Designed Bifunctional Phosphine Ligand-Enabled Gold-Catalyzed Isomerizations of Ynamides and Allenamides: Stereoselective and Regioselective Formation of 1-Amido-1,3-dienes

By using designed biphenyl-2-ylphosphines functionalized with a remote basic groups as ligands, N-alkynyl-o-nosylamides are directly converted to (1E,3E)-1-amido-1,3-dienes with excellent diastereoselectivities under gold catalysis. With allenamides as substrates, the gold-catalyzed isomerizations are high yielding and applicable to a broad substrate scope including various nitrogen protecting groups and exhibit unprecedented (3E)-selectivities for the distal C-C double bond and good regioselectivities. Combining this gold catalysis with one-pot Diels-Alder reactions leads to rapid assembly of valuable bicyclic compounds.