Catalytic and regioselective synthesis of gem- or trans-alpha,beta-unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II)and phosphine

摘要

The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfully achieved by a catalytic system formed of Pd(OAc)_2 and a suitable bidentate phosphine ligand.The reaction led mainly to gem-alpha,beta-unsaturated amides(3)with Pd(OAs)_2/1,3-bis(diphenylphosphino)propane/p-tluenesulfonic acid/CO as the catalytic system.However,the reaction catalyzed by Pd(OAs)/1,4-bis(diphenylphosphino)butane/H_2/CO in CH_2Cl_2 as a solvent affords trans-alpha,beta-unsaturated amides(4)as the major product.