Recent Advances in Radical Hydrofunctionalization of Alkenes and Dienes via Reductive Metal‐Hydride Hydrogen Atom Transfer (MHAT)

The metal‐hydride hydrogen atom transfer strategy (MHAT) has emerged as a robust approach for the radical hydrofunctionalization of alkenes, demonstrating exceptional functional group tolerance and chemoselectivity. Traditional methods for generating metal‐hydride (M‐H) species typically require oxidative conditions that depend on stoichiometric oxidants and hydride donors, posing challenges to sustainability and scalability. In contrast, the reductive MHAT strategy, which forms M‐H species through the transfer of a proton and an electron, offers a more concise and sustainable pathway for radical alkene hydrofunctionalization. This review provides a comprehensive summary of the key advances in reductive MHAT catalysis since 2019, highlighting recent innovations and discussing potential future directions for the field.