Efficient and Direct Functionalization of Allylic sp3 C−H Bonds with Concomitant CO2 Reduction

Abstract Solar‐driven CO 2 reduction integrated with C−C/C−X bond‐forming organic synthesis represents a substantially untapped opportunity to simultaneously tackle carbon neutrality and create an atom‐/redox‐economical chemical synthesis. Herein, we demonstrate the first cooperative photoredox catalysis of efficient and tunable CO 2 reduction to syngas, paired with direct alkylation/arylation of unactivated allylic sp 3 C−H bonds for accessing allylic C−C products, over SiO 2 ‐supported single Ni atoms‐decorated CdS quantum dots (QDs). Our protocol not only bypasses additional oxidant/reductant and pre‐functionalization of organic substrates, affording a broad of allylic C−C products with moderate to excellent yields, but also produces syngas with tunable CO/H 2 ratios (1 : 2–5 : 1). Such win‐win coupling catalysis highlights the high atom‐, step‐ and redox‐economy, and good durability, illuminating the tantalizing possibility of a renewable sunlight‐driven chemical feedstocks manufacturing industry.