Recent advances in manganese-catalyzed sp³ C-H functionalization

Manganese, the 12^th most abundant element in Earth's crust, offers unprecedented opportunities to produce valuable products from simple hydrocarbon scaffolds via C-H bond transformations. Owing to its rich redox chemistry, low toxicity, and natural abundance, manganese has emerged as a versatile tool for derivatizing sp³ C-H bonds, particularly unactivated ones. Its outstanding tunability and ability to generate high-valent, redox-active intermediates have enabled direct modification and activation of a remote sp³ C-H bond. Decades of studies show that manganese has been used to convert unactivated sp³ C-H bonds into vital C-Z bonds. These protocols demonstrate that manganese, combined with selective oxidants and additives, provides powerful synthetic utility for the functionalization of distant, unactivated sp³ C-H bonds into desired C-Z bonds. This review offers a thorough summary of current developments and limitations in manganese-catalyzed functionalization of unactivated sp³ C-H bonds, reported in the past seven years (2020-2026).