DMF as a source of oxygen and aminomethine: stereoselective 1,2-insertion of rhodium(II) azavinyl carbenes into the C═O bond of formamides for the synthesis of cis-diamino enones.

A new catalytic reaction in which all the atoms of a formamide are incorporated into the product through a formal stereoselective 1,2-insertion of rhodium(II) azavinyl carbenes, generated in situ from readily available N-sulfonylated 1,2,3-triazoles, into the C═O bond of DMF and other N,N-disubstituted formamides to afford cis-diamino enones is described.