Triply Selective & Sequential Diversification at C_sp³: Expansion of Alkyl Germane Reactivity for C−C & C−Heteroatom Bond Formation

Abstract

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.