Radical-Mediated Functionalization of Internal Alkenes: Synthesis of Multisubstituted Allylic and Homoallylic Azides.

Abstract

Radical-mediated functionalization of alkenes provides a powerful tool for transformation of simple alkenes into numerous value-added products. The precedent radical functionalization of alkenes is mainly restricted to terminal alkenes, while the conversion of internal alkenes generally remains challenging, as the increased steric congestion on alkenes significantly conflicts with the intermolecular addition of radicals. Herein, we describe an efficient photoredox catalytic functionalization of internal trisubstituted alkenes, leading to a plethora of valuable multifunctionalized allylic and homoallylic azides, which are otherwise difficult to obtain. The azide products serve as versatile feedstock for construction of useful heterocycles. Allylic or homoallylic azides are selectively generated in the transformation, regulated by the regioselective deprotonation process. This method also features mild reaction conditions and high product diversity.