Abstract
C—H bond functionalization catalyzed by high-valent-cobalt species with the aid of
bidentate chelation has come a long way since the pioneering report by Daugulis almost
a decade ago. Further study of the reaction mechanisms revealed that stoichiometric
amounts of metal salts could be replaced with photocatalysts or electricity as one-electron
oxidants, and approaches based on these strategies can be considered more environmentally
friendly than the initially developed catalytic systems. Systematic investigations
have led to a better understanding of the coordination environment of the in-situ-formed
cobaltacycle, and this has led to the development of external chiral ligands for cobalt-catalyzed
asymmetric C—H functionalizations. This review is a comprehensive summary of the documented
methods for cobalt-catalyzed, bidentate-chelation-assisted C—H bond functionalizations
as of early 2023.
