Research News, May 1, 2010
研究室工作進展 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
（慶祝beat365化學學科創立100周年專集）
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.
本文報道了從α-矽基取代的1,4-二锂-1,3-丁二烯（雙锂試劑）制備α-锂代矽雜環戊二烯衍生物的新方法。此方法條件溫和、簡單實用，具有良好的官能團兼容性，不僅能高效地制備各種取代基不同的矽雜環戊二烯，更能方便地獲得橋聯雙矽雜環戊二烯衍生物。作者還通過實驗詳細研究了該反應機理。結果表明，此反應經曆了1-锂-1-矽基-碳碳雙鍵的構型翻轉、另一烯基碳锂鍵對矽的親核進攻、以及C-Si鍵的形成和切斷等關鍵步驟。
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.（創刊五十周年邀請論文）
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.