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 Csp3 carbon carrying Cl, Bpin and GeEt3 for the modular and programmable construction of sp3‐rich molecules. Various functionalizations of Csp3−Cl and Csp3−BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by the Csp3−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 Csp3‐[Ge] bond. [ABSTRACT FROM AUTHOR]