多元醇亚锡烯的分子间迁移作为一种反应，对取代的区域选择性有贡献。

The intermolecular migration of polyol stannylenes as a reaction contributing to the regioselectivity of substitution.

作者信息

David S, Malleron A

机构信息

Institute de Chimie Moléculaire, Universite de Paris-Sud, Orsay, France.

出版信息

Carbohydr Res. 2000 Oct 20;329(1):215-8. doi: 10.1016/s0008-6215(00)00147-6.

DOI:10.1016/s0008-6215(00)00147-6

PMID:11086702

Abstract

Pairs of the partially protected glycosides benzyl 4,6-O-benzylidene-beta-D-galactopyranoside, benzyl 2,3-di-O-benzyl-beta-D-galactopyranoside, benzyl 2,6-di-O-benzyl-alpha-D-galactopyranoside, and benzyl 2,3-di-O-benzyl-alpha-D-glucopyranoside were treated with equimolar proportions of Bu2SnO in benzene in the conditions of stannylene formation, and the resulting mixture was benzoylated in situ with benzoyl chloride. Estimation of the product of benzoylation led to the following order of reactivity in the stannylenation reaction: 2,3-diol > 4,6-diol, and 2,3-diol > 3,4-diol. An intermolecular migration of dibutyltin between sugars was demonstrated. It is considered that these migrations contribute efficiently to the regiospecificity of the stannylene reaction.

摘要

将等摩尔比例的二丁基氧化锡与部分保护的糖苷对，即苄基4,6 - O - 亚苄基 - β - D - 吡喃半乳糖苷、苄基2,3 - 二 - O - 苄基 - β - D - 吡喃半乳糖苷、苄基2,6 - 二 - O - 苄基 - α - D - 吡喃半乳糖苷和苄基2,3 - 二 - O - 苄基 - α - D - 吡喃葡萄糖苷，在苯中于亚锡烯形成的条件下进行处理，然后用苯甲酰氯对所得混合物进行原位苯甲酰化。对苯甲酰化产物的评估得出亚锡烯化反应中如下的反应活性顺序：2,3 - 二醇＞4,6 - 二醇，且2,3 - 二醇＞3,4 - 二醇。证实了二丁基锡在糖之间的分子间迁移。据认为，这些迁移有效地促进了亚锡烯反应的区域特异性。