S-α-硅基苄基硫酯的1,4-硅迁移：通过硫代羰基叶立德形成碳-碳键并生成硅基烯醇醚和二烯醇醚的便捷途径。

1,4-silatropy of S-alpha-silylbenzyl thioesters: a convenient route to silyl enol and dienol ethers accompanied by C-C bond formation via thiocarbonyl ylides.

作者信息

Choi Jinil, Imai Eiichiro, Mihara Masatoshi, Oderaotoshi Yoji, Minakata Satoshi, Komatsu Mitsuo

机构信息

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871, Japan.

出版信息

J Org Chem. 2003 Aug 8;68(16):6164-71. doi: 10.1021/jo026211z.

DOI:10.1021/jo026211z

PMID:12895046

Abstract

A novel convenient method for the generation of thiocarbonyl ylides from readily accessible starting materials and the first synthetic application of in situ generated ylides in the synthesis of silyl enol and dienol ethers, accompanied by C-C bond formation, is described. Under completely neutral conditions without any catalyst or additive, thermal reactions of S-alpha-silylbenzyl thioesters in sealed tubes at 180 degrees C provided silyl enol and dienol ethers in good to excellent yields with high stereoselectivities. This procedure consists of a multistep reaction in a one-pot process, i.e., 1,4-silatropy of S-alpha-silylbenzyl thioesters to give thiocarbonyl ylides, 1,3-electrocyclization of the ylides to give thiiranes, and the extrusion of sulfur from thiiranes to give silyl enol and dienol ethers.

摘要

本文描述了一种从易于获得的起始原料生成硫代羰基叶立德的新颖简便方法，以及原位生成的叶立德在硅烯醇醚和二烯醇醚合成中的首次合成应用，该过程伴随着碳 - 碳键的形成。在完全中性条件下，无需任何催化剂或添加剂，密封管中S-α-硅基苄基硫酯在180℃下的热反应能以良好至优异的产率和高立体选择性提供硅烯醇醚和二烯醇醚。该过程由一锅法中的多步反应组成，即S-α-硅基苄基硫酯的1,4-硅迁移生成硫代羰基叶立德，叶立德的1,3-电环化生成硫杂环丙烷，以及硫杂环丙烷中硫的挤出以生成硅烯醇醚和二烯醇醚。