Electrochemical Ni‐Catalyzed Decarboxylative C(sp3)−N Cross‐Electrophile Coupling

• Published in: Angewandte Chemie International Edition Vol. 63; no. 12; pp. e202315222 - n/a
• Main Authors: Cai, Yue‐Ming, Liu, Xiao‐Ting, Xu, Lin‐Lin, Shang, Ming
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 18.03.2024; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: carboxylic acid; Carboxylic acids; Catalysis; Catalysts; Chemical reduction; Chemistry; Chemistry, Multidisciplinary; cross-electrophile coupling; Electrochemistry; Functional groups; iminyl radical; late-stage functionalization; Nickel; Physical Sciences; Radicals; Reagents; Science & Technology; cross-electrophile coupling; iminyl radical; carboxylic acid; electrochemistry; late-stage functionalization
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202315222

A new electrochemical transformation is presented that enables chemists to couple simple alkyl carboxylic acid derivatives with an electrophilic amine reagent to construct C(sp3)−N bond. The success of this reaction hinges on the merging of cooperative electrochemical reduction with nickel catalysis. The chemistry exhibits a high degree of practicality, showcasing its wide applicability with 1°, 2°, 3° carboxylic acids and remarkable compatibility with diverse functional groups, even in the realm of late‐stage functionalization. Furthermore, extensive mechanistic studies have unveiled the engagement of alkyl radicals and iminyl radicals; and elucidated the multifaceted roles played by iPr2O, Ni catalyst, and electricity. Ni‐catalyzed decarboxylative C(sp3)−N cross‐coupling of redox active ester and oxime esters was realized through electrochemical cathodic reduction. Mechanistic studies unveil a high‐valent nickel species‐driven reductive elimination pathway, rather than direct radical‐radical coupling. The utility of this methodology was demonstrated through a broad scope (1°, 2°, 3° carboxylic acids) and late‐stage functionalization of complex molecules.