Recent advances in applications of metal hydride hydrogen atom transfer for natural product synthesis

Metal hydride hydrogen atom transfer (MHAT) has emerged as a powerful strategy for alkene hydrofunctionalization, offering high levels of chemo-, regio-, and stereocontrol. In recent years, this reaction has provided new retrosynthetic disconnections in the total synthesis of natural products. Its intrinsic Markovnikov selectivity, broad steric and functional group tolerance, and ability to enable polarity inversion make MHAT particularly well suited for tackling synthetic challenges in complex molecular architectures. This review highlights recent total syntheses that employ MHAT-induced reactions as the key steps, with particular emphasis on reaction optimization and the mechanistic basis of chemo- and stereoselectivity. The advantages and limitations of MHAT relative to traditional hydrofunctionalization approaches are also discussed. Together, these advances underscore the versatility and impact of MHAT as a central platform in natural product synthesis.