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.