碳苷研究(Ⅳ)——1-α-氯代,1-α-溴代,1-α-碘代,1-α-对-甲苯磺酰氧基-2,3,4,6-四-O-苯甲酰基-D-吡喃葡萄糖与取代芳基溴化镁的反应

高等学校化学学报 ›› 1988, Vol. 9 ›› Issue (5): 450.

碳苷研究(Ⅳ)——1-α-氯代,1-α-溴代,1-α-碘代,1-α-对-甲苯磺酰氧基-2,3,4,6-四-O-苯甲酰基-D-吡喃葡萄糖与取代芳基溴化镁的反应

蔡孟深, 董领娇, 高亦工

北京医科大学药学院

收稿日期:1986-11-10 出版日期:1988-05-24 发布日期:1988-05-24
通讯作者: 蔡孟深
基金资助:
中国科学院科学基金

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

Cai Mengshen, Dong Lingjiao, Gao Yigong

School of Pharmacy, Beijing Medical University, Beijing

Received:1986-11-10 Online:1988-05-24 Published:1988-05-24

摘要/Abstract

摘要： C₁位不同离去基团的卤代酰化糖(包括C₁-OTs)与芳基溴化镁在乙醚或THF中反应生成碳苷。不同离去基团的活性,影响端基异构体生成的比例,活性大者,易生成α体;格氏试剂亲核性大者,易生成β体;位阻大者,易生成α体,并通过¹HNMR计算出碳苷混合物中端基异构体的相对比例。

关键词: 碳苷, 格氏试剂, 离去基, 端基异构体

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

TrendMD:

蔡孟深, 董领娇, 高亦工. 碳苷研究(Ⅳ)——1-α-氯代,1-α-溴代,1-α-碘代,1-α-对-甲苯磺酰氧基-2,3,4,6-四-O-苯甲酰基-D-吡喃葡萄糖与取代芳基溴化镁的反应. 高等学校化学学报, 1988, 9(5): 450.

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. Chem. J. Chinese Universities, 1988, 9(5): 450.

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