Studies on C-glycosides (Ⅳ)——The Reactions of 1-α-Chloro-,1-α-Bromo-,1-α-lodo-,and 1-α-Tosyloxy-2,3,4,6,-tetra-O-benzoyl-D-gluco-pyranose with Substituted Phenylmagnesium Bromides

Abstract

Abstract: Acyl glucopyranosyl halides with different leaving groups attached to C-1, including-OTs, reacted with aryl magnesium bromides in ether or THFto give C-glycosides in 30-80% yield. Acetyl glucopyranosyl halides gave better yields than benzoyl derivatives. The reaction products were affected by the solvent used in the reaction, thus THFfavored the formation of C-2 aryl substituted by-product and lowered the yield of C-glucosides. The ratio of the anomers formed in the reaction mixture was affected by the activity of different leaving groups. More α-anomer was obtained from glucopyranosyl halides with leaving group of higher activity. More β-anomer was formed from Grignard reagents with higher nucleophilicity, but more a-anomer from Grignard reagents with higher steric hindrance. The ratio of theα- and β-anomers in C-glucoside mixtures was calculated from the areas of ¹HNMR peaks.

Key words: C-glyeoside, Grignard reagent, Leaving gronps, Anomer ratio

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Cai Mengshen, Dong Lingjiao, Gao Yigong . Studies on C-glycosides (Ⅳ)——The Reactions of 1-α-Chloro-,1-α-Bromo-,1-α-lodo-,and 1-α-Tosyloxy-2,3,4,6,-tetra-O-benzoyl-D-gluco-pyranose with Substituted Phenylmagnesium Bromides[J]. Chem. J. Chinese Universities, 1988, 9(5): 450.

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Studies on C-glycosides (Ⅳ)——The Reactions of 1-α-Chloro-,1-α-Bromo-,1-α-lodo-,and 1-α-Tosyloxy-2,3,4,6,-tetra-O-benzoyl-D-gluco-pyranose with Substituted Phenylmagnesium Bromides

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