Computational study on palladium-catalyzed alkenylation of remote δ-C(sp 3 )-H bonds with alkynes: a new understanding of mechanistic insight and origins of site-selectivity.

Palladium-catalyzed alkenylation of δ-C(sp 3 )-H bonds with alkynes was conducted by density functional theory calculations. The present study shows that the dimeric Pd 2 (OAc) 4 mechanism reproduces experimental observations well, including regioselectivity and provides a deep mechanistic insight complementing the monomeric Pd(OAc) 2 mechanism recently reported by Chen's group. In addition, the economical heterodimeric Ni-Pd(OAc) 4 was predicted to be a potential species for such alkenylation of δ-C(sp 3 )-H bonds.