Details

Autor(en) / Beteiligte

• Cai, Yue‐Ming
• Liu, Xiao‐Ting
• Xu, Lin‐Lin
• Shang, Ming

Titel

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

Ist Teil von

• Angewandte Chemie International Edition, 2024-03, Vol.63 (12), p.e202315222-n/a

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2024

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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.