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Synthesis of chiral 1,3-diamines derived from cis-2-benzamidocyclohexanecarboxylic acid and their application in the Cu-catalyzed enantioselective Henry reaction.
Chemistry. 2011 Nov 25; 17(48):13584-92.C

Abstract

In this study, 13 different chiral 1,3-diamines were synthesized from (-)-cis-2-benzamidocyclohexanecarboxylic acid. They were successfully applied as ligands in the Cu-catalyzed asymmetric Henry reaction between benzaldehyde and nitromethane. It was confirmed that the enantioselectivity of the product could be controlled by the substituents on the two amino groups. A time-course study revealed a decrease in product enantioselectivity caused by spontaneous retro-Henry reaction, which was suppressed by conducting the reaction at 0 °C. This versatile reaction afforded various β-nitroalcohols in excellent yields and enantioselectivities (up to 98% yield, 91% enantiomeric excess) under the optimized reaction conditions. The chiral induction mechanism was explained on the basis of a previously proposed transition-state model.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Kodama K
Department of Applied Chemistry, Graduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Saitama 338-8570, Japan. kodama@mail.saitama-u.ac.jp
Sugawara K
No affiliation info available
Hirose T
No affiliation info available

MeSH

BenzamidesCatalysisCopperCyclohexanesDiaminesLigandsMolecular StructureStereoisomerism

Pub Type(s)

Journal Article

Language

eng

PubMed ID

22025350

Citation

Kodama, Koichi, et al. "Synthesis of Chiral 1,3-diamines Derived From Cis-2-benzamidocyclohexanecarboxylic Acid and Their Application in the Cu-catalyzed Enantioselective Henry Reaction." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 17, no. 48, 2011, pp. 13584-92.
Kodama K, Sugawara K, Hirose T. Synthesis of chiral 1,3-diamines derived from cis-2-benzamidocyclohexanecarboxylic acid and their application in the Cu-catalyzed enantioselective Henry reaction. Chemistry. 2011;17(48):13584-92.
Kodama, K., Sugawara, K., & Hirose, T. (2011). Synthesis of chiral 1,3-diamines derived from cis-2-benzamidocyclohexanecarboxylic acid and their application in the Cu-catalyzed enantioselective Henry reaction. Chemistry (Weinheim an Der Bergstrasse, Germany), 17(48), 13584-92. https://doi.org/10.1002/chem.201102136
Kodama K, Sugawara K, Hirose T. Synthesis of Chiral 1,3-diamines Derived From Cis-2-benzamidocyclohexanecarboxylic Acid and Their Application in the Cu-catalyzed Enantioselective Henry Reaction. Chemistry. 2011 Nov 25;17(48):13584-92. PubMed PMID: 22025350.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Synthesis of chiral 1,3-diamines derived from cis-2-benzamidocyclohexanecarboxylic acid and their application in the Cu-catalyzed enantioselective Henry reaction. AU - Kodama,Koichi, AU - Sugawara,Kazuyuki, AU - Hirose,Takuji, Y1 - 2011/10/25/ PY - 2011/07/12/received PY - 2011/10/26/entrez PY - 2011/10/26/pubmed PY - 2012/4/7/medline SP - 13584 EP - 92 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 17 IS - 48 N2 - In this study, 13 different chiral 1,3-diamines were synthesized from (-)-cis-2-benzamidocyclohexanecarboxylic acid. They were successfully applied as ligands in the Cu-catalyzed asymmetric Henry reaction between benzaldehyde and nitromethane. It was confirmed that the enantioselectivity of the product could be controlled by the substituents on the two amino groups. A time-course study revealed a decrease in product enantioselectivity caused by spontaneous retro-Henry reaction, which was suppressed by conducting the reaction at 0 °C. This versatile reaction afforded various β-nitroalcohols in excellent yields and enantioselectivities (up to 98% yield, 91% enantiomeric excess) under the optimized reaction conditions. The chiral induction mechanism was explained on the basis of a previously proposed transition-state model. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/22025350/Synthesis_of_chiral_13_diamines_derived_from_cis_2_benzamidocyclohexanecarboxylic_acid_and_their_application_in_the_Cu_catalyzed_enantioselective_Henry_reaction_ L2 - https://doi.org/10.1002/chem.201102136 DB - PRIME DP - Unbound Medicine ER -