Catallytic and regioselective synthesis of gem- or trans-α,β-unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II) and phosphine

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(OAc)(2)/1,3-bis(diphenylphosphino)propane/p-toluenesulfonic acid/CO as the catalytic system. However, the reaction catalyzed by Pd(OAc)(2)/1,4-bis(diphenylphosphino)butane/H-2/CO in CH2Cl2 as a solvent affords trans-alpha,beta-unsaturated amides (4) as the major product. Copyright (C) 2003 John Wiley Sons, Ltd.