Alkyl Radical Generation from Alkylboronic Pinacol Esters through Substitution with Aminyl Radicals

Alkylboronic pinacol esters (APEs) are highly versatile reagents in organic synthesis. However, the direct generation of alkyl radicals from commonly used, bench-stable APEs has not been well explored. In this communication, alkyl radical generation from APEs through reaction with aminyl radicals is reported. The aminyl radicals are readily generated by visible-light-induced homolytic cleavage of the N-N bond in N-nitrosamines, and C radical generation occurs through nucleohomolytic substitution at boron. As an application, the highly efficient photochemical radical alkyloximation of alkenes with APEs and N-nitrosamines under mild conditions is presented. A wide range of primary, secondary, and tertiary APEs engage in this transformation that is easily scaled up.