带有氨基的乙烯基硅烷的1,2-硅基迁移环化反应。

1,2-Silyl-migrative cyclization of vinylsilanes bearing an amino group.

作者信息

Miura Katsukiyo, Takahashi Tatsuyuki, Hondo Takeshi, Hosomi Akira

机构信息

Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.

出版信息

Chirality. 2003 Jan;15(1):41-52. doi: 10.1002/chir.10150.

DOI:10.1002/chir.10150

PMID:12467042

Abstract

In the presence of an acid catalyst, alpha-alkyl-substituted (Z)-vinylsilanes 1, bearing a tosylamino group, were smoothly cyclized to trans-2-alkyl-3-silylpiperidines 2 (1,2-silyl-migration products) and (2R*, 1'S*)-2-(1'-silylalkyl)pyrrolidines 3. The elaboration of the reaction conditions enabled the selective preparation of each cyclized product. The acid-catalyzed cyclization of (Z)-vinylsilane 5, whose methylene tether is shorter than that of 1 by one carbon, formed only the 1,2-silyl-migration product 6 with high trans-selectivity. These cyclizations were found to proceed in a stereospecific manner.

摘要

在酸催化剂存在下，带有对甲苯磺酰氨基的α-烷基取代的(Z)-乙烯基硅烷1顺利环化生成反式-2-烷基-3-硅基哌啶2（1,2-硅基迁移产物）和(2R*, 1'S*)-2-(1'-硅基烷基)吡咯烷3。反应条件的优化使得能够选择性地制备每种环化产物。亚甲基连接链比1短一个碳原子的(Z)-乙烯基硅烷5的酸催化环化仅以高反式选择性生成1,2-硅基迁移产物6。发现这些环化反应以立体专一的方式进行。