Deammoniative Condensation of Primary Allylic Amines with Nonallylic Amines  

作　　者：Yong Wang Manbo Li Xiantao Ma Congrong Liu Yonghong Gu Shi-Kai Tian 

机构地区：[1]Department of Chemistry,University of Science and Technology of China,Hefei,Anhui 230026,China [2]Department of Environmental Engineering,Nanjing Institute of Technology,Nanjing,Jiangsu 211167,China

出　　处：《Chinese Journal of Chemistry》2014年第8期741-751,共11页中国化学（英文版）

基　　金：We are grateful for the financial support from the National Natural Science Foundation of China(Nos.21232007,21202154 and 21172206);the National Key Basic Research Program of China(No.2014CB931800).

摘　　要：An unprecedented deammoniative condensation reaction of primary allylic amines with nonallylic amines has been developed through C-N bond cleavage.In the presence of 5 mol%palladium diacetate,10 mol%1,4-bis(diphenylphosphino)butane(dppb),and 5 mol%p-toluenesulfonic acid(TsOH),a range of α-unbranched primary allylic amines smoothly underwent deammoniative condensation with nonallylic amines in an α-selective fashion to give structurally diverse secondary and tertiary amines in good to excellent yields and E selectivity.Replacing dppb with racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl(BINAP)permitted the deammoniative condensation of enantioenriched α-chiral primary allylic amines with nonallylic amines to proceed with complete retention of configuration.Electrospray ionization(ESI)mass spectrometric analysis of the reaction mixture permitted the identification of some π-allylpalladium intermediates,and plausible mechanisms have been proposed to account for the regioselectivity and stereospecificity of the deammoniative condensation reaction.

关 键 词：AMINES deammoniation PALLADIUM SUBSTITUTION STEREOSPECIFICITY 

分 类 号：O62[理学—有机化学]