%0 Journal Article
%T Rhodium-Catalyzed Cycloisomerization of 1,6-Enynes with an Intramolecular Halogen Shift<br>铑催化的1,6-烯炔环异构化反应研究（英文）
%A TONG Xiao-Feng
%A ZHANG Zhao-Guo
%A ZHANG Xu-Mu
%A <br>童晓峰
%A 张兆国
%A 张绪穆
%J 中国科学院研究生院学报
%D 2006
%I 
%X A Rhodium (Ⅰ)-species catalyzed cycloisomerization reaction of a wide spectrum of 1,6- enynes with an unusual intramolecular halogen shift was investigated. This Rh-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined α-halomethylene-γ-butyrolactones,lactams, tetrahydrofurans, pyrrolidines and cyclopentanes. Coordinatively unsaturated rhodium species ( Rh(COD)Cl]2 + dppb + AgSbF6 ) only catalyzes the reaction with enyne substrates bearing a Z-form double bond. Neutral rhodium species (RhCl(PPh3)3 ) can catalyze enyne substrates bearing a Z- or E-form double bond to form the desired products and has a wider substrate scope. The mechanism of the reaction was studied by the employment of control experiments with different enyne isomers and a π-allyl rhodium intermediate was suggested to explain the formation of the cyclic products with an intramolecular halogen shift. Further transformation of the halo-alkenyl species can be readily achieved through metalcatalyzed Suzuki cross-coupling reactions.
%K Rhodium-catalyzed
%K cycloisomerization of 1
%K 6-enynes
%K intramolecular halogen shift<br>铑催化
%K 1
%K 6-烯炔环异构化
%K 分子内卤素迁移
%U http://www.alljournals.cn/get_abstract_url.aspx?pcid=B5EDD921F3D863E289B22F36E70174A7007B5F5E43D63598017D41BB67247657&cid=B47B31F6349F979B&jid=67CDFDECD959936E166E0F72DE972847&aid=B1B002ECCD4B0811&yid=37904DC365DD7266&vid=EA389574707BDED3&iid=38B194292C032A66&sid=1FF3CD54EFC256A1&eid=BA48F0B914ED890A&journal_id=1002-1175&journal_name=中国科学院研究生院学报&referenced_num=0&reference_num=17