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Well-defined binuclear chiral spiro copper catalysts for enantioselective N-H insertion.
J Am Chem Soc. 2012 Jan 11; 134(1):436-42.JA

Abstract

An asymmetric N-H insertion of α-diazoesters with anilines catalyzed by well-defined copper complexes of chiral spiro bisoxazoline ligands was studied in detail. The copper-catalyzed asymmetric N-H insertion of a wide range of α-alkyl-α-diazoacetates with anilines was accomplished with excellent enantioselectivity (up to 98% ee) and provided an efficient method for the preparation of optically active α-amino acid derivatives. A correlation study of the electronic properties of the substrates with the enantioselectivity of the N-H insertion reaction supports a stepwise insertion mechanism, and the significant first-order kinetic isotope effect proves that the proton transfer is most likely the rate-limiting step. A binuclear chiral spiro copper catalyst having 14-electron copper centers, a trans coordination model, a perfect C(2)-symmetric chiral pocket, and significant Cu-Cu interaction was isolated and extensively studied. The novel structure of the binuclear chiral spiro copper catalyst leads to unique reactivity as well as enantioselectivity in the N-H insertion reaction.

Authors+Show Affiliations

State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

22066865

Citation

Zhu, Shou-Fei, et al. "Well-defined Binuclear Chiral Spiro Copper Catalysts for Enantioselective N-H Insertion." Journal of the American Chemical Society, vol. 134, no. 1, 2012, pp. 436-42.
Zhu SF, Xu B, Wang GP, et al. Well-defined binuclear chiral spiro copper catalysts for enantioselective N-H insertion. J Am Chem Soc. 2012;134(1):436-42.
Zhu, S. F., Xu, B., Wang, G. P., & Zhou, Q. L. (2012). Well-defined binuclear chiral spiro copper catalysts for enantioselective N-H insertion. Journal of the American Chemical Society, 134(1), 436-42. https://doi.org/10.1021/ja2084493
Zhu SF, et al. Well-defined Binuclear Chiral Spiro Copper Catalysts for Enantioselective N-H Insertion. J Am Chem Soc. 2012 Jan 11;134(1):436-42. PubMed PMID: 22066865.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Well-defined binuclear chiral spiro copper catalysts for enantioselective N-H insertion. AU - Zhu,Shou-Fei, AU - Xu,Bin, AU - Wang,Guo-Peng, AU - Zhou,Qi-Lin, Y1 - 2011/12/19/ PY - 2011/11/10/entrez PY - 2011/11/10/pubmed PY - 2012/5/9/medline SP - 436 EP - 42 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 134 IS - 1 N2 - An asymmetric N-H insertion of α-diazoesters with anilines catalyzed by well-defined copper complexes of chiral spiro bisoxazoline ligands was studied in detail. The copper-catalyzed asymmetric N-H insertion of a wide range of α-alkyl-α-diazoacetates with anilines was accomplished with excellent enantioselectivity (up to 98% ee) and provided an efficient method for the preparation of optically active α-amino acid derivatives. A correlation study of the electronic properties of the substrates with the enantioselectivity of the N-H insertion reaction supports a stepwise insertion mechanism, and the significant first-order kinetic isotope effect proves that the proton transfer is most likely the rate-limiting step. A binuclear chiral spiro copper catalyst having 14-electron copper centers, a trans coordination model, a perfect C(2)-symmetric chiral pocket, and significant Cu-Cu interaction was isolated and extensively studied. The novel structure of the binuclear chiral spiro copper catalyst leads to unique reactivity as well as enantioselectivity in the N-H insertion reaction. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/22066865/Well_defined_binuclear_chiral_spiro_copper_catalysts_for_enantioselective_N_H_insertion_ L2 - https://doi.org/10.1021/ja2084493 DB - PRIME DP - Unbound Medicine ER -