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Asymmetric Diels-Alder and inverse-electron-demand hetero-Diels-Alder reactions of β,γ-unsaturated α-ketoesters with cyclopentadiene catalyzed by N,N'-dioxide copper(II) complex.
Chemistry. 2010 Oct 18; 16(39):11963-8.C

Abstract

Highly enantioselective Diels-Alder (DA) and inverse-electron-demand hetero-Diels-Alder (HDA) reactions of β,γ-unsaturated α-ketoesters with cyclopentadiene catalyzed by chiral N,N'-dioxide-Cu(OTf)(2) (Tf=triflate) complexes have been developed. Quantitative conversion of β,γ-unsaturated α-ketoesters and excellent diastereoselectivities (up to 99:1) and enantioselectivities (up to >99% ee) were observed for a broad range of substrates. Both aromatic and aliphatic β,γ-unsaturated α-ketoesters were found to be suitable substrates for the reactions. Moreover, the chemoselectivity of the DA and HDA adducts were improved by regulating the reaction temperature. Good to high chemoselectivity (up to 94%) of the DA adducts were obtained at room temperature, and moderate chemoselectivity (up to 65%) of the HDA adducts were achieved at low temperature. The reaction also featured mild reaction conditions, a simple procedure, and remarkably low catalyst loading (0.1-1.5 mol%). A strong positive nonlinear effect was observed.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Zhu Y
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P.R. of China.
Chen X
No affiliation info available
Xie M
No affiliation info available
Dong S
No affiliation info available
Qiao Z
No affiliation info available
Lin L
No affiliation info available
Liu X
No affiliation info available
Feng X
No affiliation info available

MeSH

CatalysisCombinatorial Chemistry TechniquesCopperCyclizationCyclopentanesEstersKetonesLewis AcidsMolecular StructureStereoisomerism

Pub Type(s)

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

Language

eng

PubMed ID

20827702

Citation

Zhu, Yin, et al. "Asymmetric Diels-Alder and Inverse-electron-demand hetero-Diels-Alder Reactions of Β,γ-unsaturated Α-ketoesters With Cyclopentadiene Catalyzed By N,N'-dioxide copper(II) Complex." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 16, no. 39, 2010, pp. 11963-8.
Zhu Y, Chen X, Xie M, et al. Asymmetric Diels-Alder and inverse-electron-demand hetero-Diels-Alder reactions of β,γ-unsaturated α-ketoesters with cyclopentadiene catalyzed by N,N'-dioxide copper(II) complex. Chemistry. 2010;16(39):11963-8.
Zhu, Y., Chen, X., Xie, M., Dong, S., Qiao, Z., Lin, L., Liu, X., & Feng, X. (2010). Asymmetric Diels-Alder and inverse-electron-demand hetero-Diels-Alder reactions of β,γ-unsaturated α-ketoesters with cyclopentadiene catalyzed by N,N'-dioxide copper(II) complex. Chemistry (Weinheim an Der Bergstrasse, Germany), 16(39), 11963-8. https://doi.org/10.1002/chem.201001365
Zhu Y, et al. Asymmetric Diels-Alder and Inverse-electron-demand hetero-Diels-Alder Reactions of Β,γ-unsaturated Α-ketoesters With Cyclopentadiene Catalyzed By N,N'-dioxide copper(II) Complex. Chemistry. 2010 Oct 18;16(39):11963-8. PubMed PMID: 20827702.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Asymmetric Diels-Alder and inverse-electron-demand hetero-Diels-Alder reactions of β,γ-unsaturated α-ketoesters with cyclopentadiene catalyzed by N,N'-dioxide copper(II) complex. AU - Zhu,Yin, AU - Chen,Xiaohong, AU - Xie,Mingsheng, AU - Dong,Shunxi, AU - Qiao,Zhen, AU - Lin,Lili, AU - Liu,Xiaohua, AU - Feng,Xiaoming, PY - 2010/9/10/entrez PY - 2010/9/10/pubmed PY - 2010/12/31/medline SP - 11963 EP - 8 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 16 IS - 39 N2 - Highly enantioselective Diels-Alder (DA) and inverse-electron-demand hetero-Diels-Alder (HDA) reactions of β,γ-unsaturated α-ketoesters with cyclopentadiene catalyzed by chiral N,N'-dioxide-Cu(OTf)(2) (Tf=triflate) complexes have been developed. Quantitative conversion of β,γ-unsaturated α-ketoesters and excellent diastereoselectivities (up to 99:1) and enantioselectivities (up to >99% ee) were observed for a broad range of substrates. Both aromatic and aliphatic β,γ-unsaturated α-ketoesters were found to be suitable substrates for the reactions. Moreover, the chemoselectivity of the DA and HDA adducts were improved by regulating the reaction temperature. Good to high chemoselectivity (up to 94%) of the DA adducts were obtained at room temperature, and moderate chemoselectivity (up to 65%) of the HDA adducts were achieved at low temperature. The reaction also featured mild reaction conditions, a simple procedure, and remarkably low catalyst loading (0.1-1.5 mol%). A strong positive nonlinear effect was observed. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/20827702/Asymmetric_Diels_Alder_and_inverse_electron_demand_hetero_Diels_Alder_reactions_of_βγ_unsaturated_α_ketoesters_with_cyclopentadiene_catalyzed_by_NN'_dioxide_copper_II__complex_ L2 - https://doi.org/10.1002/chem.201001365 DB - PRIME DP - Unbound Medicine ER -