Intra- and intermolecular amidation of C-C unsaturated bonds through palladium-catalyzed reactions of carbamoyl derivatives.

Toward concise access to functionalized amides and lactams, palladium-catalyzed amidations of alkynes and alkenes with formamide derivatives were developed. Cyanoformamides having an alkynyl group were found to undergo intermolecular cyanoamidation in the presence of palladium catalyst to afford alpha-alkylidene lactams. Whereas, when cyanoformamides that possess a 1,1-disubstituted alkenyl group were used as starting materials, alpha,alpha-disubstituted lactams were obtained. The latter reaction was extended to enantioselective transformation by utilizing optically active phosphoramidites as ligand. Furthermore, chloroformamides having a 1,1,2-trisubsituted alkenyl group were found to give alpha-vinyl-lactams in the presence of palladium catalyst, base and silver salt. Additionally, formal intermolecular hydroamidation of alkenes was performed through one-pot hydroboration-carbamoylation sequence. 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.