Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, 202, Chengfu Rd, Beijing, 100871 P.R. China.
Chem Asian J. 2010 May 3;5(5):1120-8. doi: 10.1002/asia.200900287.
A full account of a useful transformation from silylated 1,4-dilithio-1,3-butadienes to alpha-lithio siloles is described. These lithio siloles formed by this procedure are general, in terms of substitution patterns and synthetic methods, affording diversified silole derivatives. Notably, some structurally complex molecules, such as bridged bis-silole compounds, have been synthesized easily and successfully by applying our protocol. The structure of the alpha-lithio silole, which adopts a dimeric fashion through two lithium bridges, was confirmed by X-ray analysis. Furthermore, a possible mechanism of the skeleton rearrangements via E/Z isomerization of 1-silyl-1-lithio alkene and nucleophilic attack on silicon is proposed, and is also proved by experimental investigations.
本文详细描述了一种将硅烷基化的 1,4-二锂-1,3-丁二烯转化为α-锂硅烷的有用方法。通过该方法形成的这些锂硅烷在取代模式和合成方法方面具有通用性，可提供各种硅烷衍生物。值得注意的是，通过应用我们的方案，一些结构复杂的分子，如桥联双硅烷化合物，已经被成功地合成出来。通过两个锂桥形成二聚体形式的α-锂硅烷的结构通过 X 射线分析得到了证实。此外，还提出了通过 1-硅基-1-锂烯的 E/Z 异构化和硅原子的亲核进攻来实现骨架重排的可能机制，并通过实验研究得到了证实。
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