Selective Reductive Elimination at Alkyl Palladium(IV) by Dissociative Ligand Ionization: Catalytic C(sp3)−H Amination to Azetidines

• Published in: Angewandte Chemie Vol. 130; no. 12; pp. 3232 - 3236
• Main Authors: Nappi, Manuel, He, Chuan, Whitehurst, William G., Chappell, Ben G. N., Gaunt, Matthew J.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 12-03-2018
• Subjects: Alcohols; Amination; Amines; Azetidine; C-H-Aktivierung; Catalysis; Chemistry; Functional groups; Hypervalente Verbindungen; Ionization; Palladium; Reaktionsmechanismen; Structure-function relationships
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201800519

A palladium(II)‐catalyzed γ‐C−H amination of cyclic alkyl amines to deliver highly substituted azetidines is reported. The use of a benziodoxole tosylate oxidant in combination with AgOAc was found to be crucial for controlling a selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral α‐amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines.
Eine PdII‐katalysierte γ‐C‐H‐Aminierung von cyclischen Alkylaminen ergibt hoch substituierte Azetidine. Die Kombination aus Benziodoxoltosylat mit AgOAc ermöglichte die selektive reduktive Eliminierung unter Bildung der Azetidine. Der Prozess ist mit einigen funktionellen Gruppen kompatibel, darunter auch chirale α‐Aminoalkohol‐Motive, und führt in diastereoselektiver Weise zu enantiomerenreinen Azetidinen.