Enantioselective C-H bond functionalization under Co(III)-catalysis.

Abstract

While progress in enantioselective C-H functionalization has been accomplished by employing 4d and 5d transition metal-based catalysts, the rapid depletion of these metals in the earth's crust poses a serious threat to making these protocols sustainable. On the other hand, because of their unique reactivity, low toxicity, and high earth abundance, newer strategies utilizing affordable 3d transition metals have come to the forefront. Among the first-row transition metals, high-valent cobalt has recently attracted a lot of attention for catalytic C-H functionalization with mono and bidentate directing groups. This approach was extended for asymmetric catalysis due to a fairly thorough knowledge of its catalytic cycles. Four major themes have been investigated as a result of this insight: (1) rational design of a chiral Cp#Co(III)-catalyst, (2) chiral carboxylic acid with achiral Cp*Co(III)-catalysts using monodentate directing groups, (3) cobalt/salox-based systems, and (4) cobalt/chiral phosphoric acid-based hybrid systems with bidentate directing groups. Herein, we highlight the recent developments in high-valent cobalt-catalyzed enantioselective C-H functionalization up to October 2023, with the strong belief that the current state-of-the-art can attract considerable interest in the synthetic community, encouraging discoveries in the evolving landscape of asymmetric catalysis.