Ruthenium‐Catalyzed Remote Difunctionalization of Nonactivated Alkenes for Double meta‐C(sp²)−H/C‐6(sp³)−H Functionalization

Abstract

Twofold distal C−H functionalization was accomplished by difunctionalization of nonactivated alkenes to provide rapid access to multifunctionalized molecules. The multicomponent ruthenium‐catalyzed remote 1,n‐difunctionalization (n=6,7) of nonactivated alkenes with fluoroalkyl halides and heteroarenes in a modular manner is reported. The meta‐C(sp2)−H/C‐6(sp3)−H distal functionalization featured mild conditions, unique selectivity, and broad substrate scope with a domino process for twofold remote C(sp2)−H/C(sp3)−H activation of the sequential formation of three different carbon‐centered radicals. A plausible mechanism was proposed based on detailed experimental and computational studies.

Visible-Light-Mediated Bimetal-Catalyzed meta-Alkylation of Arenes

“…Although the meta -alkylation of arenes under Ru/photoredox dual catalysis has been demonstrated, the photoinduced Ru-catalyzed meta -fluoroalkylation of arenes has been unknown until now. The three-component Ru-catalyzed meta -alkylation of arenes has been investigated under thermal conditions and provides a new approach to the (fluoro)alkylarylation of alkenes (Scheme b) . Nevertheless, the visible-light-enabled counterpart remains unexplored.…”

Ruthenium-Catalyzed Difunctionalization of Vinyl Cyclopropanes for Double m-C(sp2)–H/C-5(sp3)–H Functionalization

“…The integration of radical addition onto alkenes, hydrogen atom transfer (HAT), and remote C–H functionalization has enabled site-selective remote olefin difunctionalizations, facilitating the assembly of structurally diverse scaffolds (Scheme b, eq 2). Moreover, Ackermann’s group has accomplished ruthenium-catalyzed remote 1,6-difunctionalization of three-component non-activated olefins through 1,5 HAT (Scheme b, eq 3). Despite undisputed progress, the development of a new strategy for achieving 1, n -difunctionalization ( n > 2) is still greatly important.…”