O-Directed C-H functionalization via cobaltacycles: a sustainable approach for C-C and C-heteroatom bond formations

This review focuses on providing comprehensive highlights of the recent advances in the field of cobalt-catalysed C-H functionalization and related synthetic concepts, relying on these through oxygen atom coordination. In recent years, 3d transition metal (Fe, Co, Cu & Ni) catalysed C-H functionalization reactions have received immense attention on account of its higher abundance and low cost, as compared to noble metals such as Ir, Rh, Ru and Pd. Among the first-row transition metals, cobalt is one of the extensively used metals for sustainable synthesis due to its unique reactivity towards the functionalization of inert C-H bonds. The functionalization of the inert C-H bond necessitates a proximal directing group. In this context, strongly coordinating nitrogen atom directed C-H functionalizations have been well explored. Nevertheless, strongly coordinating nitrogen-containing scaffolds, such as pyridine, pyrimidine, and 8-aminoquinoline, have to be installed and removed in a separate process. In contrast, C-H functionalizations through weakly coordinating atoms, such as oxygen, are largely underdeveloped. Since the oxygen atom is a part of many readily available functional groups, such as aldehydes, ketones, carboxylic acids, and esters, it could be used as directing groups for selective C-H functionalization reactions without any modification. Thus, the use of 3d transition metals, such as cobalt, along with weakly coordinating (oxygen) directing groups for C-H functionalization reactions are more sustainable, especially for the large-scale production of pharmaceuticals in industries. During the last decade, notable progress has been made using this concept. Nonetheless, almost all the reports are restricted to the formation of C-C and C-N bond. Therefore, there is a wide scope for developing this area for the formation of other bonds, such as C-X (halogens), C-B, C-S, and C-Se.

Automated summary

This review highlights recent advances in cobalt-catalysed C-H functionalization, emphasizing the use of oxygen atom coordination for sustainable synthesis. While nitrogen-directed functionalizations are well explored, the use of oxygen as a weakly coordinating atom for C-H activation remains largely underdeveloped. The application of cobalt and weakly coordinating directing groups, such as oxygen, shows promise for selective C-H functionalization reactions in the pharmaceutical industry, with potential for further development beyond C-C and C-N bond formation.