Catalytic Reductive Homocoupling of Benzyl Chlorides Enabled by Zirconocene and Photoredox Catalysis

The bibenzyl skeleton is prevalent in numerous natural products and other biologically active compounds. Radical homocoupling provides a straightforward approach for synthesizing bibenzyls in a single step with the reductive homocoupling of benzyl halides undergoing extensive development. Unlike benzyl bromides and other tailored precursors used in visible-light-mediated homocoupling, benzyl chlorides offer greater abundance and chemical stability. Nevertheless, achieving chemoselective cleavage of the C-Cl bond poses significant challenges, with only a limited number of studies reported to date. Herein, we demonstrate a catalytic reductive homocoupling of benzyl chlorides facilitated by zirconocene and photoredox catalysis. This cooperative catalytic system promotes C-Cl bond cleavage in benzyl chlorides under mild conditions and supports the homocoupling of a wide range of benzyl chlorides, including those derived from pharmaceutical agents. Our preliminary mechanistic investigations highlight the pivotal role of hydrosilane in the catalytic cycle.