Lewis-Acid-Promoted Visible-Light-Mediated C(sp3)-H Bond Functionalization of Arylvinylpyridines via Diradical Hydrogen Atom Transfer.

ABSTRACT

A visible-light-induced intramolecular diradical-mediated hydrogen atom transfer (DHAT) of primary, secondary, and tertiary C(sp3)-H bonds and subsequent cyclization is described. This transformation is enabled by triplet energy transfer upon Lewis acid coordination to alkyl-substituted arylvinylpyridines and gives access to a variety of benzocyclobutenes (>40 examples, 32-96% yield). Notably, tri- and tetrasubstituted olefins with tertiary C(sp3)-H bonds effectively delivered sterically hindered products with adjacent all-carbon quaternary centers. Mechanistic evidence and density functional theory (DFT) calculations suggest that Lewis acid coordination was crucial for the success by modulating the reactivity of the diradical intermediates to unlock a challenging carbon-to-carbon DHAT and subsequent cyclization with a rather low barrier, which allows the functionalization of benzylic C(sp3)-H bonds to construct otherwise inaccessible benzocyclobutenes.