Nickel‐Catalyzed Reductive C−Ge Coupling of Aryl/Alkenyl Electrophiles with Chlorogermanes

Abstract

Cross‐electrophile coupling has emerged as a promising tool for molecular synthesis; however, current studies have focused mainly on forging C−C bonds. We report a cross‐electrophile C−Ge coupling reaction and thereby demonstrate the possibility of constructing organogermanes from carbon electrophiles and chlorogermanes. The reaction proceeds under mild conditions and offers access to both aryl and alkenyl germanes. Electron‐rich, electron‐poor, and ortho‐/meta‐/para‐substituted (hetero)aryl electrophiles, as well as cyclic and acyclic alkenyl electrophiles, were coupled. Gram‐scale reaction, incorporation of the ‐GeR3 moiety into complex biologically active molecules, and derivatization of formed organogermanes are demonstrated.

Enantio- and Regioconvergent Synthesis of γ-Stereogenic Vinyl Germanes and Their Use as Masked Vinyl Halides

“…This pertains not only to the preparation of germaniumcontaining molecules but also to their further use in organic synthesis. These fields were recently revived by the advances made by Schoenebeck, 4 Xiao, 5 and Shu 6 and a few contributions by us. 7 To the best of our knowledge, there has been little progress regarding the formation of chiral germanium-substituted building blocks.…”