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

Abstract

Solar-driven CO2 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 CO2 reduction to syngas, paired with direct alkylation/arylation of unactivated allylic sp3 C-H bonds for accessing allylic C-C products, over SiO2 -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/H2 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.