Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β‐Acetoxy Elimination

Abstract

Palladium-catalyzed remote arylative substitution was achieved for the reaction of arylboronic acids with alkenes possessing a distant acetoxy group to provide arylation products having an alkene moiety at the remote position. The use of b-acetoxy elimination as a key step in the catalytic cycle allowed for regioselective formation of unstabilized alkenes after chain walking. This reaction was applicable to various arylboronic acids as well as alkene substrates.

Radical Addition-Triggered Remote Migratory Isomerization of Unactivated Alkenes to Difluoromethylene-Containing Alkenes Enabled by Bimetallic Catalysis

“…9 In addition, when we prepared this paper, Cochi and co-workers reported a Pdcatalyzed redox relay remote Heck type arylative substitution of alkenes via β-acetoxy elimination. 10 Compared to tremendous progress on conventional chain-walking progress triggered by ionic insertion of M−R species into CC bond, an alternative and fascinating alkene isomerization approach engendered by radical addition to CC bond remains an almost unexploited realm. In this domain, only Shenvi and Norton have independently reported CoH-catalyzed radical isomerization of olefins, and Schoenebeck elegantly demonstrated a reductant-free metalloradical (Ni I )-induced 1,3-H atom relocation to yield E-olefins in 2019 (Scheme 1C).…”