Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes

Because of their robustness and orthogonal reactivity features, alkyl germanes bear significant potential as functional handles for the construction of C(sp3)-rich scaffolds, especially in the context of modular synthetic approaches. However, to date, only radical-based reactivity has been accessible from these functional handles, which limits the types of possible decorations. Here, we describe the first general C(sp3)–heteroatom bond formation of alkyl germanes (−GeEt3) by leveraging electrochemistry to unlock polar reactivity. This approach allowed us to couple C(sp3)–GeEt3 with a variety of nucleophiles to construct ethers, esters, amines, amides, sulfonamides, sulfides, as well as C–P, C–F, and C–C bonds. The compatibility of the electrochemical approach with a modular synthetic strategy of a C1 motif was also showcased, involving the sequential functionalization of Cl, Bpin, and ultimately GeEt3 via electrochemistry.