Ethanethiol → Ethyl 2,4,6-Tri-O-acetyl-3-O-methyl-1-thio-beta-D-glucopyranoside

HRID 1861689Notes

Reaction equation

HRID 1861689 reaction equation
C(O[C@@H:5]1[O:20][C@H:19]([CH2:21][O:22][C:23](=[O:25])[CH3:24])[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:11]([O:12][CH3:13])[C@H:6]1[O:7][C:8](=[O:10])[CH3:9])(=O)C.[CH2:26]([SH:28])[CH3:27].B(F)(F)F.CCOCC.C(=O)([O-])O.[Na+]>C1(C)C=CC=CC=1>[C:8]([O:7][C@@H:6]1[C@@H:11]([O:12][CH3:13])[C@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@@H:19]([CH2:21][O:22][C:23](=[O:25])[CH3:24])[O:20][C@H:5]1[S:28][CH2:26][CH3:27])(=[O:10])[CH3:9]

Participants

6

Reactant 4

HCID 6343EthanethiolHCID 8000Boron trifluoride etherateHCID 516892Sodium BicarbonateHCID 14187922HCID 14187922, compound

Product 1

HCID 69945368Ethyl 2,4,6-Tri-O-acetyl-3-O-methyl-1-thio-beta-D-glucopyranosideYield 53,438.801%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

1,2,4,6-Tetra-O-acetyl-3-O-methyl-β-D-glucopyranose 1 (69 g, 0.19 mmol), (B. Helferich et al., J. prakt. Chem., 132, 321 (1932)) is dissolved in toluene (580 ml). Ethanethiol (28 ml, 0.38 mmol) is added, followed by dropwise addition of a solution of trifluoroborane diethyl etherate (1 M in toluene, 190 ml). The mixture is left stirring for 1.5 hours (TLC), solid sodium hydrogen carbonate is introduced and the mixture is filtered, washed with water, dried and concentrated. Chromatography on a column of silica (3/1 cyclohexane/ethyl acetate) gives 2 (37 g, 54%) [α]D−26 (c=1. dichloromethane). 1H NMR (CDCl3). δ 5.05-4.96 (m, 2H, H-2, H-4), 4.39, (d, 1H, J=9.5 Hz, H-1), 4.18-4.12 (m, 2H, H-6, H-6′), 3.60 (m, 1H, H-5), 3.50 (dd, 1H, J=9.3 Hz, H-3), 3.41 (s, 3H, OCH3), 2.65-2.53 (m, 2H, SCH2CH3), 2.12, 2.11, 2.09 (3s, 9H, 3 Ac), 1.25 (t, 1H, SCH2CH3)

Workup

  1. waitThe mixture is left
  2. additionis introduced
  3. filtrationthe mixture is filtered
  4. washwashed with water
  5. customdried
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-619f1b80308a4994bd9e1a0dd3b5f2e6
Source dataset
uspto-grants-2003_03
Patent number
US06534481B1

Reaction notes

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