Direct Aerobic Carbonylation of C(sp(2))-H and C(sp(3))-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source.

Journal of the American Chemical Society

PubMedID: 25815529

Wu X, Zhao Y, Ge H. Direct Aerobic Carbonylation of C(sp(2))-H and C(sp(3))-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source. J Am Chem Soc. 2015;.
The direct carbonylation of aromatic sp(2) and unactivated sp(3) C-H bonds of amides was achieved via nickel/copper catalysis under atmospheric O2 with the assistance of a bidentate directing group. The sp(2) C-H functionalization showed high regioselectivity and good functional group compatibility. The sp(3) C-H functionalization showed high site-selectivity by favoring the C-H bonds of a-methyl groups over those of the a-methylene, ß- or ?-methyl groups. Moreover, this reaction showed a predominant preference for functionalizing the a-methyl over a-phenyl group. Mechanistic studies revealed that nickel/copper synergistic catalysis is involved in this process.