Facile Construction of Quaternary Carbon Centers via Dinuclear Titanium(III)‐Catalyzed Reductive Coupling of Tertiary Chlorides and Activated Olefins

Abstract The establishment of all‐carbon quaternary carbon centers represents a pivotal aspect in the synthesis of numerous natural products and pharmaceutical compounds, underscoring its paramount significance in synthetic organic chemistry. Herein, we present a novel synthetic strategy for the generation of quaternary carbon centers through the reductive coupling of tertiary halides, catalyzed by dinuclear (salen)titanium catalysts. This catalytic framework demonstrates notable reactivity towards tertiary chlorides while maintaining inertness towards secondary and primary chlorides, thereby facilitating exceptional chemoselectivity for C−C bond formation. The reaction proceeds with remarkable efficiency across a diverse range of substrates under mild reaction conditions.