Schoetz Markus D, Deckers Kristina, Singh Gurdeep, Ahrweiler Eric, Hoeppner Annika, Schoenebeck Franziska
Institute of Organic Chemistry, RWTH Aachen University, 52074 Aachen, Germany.
J Am Chem Soc. 2024 Aug 7;146(31):21257-21263. doi: 10.1021/jacs.4c08008. Epub 2024 Jul 26.
Because of their robustness and orthogonal reactivity features, alkyl germanes bear significant potential as functional handles for the construction of C(sp)-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(sp)-heteroatom bond formation of alkyl germanes (-GeEt) by leveraging electrochemistry to unlock polar reactivity. This approach allowed us to couple C(sp)-GeEt 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 C motif was also showcased, involving the sequential functionalization of Cl, Bpin, and ultimately GeEt via electrochemistry.
由于其稳定性和正交反应性特征，烷基锗作为构建富含C(sp)骨架的功能基团具有巨大潜力，特别是在模块化合成方法的背景下。然而，迄今为止，这些功能基团仅能实现基于自由基的反应性，这限制了可能的修饰类型。在此，我们描述了通过利用电化学来开启极性反应性，首次实现烷基锗（-GeEt）的通用C(sp)-杂原子键形成。这种方法使我们能够将C(sp)-GeEt与多种亲核试剂偶联，构建醚、酯、胺、酰胺、磺酰胺、硫化物以及C-P、C-F和C-C键。还展示了电化学方法与C基序模块化合成策略的兼容性，包括通过电化学对Cl、Bpin以及最终的GeEt进行顺序官能化。
