Donets, Pavel A.Cramer, Nicolai2013-10-012013-10-012013-10-01201310.1021/ja406730thttps://infoscience.epfl.ch/handle/20.500.14299/95624WOS:000323241200024Chiral trivalent phosphorus species are the dominant class of ligands and the key controlling element in asymmetric homogeneous transition-metal catalysis. Here, novel chiral diaminophosphine oxide ligands are described. The arising catalyst system with nickel(0) and trimethylaluminum efficiently activates formamide C-H bonds under mild conditions providing pyrrolidones via intramolecular hydrocarbamoylation in a highly enantioselective manner with as little as 0.25% mol catalyst loading. Mechanistically, the secondary phosphine oxides behave as bridging ligands for the nickel center and the Lewis acidic organoaluminum center to give a heterobimetallic catalyst with superior reactivity.text::journal::journal article::research article