Abstract
Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via open-shell reactivity. The introduction of new C(sp3)-coupling partners within this paradigm can provide entry to novel, medicinally-relevant chemical space. Alkenes are abundant, bench-stable and undergo facile C(sp3)-radical reactivity via metal-hydride hydrogen atom transfer (MHAT), yet metallaphotoredox methodologies invoking this strategy remain underdeveloped. Importantly, the merger of MHAT activation with metallaphotoredox catalysis could enable cross-coupling of olefins with feedstock radical partners only activated via photocatalysis, such as alcohols. Herein, we report the first C(sp3)–C(sp3) coupling of MHAT-activated alkenes with alcohols (i.e. deoxygenative hy-droalkylation) via triple co-catalysis. Through synergistic Ir photocatalysis, Mn MHAT and Ni radical sorting pathways, this branch-selective protocol pairs diverse olefins with methanol or primary alcohols, displays remarkable functional group tolerance, and enables the rapid construction of complex aliphatic frameworks.