aculeximycin 的合成研究：通过 Kobayashi 羟醛缩合和环氧化物重排合成 C24-C40 片段。

Synthetic studies on aculeximycin: synthesis of C24-C40 segment by Kobayashi aldolization and epoxide rearrangements.

机构信息

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan.

出版信息

Org Lett. 2015 May 1;17(9):2274-7. doi: 10.1021/acs.orglett.5b00965. Epub 2015 Apr 23.

DOI:10.1021/acs.orglett.5b00965

PMID:25905567

Abstract

Stereoselective synthesis of the C24-C40 segment of aculeximycin has been achieved by using the Kobayashi aldol reactions and epoxy-opening rearrangement reactions. The C33-C40 segment was synthesized by the Kobayashi aldol reaction followed by epoxidation and Jung rearrangement of epoxide 9, while the C25-C32 segment was constructed by the Kobayashi aldol reaction followed by epoxidation and the epoxy-opening rearrangement reaction of epoxide 13. These segments were connected by the aldol reaction and the sequential dehydration, reduction, and conversion of ethyl ester to ethyl ketone to give the C24-C40 segment 1. All stereogenic centers were constructed by substrate-controlled stereoselective reactions.

摘要

通过使用小林缩合反应和环氧开环重排反应，实现了阿克拉霉素 C24-C40 片段的立体选择性合成。C33-C40 片段通过小林缩合反应、环氧化和环氧 9 的荣格重排反应合成，而 C25-C32 片段则通过小林缩合反应、环氧化和环氧 13 的环氧开环重排反应构建。这些片段通过羟醛缩合反应以及乙酯的顺序脱水、还原和转化为乙基酮连接，得到 C24-C40 片段 1。所有的立体中心都是通过底物控制的立体选择性反应构建的。