Site-selective coupling of remote C(sp³)-H/meta-C(sp²)-H bonds enabled by Ru/photoredox dual catalysis and mechanistic studies.

ABSTRACT: Construction of C(sp²)-C(sp³) bonds via regioselective coupling of C(sp²)-H/C(sp³)-H bonds is challenging due to the low reactivity and regioselectivity of C-H bonds. Here, a novel photoinduced Ru/photocatalyst-cocatalyzed regioselective cross-dehydrogenative coupling of dual remote C-H bonds, including inert γ-C(sp³)-H bonds in amides and meta-C(sp²)-H bonds in arenes, to construct meta-alkylated arenes has been accomplished. This metallaphotoredox-enabled site-selective coupling between remote inert C(sp³)-H bonds and meta-C(sp²)-H bonds is characterized by its unique site-selectivity, redox-neutral conditions, broad substrate scope and wide use of late-stage functionalization of bioactive molecules. Moreover, this reaction represents a novel case of regioselective cross-dehydrogenative coupling of unactivated alkanes and arenes via a new catalytic process and provides a new strategy for meta-functionalized arenes under mild reaction conditions. Density functional theory (DFT) calculations and control experiments explained the site-selectivity and the detailed mechanism of this reaction.

SUBMITTER: Liu HC 

PROVIDER: S-EPMC9093131 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature