Thiophenol → 1-Thiophenyl-3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranose

HRID 1637128Notes

Reaction equation

HRID 1637128 reaction equation
C([O:4][C@@H:5]1[O:18][C@H:17]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[C@@H:12]([O:13][C:14](=[O:16])[CH3:15])[C@H:7]([O:8][C:9](=[O:11])[CH3:10])[C@H:6]1[N:24]1[C:28](=[O:29])[C:27]2=[CH:30][CH:31]=[CH:32][CH:33]=[C:26]2[C:25]1=[O:34])(=O)C.[C:35]1([SH:41])[CH:40]=[CH:39][CH:38]=CC=1.[Sn](Cl)(Cl)(Cl)Cl>ClCCl>[S:41]1[CH:35]=[CH:40][CH:39]=[C:38]1[C@:5]1([O:18][C@H:17]([CH2:12][O:13][C:14](=[O:16])[CH3:15])[C@@H:19]([O:20][C:21](=[O:23])[CH3:22])[C@H:7]([O:8][C:9](=[O:11])[CH3:10])[C@H:6]1[N:24]1[C:25](=[O:34])[C:26]2=[CH:33][CH:32]=[CH:31][CH:30]=[C:27]2[C:28]1=[O:29])[OH:4]

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 24287Tin tetrachlorideHCID 2728904beta-D-Glucopyranose, 2-deoxy-2-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-, 1,3,4,6-tetraacetate

Product 1

HCID 867491291-Thiophenyl-3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranoseYield 99%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Compound [2] (0.31-8.02 g, 0.68-17.7 mmol) is dissolved in 3.2-100 ml of dry dichloromethane, and thiophenol (0.15-3.9 g, 1.36-35.4 mmol) and tin tetrachloride (0.35-9.22 g, 1.36-35.4 mmol) are added and the mixture is stirred until reaction is complete. The reaction mixture is diluted and then washed with saturated sodium bicarbonate solution. The crude product compound [3] obtained in this way is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.27-7.14 g, 0.54-14.2 mmol, about 80%) and is dissolved in anhydrous methanol (3-90 ml) and catalytic amounts of sodium methylate (prepared from 0.002-0.05 g of sodium in 0.1-2 ml of methanol) are added. After the reaction is complete, the mixture is neutralized with an acidic ion exchanger (0.2-5 g Amberlite IR-120, H+ -form) (4: 0.21-5.31 g, 0.54-14.1 mmol, about 99% yield). FAB-MS: M+H+ =378. NMR data consistent with Nicolaou et al., J. Am. Chem. Soc. 112:3695 (1990)) and T. J. Caulfield, Ph. D. Dissertation, The University of Pennsylvania (1991).

Workup

  1. additionThe reaction mixture is diluted
  2. washwashed with saturated sodium bicarbonate solution

Sources & evidence

ORD record
ord-372664b612e944059c159211bca91cb0
Source dataset
uspto-grants-2000_03
Patent number
US06037467

Reaction notes

Loading…