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Scope and mechanism of tandem aza-Michael reaction/enantioselective protonation using a Pd-μ-hydroxo complex under mild conditions buffered with amine salts.
Chem Asian J. 2011 Feb 01; 6(2):658-68.CA

Abstract

The tandem aza-Michael reaction/enantioselective protonation of α-substituted α,β-unsaturated carbonyl compounds is described in detail. The key to success is the combined use of a Brønsted basic palladium-μ-hydroxo complex and amine salts, which allows for the controlled generation of active catalyst and nucleophilic free amines. This catalytic system was applicable to various acceptors and aromatic amines, and the desired β-amino acid derivatives with a chiral center at the α position were produced in good yield with excellent enantioselectivity (up to 98% ee). For electron-deficient amines, the introduction of free amine as an additive was effective in promoting the reaction. The results of mechanistic studies, including determination of the absolute configuration of the product, are discussed.

Authors+Show Affiliations

Synthetic Organic Chemistry Laboratory, Advanced Science Institute, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-10198, Japan.No affiliation info availableNo 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

21254440

Citation

Hamashima, Yoshitaka, et al. "Scope and Mechanism of Tandem aza-Michael Reaction/enantioselective Protonation Using a Pd-μ-hydroxo Complex Under Mild Conditions Buffered With Amine Salts." Chemistry, an Asian Journal, vol. 6, no. 2, 2011, pp. 658-68.
Hamashima Y, Suzuki S, Tamura T, et al. Scope and mechanism of tandem aza-Michael reaction/enantioselective protonation using a Pd-μ-hydroxo complex under mild conditions buffered with amine salts. Chem Asian J. 2011;6(2):658-68.
Hamashima, Y., Suzuki, S., Tamura, T., Somei, H., & Sodeoka, M. (2011). Scope and mechanism of tandem aza-Michael reaction/enantioselective protonation using a Pd-μ-hydroxo complex under mild conditions buffered with amine salts. Chemistry, an Asian Journal, 6(2), 658-68. https://doi.org/10.1002/asia.201000740
Hamashima Y, et al. Scope and Mechanism of Tandem aza-Michael Reaction/enantioselective Protonation Using a Pd-μ-hydroxo Complex Under Mild Conditions Buffered With Amine Salts. Chem Asian J. 2011 Feb 1;6(2):658-68. PubMed PMID: 21254440.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Scope and mechanism of tandem aza-Michael reaction/enantioselective protonation using a Pd-μ-hydroxo complex under mild conditions buffered with amine salts. AU - Hamashima,Yoshitaka, AU - Suzuki,Shoko, AU - Tamura,Toshihiro, AU - Somei,Hidenori, AU - Sodeoka,Mikiko, Y1 - 2010/12/16/ PY - 2010/10/09/received PY - 2011/1/22/entrez PY - 2011/1/22/pubmed PY - 2011/5/10/medline SP - 658 EP - 68 JF - Chemistry, an Asian journal JO - Chem Asian J VL - 6 IS - 2 N2 - The tandem aza-Michael reaction/enantioselective protonation of α-substituted α,β-unsaturated carbonyl compounds is described in detail. The key to success is the combined use of a Brønsted basic palladium-μ-hydroxo complex and amine salts, which allows for the controlled generation of active catalyst and nucleophilic free amines. This catalytic system was applicable to various acceptors and aromatic amines, and the desired β-amino acid derivatives with a chiral center at the α position were produced in good yield with excellent enantioselectivity (up to 98% ee). For electron-deficient amines, the introduction of free amine as an additive was effective in promoting the reaction. The results of mechanistic studies, including determination of the absolute configuration of the product, are discussed. SN - 1861-471X UR - https://www.unboundmedicine.com/medline/citation/21254440/Scope_and_mechanism_of_tandem_aza_Michael_reaction/enantioselective_protonation_using_a_Pd_μ_hydroxo_complex_under_mild_conditions_buffered_with_amine_salts_ L2 - https://doi.org/10.1002/asia.201000740 DB - PRIME DP - Unbound Medicine ER -