Multiple Halogenation of Aliphatic C-H Bonds within the Hofmann- Löffler Manifold

Abstract

An innovative approach to position-selective polyhalogenation of aliphatic hydrocarbon bonds is presented. The reaction proceeds within the Hofmann-Löffler manifold with amidyl radicals as the sole mediators to induce selective 1,5- and 1,6- hydrogen atom transfer followed by halogenation. Multiple halogenation events of up to four innate C-H bond functionalizations have been accomplished. The broad applicability of this new entry into polyhalogenation and the resulting synthetic possibilities are demonstrated for a total of 27 different examples including mixed halogenations.