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Deammoniative Condensation of Primary Allylic Amines with Nonallylic Amines
Author(s) -
Wang Yong,
Li Manbo,
Ma Xiantao,
Liu Congrong,
Gu Yonghong,
Tian ShiKai
Publication year - 2014
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201400406
Subject(s) - chemistry , allylic rearrangement , stereospecificity , medicinal chemistry , primary (astronomy) , regioselectivity , amination , organic chemistry , condensation , condensation reaction , catalysis , physics , astronomy , thermodynamics
An unprecedented deammoniative condensation reaction of primary allylic amines with nonallylic amines has been developed through CN 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.