化学选择性
炔烃
电化学
组合化学
化学
循环伏安法
废止
催化作用
过渡金属
氧化还原
纳米技术
有机化学
材料科学
电极
物理化学
作者
M. GHOSH,Tirtha Mandal,Mattia Lepori,Joshua P. Barham,Julia Rehbein,Oliver Reiser
标识
DOI:10.1002/anie.202411930
摘要
We disclose a mediated electrochemical [2+2+2] annulation of alkynes with nitriles, forming substituted pyridines in a single step from low‐cost, readily available starting materials. The combination of electrochemistry and a triarylamine redox mediator obviates the requirements of transition metals and additional oxidants. Besides the formation of diarylpyridine moieties via the homocoupling of two identical alkynes, the heterocoupling of two different alkynes depending on their electronic nature is possible, highlighting the unprecedented control of chemoselectivity in this catalytic [2+2+2] process. Mechanistic investigations like cyclic voltammetry and crossover experiments combined with DFT calculations indicate the initial oxidation of an alkyne as the key step leading to the formation of a vinyl radical cation intermediate. The utilization of continuous flow technology proved instrumental for an efficient process scale‐up. The utility of the products is exemplified by the synthesis of π‐extended molecules, being relevant for material or drug synthesis.
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