Silicon-mediated enantioselective synthesis of structurally diverse α-amino acid derivatives

• Published in: Science China. Chemistry 2020-08, Vol.63 (8), p.1082-1090
• Main Authors: Ma, Jun-Han, Li, Li, Sun, Yu-Li, Xu, Zheng, Bai, Xing-Feng, Yang, Ke-Fang, Cao, Jian, Cui, Yu-Ming, Yin, Guan-Wu, Xu, Li-Wen
• Format: Article
• Language: English
• Subjects: Aldehydes; Amino acids; Carbon; Catalysis; Chemical synthesis; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Chromatography; Cinnamaldehyde; Copper; Cycloaddition; Enantiomers; Esters; Fluorides; Silicon; Substitutes
• ISSN: 1674-7291; 1869-1870
• DOI: 10.1007/s11426-020-9768-x

The catalytic asymmetric synthesis of novel and chiral amino acid derivatives with unconventional chemo-, diastereo-, and enantio-selectivity remains a paramount challenge. Herein we reported a novel protocol for the use of highly enantioselective copper-catalyzed cycloaddition of α,β-unsaturated acylsilanes as a springboard reaction for the facile synthesis of structurally diversified pyrrolidines and complicated α-amino esters by desilylation. The newly developed process could provide a wide range of synthetically useful acylsilane-substituted pyrrolidines (ASiP) in high yields and excellent diastereo- and enantio-selectivities with Cu/(R)-XylBINAP complex as the catalyst. And the downstream desilylation transformation enables to expand the potntial applications of 1,3-dipolar cycloaddition in the construction of structurally unique amino acid derivatives, in which an unprecedented and concerted fluoride anion-promoted C-X (X=H, Si, N, C) bond cleavage occurred to the enantioselective construction of aldehyde-substituted pyrrolidines, linear cinnamaldehyde or alkene-substituted amino esters in high ee values.