Triply Selective & Sequential Diversification at Csp3: Expansion of Alkyl Germane Reactivity for C‐C & C‐Heteroatom Bond Formation

We report the triply selective and sequential diversification of a single C_sp³ carbon carrying Cl, Bpin and GeEt₃ for the modular and programmable construction of sp³‐rich molecules. Various functionalizations of C_sp³−Cl and C_sp³−BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by the C_sp³−GeEt₃ group. Moreover, the methodological repertoire of alkyl germane functionalization was significantly expanded beyond the hitherto known Giese addition and arylation to alkynylation, alkenylation, cyanation, halogenation, azidation, C−S bond formation as well as the first demonstration of stereo‐selective functionalization of a C_sp³‐[Ge] bond.