Asymmetric Aminations and Kinetic Resolution of Acyclic α‐Branched Ynones

• Published in: Chinese journal of chemistry Vol. 40; no. 1; pp. 15 - 20
• Main Authors: He, Faqian, Shen, Guosong, Yang, Xiaoyu
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag GmbH & Co. KGaA 01-01-2022; Wiley Subscription Services, Inc
• Subjects: Amination; Asymmetric catalysis; Asymmetric synthesis; Asymmetry; Catalysis; Chiral phosphoric acids; Enantiomers; Ketones; Kinetic resolution; Phosphoric acid; Substitutes; α‐Branched ynones
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.202100514

Comprehensive Summary
An efficient method for asymmetric synthesis of acyclic α‐tertiary amine derivatives has been achieved through enantioselective aminations of α‐branched ynones with azodicarboxylates enabled by chiral phosphoric acid catalysis. Moreover, kinetic resolution of racemic starting material was realized under these conditions, which gave access to valuable enantioenriched α‐substituted ketones. A wide array of α‐aryl and alkyl‐substitutions, and the substituted alkynyl groups were well compatible with this method, producing both the amination products and the recovered ketones with good to high enantioselectivities.
An efficient method for asymmetric synthesis of acyclic α‐tertiary amine derivatives has been realized through direct enantioselective aminations of α‐branched ynones under chiral phosphoric acid catalysis. In addition, kinetic resolution of the racemic ketones was also achieved under these conditions, which provided access to chiral α‐substituted ketones with high enantioselectivities.