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-sp(3) carbon carrying Cl, Bpin and GeEt3 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)-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-sp(3)-[Ge] bond.