Synergistic Photocatalysis and Hydrogen Atom Transfer Strategy for Acylgermylation of Alkenes

Construction of functionalized molecules is a long-standing interest, yet controlling the reactivity and selectivity among more than two molecules remains challenging. We report a combined photocatalysis and hydrogen atom transfer method for acylgermylation of alkenes using readily available germanium hydrides and acyl azoliums as starting materials. Mechanistic experiments and density functional theory (DFT) calculations support a radical relay mechanism, involving the generation of germyl and ketyl radicals and the sequential selective coupling of two radicals with an alkene. This protocol features mild reaction conditions, is transition-metal-free, and offers a broad substrate scope. Late-stage functionalization of complex bioactive molecules underscores the potential of this protocol in drug discovery.