Stereodivergent Pd/Cu Catalysis for the Dynamic Kinetic Asymmetric Transformation of Racemic Unsymmetrical 1,3-Disubstituted Allyl Acetates

• Published in: Journal of the American Chemical Society Vol. 142; no. 18; pp. 8097 - 8103
• Main Authors: He, Rui, Huo, Xiaohong, Zhao, Ling, Wang, Feijun, Jiang, Liyin, Liao, Jian, Zhang, Wanbin
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.05.2020; Amer Chemical Soc
• Subjects: acetates; aldimines; amino acids; catalysts; catalytic activity; Chemistry; Chemistry, Multidisciplinary; copper; diastereoselectivity; enantioselectivity; ligands; palladium; Physical Sciences; Science & Technology; stereoisomers; ALCOHOLS; ENANTIOSELECTIVE SYNTHESIS; SYNERGISTIC IRIDIUM; C-O; ALKYLATION; ESTERS; ALPHA-AMINO-ACIDS; SUBSTITUTION-REACTIONS; DIASTEREODIVERGENT ACCESS; DUAL IRIDIUM
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.0c02150

A stereodivergent Pd/Cu catalyst system has been developed for the unprecedented dynamic kinetic asymmetric transformation (DyKAT) of racemic unsymmetrical 1,3-disubstituted allylic acetates with prochiral aldimine esters. A series of α,α-disubstituted α-amino acids bearing vicinal stereocenters were easily prepared with excellent enantioselectivities (up to >99% ee) and diastereoselectivities (up to >20:1 dr). Moreover, all four stereoisomers of the product can be readily obtained simply by switching the configurations of the two chiral metal catalysts. Furthermore, the present work highlights the power of synergistic Pd/Cu catalysis consisting of two common bidentate chiral ligands for stereodivergent synthesis.