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

Abstract We report the triply selective and sequential diversification of a single C sp 3 carbon carrying Cl, Bpin and GeEt 3 for the modular and programmable construction of sp 3 ‐rich molecules. Various functionalizations of C sp 3 −Cl and C sp 3 −BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by the C sp 3 −GeEt 3 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 sp 3 ‐[Ge] bond.