4-Toluenesulfonyl chloride → (3R,3aS,6R,6aS)-6-[(4-methylbenzenesulfonyl)oxy]-hexahydrofuro[3,2-b]furan-3-yl 4-methylbenzene-1-sulfonate

HRID 1887376Notes

Reaction equation

[CH2:1]1[O:5][C@@H:4]2[C@H:6]([OH:9])[CH2:7][O:8][C@@H:3]2[C@@H:2]1[OH:10].[C:11]1([CH3:21])[CH:16]=[CH:15][C:14]([S:17](Cl)(=[O:19])=[O:18])=[CH:13][CH:12]=1.[OH-:22].[K+]>C(Cl)(Cl)(Cl)Cl.ClCCl.O>[CH3:21][C:11]1[CH:16]=[CH:15][C:14]([S:17]([O:10][C@@H:2]2[CH2:1][O:5][C@@H:4]3[C@H:6]([O:9][S:17]([C:14]4[CH:15]=[CH:16][C:11]([CH3:21])=[CH:12][CH:13]=4)(=[O:18])=[O:22])[CH2:7][O:8][C@H:3]23)(=[O:19])=[O:18])=[CH:13][CH:12]=1

Participants

Conditions

Temperature: 0 °C

Procedure

Isomannide (40) (50 g, 342.5 mmol) and p-toluenesulphonyl chloride (143.6 g, 753.2 mmol) were dissolved in a mixture of carbon tetrachloride (300 mL), dichloromethane (30 mL) and water (250 mL). The flask was cooled to 0° C. and a solution of potassium hydroxide (42.0 g, 750.0 mmol) in water (42 mL) added dropwise over 2 hours with stirring under argon. The resulting biphasic mixture was stirred vigorously at 0° C. for 24 hours. The resulting off-white precipitate, comprising a mixture of mono- and bistosylates (approximately 1:1), was collected by filtration in vacuo. The filter cake was washed with water then triturated with methanol (500 mL). The solid was isolated by filtration in vacuo to obtain ditosylate (39) as an off-white powder (75 g, 48%). [α]D18+96.7° (c=10.5, CHCl3).

Workup

stirringThe resulting biphasic mixture was stirred vigorously at 0° C. for 24 hours
filtrationwas collected by filtration in vacuo
washThe filter cake was washed with water
customthen triturated with methanol (500 mL)
customThe solid was isolated by filtration in vacuo

Sources & evidence

ORD record: ord-a883f43a73f0451b8af06f6cc4b92722
Source dataset: uspto-grants-2013_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08501744B2

Reaction notes

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