Issue 18, 2022

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Feb 2022
Accepted
11 Apr 2022
First published
12 Apr 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 5382-5389

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

H. Liu, X. Kong, X. Gong, Y. Li, Z. Niu, X. Gou, X. Li, Y. Wang, W. Shi, Y. Huang, X. Liu and Y. Liang, Chem. Sci., 2022, 13, 5382 DOI: 10.1039/D2SC00764A

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