Photocatalytic Germylation via Direct Hydrogen Atom Transfer
Wenshan Wang, Yan Liu, Gonghong Qiu, Igor B. Krylov, Alexander O. Terent’ev, Shuxia Cao, Kai Sun, Xiaolan Chen, Lingbo Qu, Bing Yu
Abstract
Comprehensive Summary An innovative visible‐light‐driven direct hydrogen atom transfer ( d ‐HAT) of Ge–H bond has been developed, wherein the photoexcited 9,10‐phenanthraquinone ( PC HAT 9 ) serves as an efficient photocatalyst for the generation of germanium‐centered radicals from germanium hydrides including Ph 3 GeH, n Bu 3 GeH, and Ph 2 GeH 2 . By employing hypervalent iodine reagents as SOMOphiles, this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed by β‐cleavage of a carboxyl radical to yield a diverse array of ethynyl‐, vinyl‐, nitrile‐, and phenyl‐functionalized germanes. The methodological leap signifies a noteworthy departure from the previous photocatalytic indirect hydrogen atom transfer ( i ‐HAT) relying on combined usage of PC SET with abstractors, which not only advances the methodology for creating germanium radicals in a photocatalytic fashion but also provides access to structurally novel and pharmaceutically promising organogermanium compounds that are difficult to synthesize by routine methods.