Electroreduction Enables Regioselective 1,2‐Diarylation of Alkenes with Two Electrophiles

• Published in: Angewandte Chemie International Edition 2023-04, Vol.62 (17), p.e202219166-n/a
• Main Authors: Yu, Weijie, Wang, Shengchun, He, Meng, Jiang, Zhou, Yu, Yi, Lan, Jinping, Luo, Jin, Wang, Pengjie, Qi, Xiaotian, Wang, Tao, Lei, Aiwen
• Format: Article
• Language: English
• Subjects: Adducts; Alkenes; Anions; Aromatic compounds; Arylation; Bromides; Catalysts; Chlorides; Coupling (molecular); Cyanides; Difunctionalization; Electrochemistry; Electrolysis; Functional groups; Halides; Iodides; Metals; Nitriles; Redox Catalysis; Reductive Cross-Coupling; Regioselectivity
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202219166

Precisely introducing two similar functional groups into bulk chemical alkenes represents a formidable route to complex molecules. Especially, the selective activation of two electrophiles is in crucial demand, yet challenging for cross‐electrophile‐coupling. Herein, we demonstrate a redox‐mediated electrolysis, in which aryl nitriles are both aryl radical precursors and redox‐mediators, enables an intermolecular alkene 1,2‐diarylation with a remarkable regioselectivity, thereby avoiding the involvement of transition‐metal catalysts. This transformation utilizes cyanoarene radical anions for activating various aryl halides (including iodides, bromides, and even chlorides) and affords 1,2‐diarylation adducts in up to 83 % yield and >20 : 1 regioselectivity with more than 80 examples, providing a feasible approach to complex bibenzyl derivatives. Utilizing cyanoarene radical anions as redox‐mediators, the electrochemical regioselective 1,2‐diarylation of alkenes with cyanoarenes and aryl halides takes place in the absence of transition‐metal catalysts. The merit of this method has been well demonstrated by its wide scope, excellent regioselectivity, and powerful scale‐up synthesis.