Ruthenium(II)‐Catalyzed C−H Difluoromethylation of Ketoximes: Tuning the Regioselectivity from the <i>meta</i> to the <i>para</i> Position

Abstract

A highly para-selective C_Ar -H difluoromethylation of ketoxime ethers under ruthenium catalysis has been developed. A wide variety of ketoxime ethers are compatible with the reaction, which leads to the corresponding para-difluoromethylated products in moderate to good yield. A mechanistic study clearly showed that chelation-assisted cycloruthenation is the key factor in the para selectivity of the difluoromethylation of ketoxime ethers. Density functional theory was used to gain a theoretical understanding of the para selectivity.