一种通过氧化和环缩合反应来合成(±)-1-去氧野尻霉素和(±)-1-去氧阿卓糖的方法。

An oxidation and ring contraction approach to the synthesis of (+/-)-1-deoxynojirimycin and (+/-)-1-deoxyaltronojirimycin.

机构信息

Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK.

出版信息

Org Lett. 2010 Jan 1;12(1):136-9. doi: 10.1021/ol902533b.

PMID:19954199

Abstract

A reaction sequence involving the chemoselective olefinic oxidation of N(1)-benzyl-2,7-dihydro-1H-azepine with m-CPBA in the presence of HBF(4) and BnOH followed by ring contraction facilitates the stereoselective preparation of either of the epoxide diastereoisomers of (2RS,3SR)-N(1)-benzyl-2-chloromethyl-3-benzyloxy-4,5-epoxypiperidine by simple modification of the reaction conditions. Epoxide ring opening, functional group interconversion, and deprotection allow the synthesis of (+/-)-1-deoxynojirimycin and (+/-)-1-deoxyaltronojirimycin.

摘要

在 m-CPBA、HBF4 和 BnOH 的存在下，通过 N(1)-苄基-2,7-二氢-1H-氮杂卓的烯烃选择性氧化反应序列，随后进行环收缩，有利于通过简单改变反应条件来立体选择性地制备（2RS,3SR）-N(1)-苄基-2-氯甲基-3-苄氧基-4,5-环氧哌啶的任意一个环氧非对映异构体。通过开环、官能团转化和脱保护，可以合成（±）-1-去氧野尻霉素和（±）-1-去氧阿托洛尼辛。