Highly Site-Selective Direct C-H Bond Functionalization of Unactivated Arenes with Propargyl α-Aryl-α-diazoacetates via Scandium Catalysis.

Abstract

Highly chemo- and regio-selective C-H bond functionalization of unactivated arenes with propargyl α-aryl-α-diazoacetates has been developed using scandium catalysis. A variety of unactivated, mildly deactivated, and electronically activated arenes have been functionalized using this protocol. The synergistic combination of scandium triflate as a catalyst and propargyl α-aryl-α-diazoacetate as a reagent played a pivotal role in the effective C-H bond functionalization of arenes without the assistance of any directing group or ligand. The practicality of the protocol has been demonstrated by the gram-scale synthesis of very useful α,α-diarylacetates including antispasmodic drug-adiphenine. Based on the experimental observations, labeling experiment, and density functional theory calculations, a plausible reaction mechanism has been outlined.