Photoredox-Catalyzed Strain-Release-Driven Aminopyridylation of Bicyclo[1.1.0]butanes with N -Aminopyridinium Ylides

An unprecedented visible-light-induced strain-release-driven aminopyridylation of bicyclo[1.1.0]butanes with bench-stable and easily accessible N -aminopyridinium ylides was developed. The photoredox-catalyzed transformation proceeds through amidyl-radical-mediated scission of the central C–C bond of bicyclo[1.1.0]butanes followed by intramolecular annulation and homolytic N–N bond cleavage. This cascade reaction delivers biologically and pharmaceutically prominent pyridine-containing polysubstituted cyclobutanecarboxamides in a regio- and diastereoseletive manner. The cyclobutanecarboxamides have a high fraction of sp 3 -hybridized carbon atoms. This reaction features mild metal-free conditions, excellent functional group compatibility, high atom economy, and potential for downstream late-stage functionalization.