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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (16): 1733-1735. 上一篇    下一篇

研究简报

二价钌催化的金属卡宾经由的硫叶立德[2,3]-σ重排反应研究

肖卿, 王剑波*   

  1. (北京分子科学国家实验室 生物有机与分子工程教育部重点实验室 北京大学化学学院 北京 100871)
  • 投稿日期:2007-03-26 修回日期:2007-06-14 发布日期:2007-08-28
  • 通讯作者: 王剑波

Investigation on Ru(II)-Catalyzed Reaction of [2,3]-Sigmatropic Rearrangement of Sulfur Ylide Generated from Metal Carbene

XIAO Qing; WANG Jian-Bo*   

  1. (Beijing National Laboratory of Molecular Sciences (BNLMS), and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871)
  • Received:2007-03-26 Revised:2007-06-14 Published:2007-08-28
  • Contact: WANG Jian-Bo

PDF

881

被引次数

6

报道烯(炔)基硫醚与α-重氮羰基化合物, 在[RuCl2(p-cymene)]2催化下, 经由金属卡宾发生硫叶立德[2,3]-σ重排反应(Doyle-Kirmse反应). 在Ru(II)作用下, α-重氮羰基化合物与烯丙基硫醚的反应以较好收率生成相应的[2,3]-σ重排产物高烯丙基硫醚. 同样条件下与炔丙基硫醚的反应则生成[2,3]-σ重排产物联烯和呋喃衍生物, 后者是联烯进一步在Ru(II)作用下重排的产物.

关键词: 二价钌催化剂, α-重氮羰基化合物, 硫叶立德[2,3]-σ重排

The Doyle-Kirmse reaction, namely the [2,3]-sigmatropic rearrangement of sulfonium ylides generated from α-diazo carbonyl compounds and sulfides has been for the first time catalyzed by [RuCl2- (p-cymene)]2. The reaction with allyl sulfides afforded the corresponding [2,3]-sigmatropic rearrangement products in moderate to good yields. The reaction with propargyl sulfide gave a mixture of allenic sulfide and furan. The former is the [2,3]-sigmatropic rearrangement product, while the latter is derived from the further rearrangement of the allene product under Ru(II) catalysis.

Key words: ruthenium(II) catalyst, α-diazo carbonyl compound, [2,3]-sigmatropic rearrangement of sulfonium ylide