Catalytic asymmetric bromination and chlorination of beta-ketoesters.
Chemistry. 2004 May 03; 10(9):2133-7.C

Abstract

The first general catalytic asymmetric bromination and chlorination of beta-ketoesters has been developed. The reactions proceed for both acyclic and cyclic beta-ketoesters catalyzed by chiral bisoxazolinecopper(II) complexes giving the corresponding optically active alpha-bromo- and alpha-chloro-beta-ketoesters in high yields and moderate to good enantioselectivities. For the optically active chlorinated products the isolated yields are in the range of 88-99 % and the enantiomeric excesses up to 77 % ee, while the optically active brominated adducts are formed in 70-99 % isolated yield and up to 82 % ee. Based on the absolute configuration of the optically active products, the face selectivity for the catalytic enantioselective halogenation is discussed based on a bidentate coordination of the beta-ketoester to the chiral catalyst and a X-ray structure of chiral alpha,gamma-diketoesterenolatebisoxazolinecopper(II) complex.

Authors+Show Affiliations

Marigo M

The Danish National Research Foundation: Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark.

Kumaragurubaran N

No affiliation info available

Jørgensen KA

No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15112201

Citation

Marigo, Mauro, et al. "Catalytic Asymmetric Bromination and Chlorination of Beta-ketoesters." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 10, no. 9, 2004, pp. 2133-7.

Marigo M, Kumaragurubaran N, Jørgensen KA. Catalytic asymmetric bromination and chlorination of beta-ketoesters. Chemistry. 2004;10(9):2133-7.

Marigo, M., Kumaragurubaran, N., & Jørgensen, K. A. (2004). Catalytic asymmetric bromination and chlorination of beta-ketoesters. Chemistry (Weinheim an Der Bergstrasse, Germany), 10(9), 2133-7.

Marigo M, Kumaragurubaran N, Jørgensen KA. Catalytic Asymmetric Bromination and Chlorination of Beta-ketoesters. Chemistry. 2004 May 3;10(9):2133-7. PubMed PMID: 15112201.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Catalytic asymmetric bromination and chlorination of beta-ketoesters. AU - Marigo,Mauro, AU - Kumaragurubaran,Nagaswami, AU - Jørgensen,Karl Anker, PY - 2004/4/28/pubmed PY - 2004/4/28/medline PY - 2004/4/28/entrez SP - 2133 EP - 7 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 10 IS - 9 N2 - The first general catalytic asymmetric bromination and chlorination of beta-ketoesters has been developed. The reactions proceed for both acyclic and cyclic beta-ketoesters catalyzed by chiral bisoxazolinecopper(II) complexes giving the corresponding optically active alpha-bromo- and alpha-chloro-beta-ketoesters in high yields and moderate to good enantioselectivities. For the optically active chlorinated products the isolated yields are in the range of 88-99 % and the enantiomeric excesses up to 77 % ee, while the optically active brominated adducts are formed in 70-99 % isolated yield and up to 82 % ee. Based on the absolute configuration of the optically active products, the face selectivity for the catalytic enantioselective halogenation is discussed based on a bidentate coordination of the beta-ketoester to the chiral catalyst and a X-ray structure of chiral alpha,gamma-diketoesterenolatebisoxazolinecopper(II) complex. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/15112201/Catalytic_asymmetric_bromination_and_chlorination_of_beta_ketoesters_ DB - PRIME DP - Unbound Medicine ER -

Tags

Catalytic asymmetric bromination and chlorination of beta-ketoesters.Chemistry. 2004 May 03; 10(9):2133-7.C