Catalytic 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‐α,β‐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 CH 2 Cl 2 as a solvent affords trans‐α,β‐unsaturated amides ( 4 ) as the major product. Copyright © 2003 John Wiley & Sons, Ltd.