Pallada-Electrocatalysis Enables Distal Regioselective and Atroposelective Olefination Reactions

Abstract

Regioselective and enantioselective C-H functionalization is a valuable method for synthesizing chiral and complex molecules. However, it often requires large amounts of toxic oxidants and high temperature, making it environmentally and economically adverse. Additionally, these traditional approaches generally suffer from regioselectivity and enantioselectivity issues. To overcome these limitations, a new mechanism is needed to control both of these simultaneously. Herein, we report the first Pd catalyzed regioselective distal and atroposelective olefination of simple arenes/biaryls via an electrooxidative reaction pathway. This unique electro-oxidative strategy with Pd(II) catalysis demonstrates unprecedented access to ‘regio-resolved’ reactions, furnishing chiral molecule synthesis under dynamic kinetic resolution without the conventional requirement of metal-based oxidants and thermal energy. Both electroanalytical studies and DFT calculations suggest the involvement of a Pd(II)/Pd(IV) catalytic cycle via a crucial Pd(III) intermediate that initiates both the distal and atroposelective olefination reactions.