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Formation of α‐Lithio Siloles from Silylated 1,4‐Dilithio‐1,3‐Butadienes: Mechanism and Applications
Author(s) -
Luo Qian,
Wang Chao,
Gu Li,
Zhang WenXiong,
Xi Zhenfeng
Publication year - 2010
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200900287
Subject(s) - silylation , isomerization , alkene , nucleophile , chemistry , lithium (medication) , molecule , mechanism (biology) , stereochemistry , nucleophilic substitution , medicinal chemistry , organic chemistry , catalysis , physics , quantum mechanics , medicine , endocrinology
Abstract A full account of a useful transformation from silylated 1,4‐dilithio‐1,3‐butadienes 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 structurally 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, 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.