Kinetic Resolution of 1,2‐Diamines via Organocatalyzed Asymmetric Electrophilic Aminations of Anilines

• Published in: Chinese journal of chemistry Vol. 40; no. 14; pp. 1674 - 1680
• Main Authors: Xie, Jinglei, Guo, Zheng, Liu, Wei, Zhang, Dekun, He, Yu‐Peng, Yang, Xiaoyu
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag GmbH & Co. KGaA 15.07.2022; Wiley; Wiley Subscription Services, Inc
• Subjects: 1,2‐Diamines; Amination; Aniline; Asymmetric catalysis; Asymmetry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Chiral phosphoric acids; Diamines; Hydrazine; Hydrazines; Kinetic resolution; Phosphoric acid; Physical Sciences; Science & Technology; BRONSTED ACID; CATALYSIS; IMINES; INDOLINES; 2-Diamines; Chiral phosphoric acids; VICINAL DIAMINES; Asymmetric catalysis; ENANTIOSELECTIVE N-ALLYLATION; DESYMMETRIZATION; 1; Amination; MANNICH-TYPE REACTION; AMINES; DIAMINATION; Kinetic resolution
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.202200125

Comprehensive Summary An efficient kinetic resolution (KR) protocol for 1,2‐diamines has been developed through asymmetric electrophilic aminations of anilines enabled by chiral phosphoric acid catalysis. A wide array of substituted 1,2‐diamines were compatible with this method, generating both the recovered staring materials and the amination products with high enantioselectivities (with s‐factor up to 218). Notably, this method is amenable to the kinetic resolution of 1,2‐diamines bearing α‐tertiary amine moieties, which represents the first KR of this type of 1,2‐diamines. Facile removal of the introduced hydrazine group and oxidative cleavage of the N‐aryl group to release the free primary amine demonstrate the value of this method. A novel kinetic resolution (KR) protocol for 1,2‐diamines has been developed through asymmetric electrophilic aminations of anilines enabled by chiral phosphoric acid catalysis. Notably, 1,2‐diamines bearing both α‐secondary and α‐tertiary amine moieties are compatible with this method, which gave good to high KR performances (with s‐factor up to 218).