研究室工作进展 May 1, 2010
研究室工作进展 May 1, 2010
Formation of α-Lithio Siloles from Silylated 1,4-Dilithio-1,3-butadienes: Mechanism and Applications
Qian Luo, Chao Wang, Li Gu, Wen-Xiong Zhang and Zhenfeng Xi*
Chem. Asian. J. 2010, 5, 1120-1128.
Dedicated to the 100th anniversary of College of Chemistry, Peking University
（庆祝北京大学化学学科创立100周年专集）
A full account about a useful transformation from silylated 1,4-dilithio-1,3-butadienes (Organo-di-Lithio reagents) to α-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 structural complex molecules such as bridged bis-silole compounds have been synthesized easily and successfully by applying our protocol. The structure of the α-lithio silole was confirmed by X-ray analysis, which adopts a dimeric fashion through two lithium bridges. Furthermore, a possible mechanism of skeleton rearrangements via E/Z isomerization of 1-silyl-1-lithio alkene and nucleophlic attack on silicon is proposed and also proved by experimental investigations.
本文报道了从α-硅基取代的1,4-二锂-1,3-丁二烯（双锂试剂）制备α-锂代硅杂环戊二烯衍生物的新方法。此方法条件温和、简单实用，具有良好的官能团兼容性，不仅能高效地制备各种取代基不同的硅杂环戊二烯，更能方便地获得桥联双硅杂环戊二烯衍生物。作者还通过实验详细研究了该反应机理。结果表明，此反应经历了1-锂-1-硅基-碳碳双键的构型翻转、另一烯基碳锂键对硅的亲核进攻、以及C-Si键的形成和切断等关键步骤。
Related publications from this group:
1. Synthesis of Functionalized Siloles from Si-tethered Diynes
Qian Luo, Li Gu, Chao Wang, Junhui Liu, Wenxiong Zhang and Zhenfeng Xi*
Tetrahedron Lett. 2009, 50, 3213-3215.（创刊五十周年邀请论文）
2. Lithio Siloles: Facile Synthesis and Applications
Chao Wang, Qian Luo, Hui Sun, Xiangyu Guo, and Zhenfeng Xi,*
J. Am. Chem. Soc. 2007, 129, 3094-3095.