Catalytic hydrofunctionalizations of alkenes via hydrogen atom transfer with 3d transition metal complexes (MHAT): A pragmatic approach to recent contributions

The growing interest in sustainable organic synthesis has led to exploring catalytic systems based on first-row transition metals, revealing their exceptional capacity to promote hydrogen atom transfer (MHAT) processes for alkene activation. Due to the high chemoselectivity and chemofidelity of the MHAT reaction, diverse catalytic hydrofunctionalizations have been successfully achieved, directly contributing to the formation of a wide variety of valuable carbon-based bonds (C−C, C−N, C−O, and C−S, among others), even in complex environments and at sterically demanding positions. Herein, we provide a practical overview of the field by examining the main reactivity trends and strategies used to achieve efficient MHAT-driven hydrofunctionalizations while also demonstrating the current versatility and synthetic utility of these methodologies. ● Tendencies in transition metals, ligands, and hydrogen sources are discussed. ● Concise descriptions of the different proposed mechanisms and their implications in reactivity are given. ● A practical overview of the broad substrate scope is presented, outlining the versatility of the MHAT-driven hydrofunctionalizations and their relevance in organic synthesis.