Nickel-Catalyzed, para-Selective, Radical-Based Alkylation of Aromatic Ketones

Org Lett. 2020 Feb 7;22(3):854-857. doi: 10.1021/acs.orglett.9b04327. Epub 2020 Jan 10.

Abstract

A direct, para-selective, radical-based alkylation of aromatic ketones with alkanes has been developed using a nickel catalyst with oxamide as the ligand. Acetophenones bearing electron-withdrawing substituents were functionalized directly with simple alkanes with high para-selectivity while acetophenones with electron-donating groups were mainly para-functionalized. A mechanistic study indicated that C-H bond activation of the aromatic ring may be the rate-determining step of the reaction.