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硅亚乙基钛醇盐配合物的生成。一种用于不饱和化合物硅亚乙基化和硅亚乙基化的通用试剂。

Generation of a silylethylene-titanium alkoxide complex. A versatile reagent for silylethylation and silylethylidenation of unsaturated compounds.

作者信息

Mizojiri R, Urabe H, Sato F

机构信息

Department of Biomolecular Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8501, Japan.

出版信息

J Org Chem. 2000 Sep 22;65(19):6217-22. doi: 10.1021/jo000925x.

DOI:10.1021/jo000925x
PMID:10987963
Abstract

(Trimethylsilyl)ethylene-titanium alkoxide complex (1) was generated from trimethyl(vinyl)silane, Ti(O-i-Pr)(4), and i-PrMgCl as a preformed alkene-titanium complex and reacted with several unsaturated compounds such as aldehyde, imine, other vinylsilane, and acetylene to give the corresponding coupling products 4a-f, 6, 8, and 10a-d in a regioselective manner. Both of the two carbon-titanium bonds of the complex 1 reacted successively with esters to afford silylcyclopropanols 11a-j, 13, and 15, some synthetic applications of which were illustrated in the preparation of beta-silyl ketones 16 and cyclopropenes 17. Asymmetric addition of 1 to a chiral acyloxazolidinone 19 gave optically active cyclopropanol (+)-11a of 50% ee.

摘要

（三甲基硅基）乙烯 - 钛醇盐配合物（1）由三甲基（乙烯基）硅烷、Ti(O-i-Pr)₄和异丙基氯化镁反应生成，作为预先形成的烯烃 - 钛配合物，并与几种不饱和化合物如醛、亚胺、其他乙烯基硅烷和乙炔反应，以区域选择性方式得到相应的偶联产物4a - f、6、8和10a - d。配合物1的两个碳 - 钛键均先后与酯反应，得到硅基环丙醇11a - j、13和15，其中一些在制备β - 硅基酮16和环丙烯17中的合成应用得到了说明。1与手性酰基恶唑烷酮19的不对称加成得到了对映体过量为50%的光学活性环丙醇（+）-11a。

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