Caging the Chlorine Radical: Chemoselective Photocatalytic C(sp³)-H Functionalization Enabled by Terminal Cu-Cl Sites in a Metal-Organic Framework.

ABSTRACT: Hydrogen atom transfer (HAT) mediated by halogen radicals represents a powerful approach for the functionalization of inert C(sp³)-H bonds. Chlorine radical (Cl^•), for example, is capable of generating carbon-centered radicals by abstracting strong C-H bonds (H-Cl bond dissociation energy = 103 kcal/mol). However, the chemoselectivity of these transformations typically suffers due to the high reactivity of Cl^•. Herein, we disclose a novel strategy employing a metal-organic framework (MOF) to tame Cl^• and effect the selective alkylation of C(sp³)-H bonds. Under light irradiation, MIT20-LiCl─an anionic Cu(II) MOF containing terminal Cu-Cl sites─undergoes ligand-to-metal charge transfer (LMCT) to generate a Cl^•-like species tha

SUBMITTER: Eaton MC 

PROVIDER: S-EPMC12768452 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature