:7][C@@H:8]([OH:9])[C@@H:10]([OH:11])[C@H:12]([OH:13])[C@@H:14]([OH:15])[CH:16]=[O:17])([C:18]([CH3:21])([CH3:20])[CH3:19])([C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 94078tert-ButyldiphenylchlorosilaneHCID 107526(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal

Product 1

HCID 713115126-O-[tert-Butyl(diphenyl)silyl]-D-glucose

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

DMF (10 mL) was placed in a 50 mL flask and cooled to 0° C. in an ice bath. 5 g of D-glucose was added, followed by 0.9 molar equiv. (6.5 mL) of tert-butylchlorodiphenylsilane. The reaction was left for 21 h at 0° C., after which it was poured into 5 mL of ethyl acetate and washed with saturated NaHCO3, brine, dried, isolated by flash column chromatography and evaporated to a yellow solid of 11 (30%). 1NMR [(300 MHz, CDCl3) 5 (ppm): 7.64 (m, 4 H), 7.32 (m, 6 H), 5.13-2.94 (m, 11 H), 1.0 (s, 9 H)], 13C NMR [(300 MHz, CDCl3) 8 (ppm): 135.5 (s, TBDPS-O), 135.45 (s, TBDPS-O), 133.3 (s, TBDPS-O), 133.2 (s, TBDPS-O), 133.0 (s, TBDPS-O), 132.9 (s, TBDPS-O), 129.6 (s, TBDPS-O), 129.5 (d, TBDPS-O), 127.6 (s, TBDPS-O), 127.55 (s, TBDPS-O), 96.6 (s, C1,β), 92.6 (s, C1,α), 77.8 to 60.7 (C2-C6), 26.7 (s, TBDPS-O, 4° C.), 19.1 (s, TBDPS-O), 19.0 (s, TBDPS-O)].

Workup

  1. washwashed with saturated NaHCO3, brine
  2. customdried
  3. customisolated by flash column chromatography
  4. customevaporated to a yellow solid of 11 (30%)
  5. custom1NMR [(300 MHz, CDCl3) 5 (ppm): 7.64 (m, 4 H), 7.32 (m, 6 H), 5.13-2.94 (m, 11 H), 1.0 (s, 9 H)], 13C NMR [(300 MHz, CDCl3) 8 (ppm): 135.5 (s, TBDPS-O), 135.45 (s, TBDPS-O), 133.3 (s, TBDPS-O), 133.2 (s, TBDPS-O), 133.0 (s, TBDPS-O), 132.9 (s, TBDPS-O), 129.6 (s, TBDPS-O), 129.5 (d, TBDPS-O), 127.6 (s, TBDPS-O), 127.55 (s, TBDPS-O), 96.6 (s, C1,β), 92.6 (s, C1,α), 77.8 to 60.7 (C2-C6), 26.7 (s, TBDPS-O, 4° C.), 19.1 (s, TBDPS-O), 19.0 (s, TBDPS-O)]

Sources & evidence

ORD record
ord-83c0ac8c82964ac3bf36e46bb3601451
Source dataset
uspto-grants-2016_03
Patent number
US09278946B2

Reaction notes

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