A new chiral bidentate N-heterocyclic carbene (NHC) ligand has been designed and synthesized. Tie NHC ligand bears a chiral diamine backbone and an achiral biphenol group; upon metal complexation (derived from Ag(I), Ru(II), or Cu(II)), the cliamine moiety induces > 98% diastereoselectivity such that the biaryl unit coordinates to the metal center to afford the desired complex as a single atropisomer. Because the ligand does not require optically pure biaryl amino alcohols, its synthesis is significantly shorter and simpler than the related first generation ligands bearing a chiral binaphthyl-based amino alcohol. The chiral NHC ligand can be used in the preparation of highly effective Ru- and Cu-based complexes (prepared and used in situ from the Ag(I) carbene) that promote enantioselective olefin metathesis and allylic alkylations with scope that is improved from previously reported protocols. In many cases, transformations promoted by the chiral NHC-based complexes proceed with higher enantioselectivity and reactivity than was observed with previously reported complexes.