Synthesis of Inherently Chiral Germepins via Rh-Catalyzed Enantioselective C–H Germylation

A rhodium-catalyzed enantioselective C–H germylation reaction was developed, enabling the synthesis of germepin derivatives with diverse substitutions. This study represents a rare application of E–H/C–H (E = Si or Ge) dehydrogenation coupling reactions in synthesizing inherently chiral molecules, marking the first successful enantioselective synthesis of inherently chiral seven-membered heterocycles containing group 14 elements. Compared to their structurally analogous tribenzosilepins, tribenzogermepins exhibit enhanced stereochemical stability under the reaction conditions. Furthermore, the compatibility of the Si–H bond under identical conditions highlights the distinct reactivity of Si–H and Ge–H bonds.