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The direct catalytic asymmetric alpha-aminooxylation reaction: development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations.
Chemistry. 2004 Aug 06; 10(15):3673-84.C

Abstract

Proline-catalyzed direct asymmetric alpha-aminooxylation of ketones and aldehydes is described. The proline-catalyzed reactions between unmodified ketones or aldehydes and nitrosobenzene proceeded with excellent diastereo- and enantioselectivities. In all cases tested, the corresponding products were isolated with >95 % ees. Methyl alkyl ketones were regiospecifically oxidized at the methylene carbon atom to afford enantiomerically pure alpha-aminooxylated ketones. In addition, cyclic ketones could be alpha,alpha'-dioxidized with remarkably high selectivity, furnishing the corresponding diaminooxylated ketones with >99 % ees. The reaction mechanism of the proline-catalyzed direct asymmetric alpha-aminooxylation was investigated, and we performed density functional theory (DFT) calculations in order to investigate the nature of the plausible transition states further. We also screened other organocatalysts for the asymmetric alpha-oxidation reaction and found that several proline derivatives were also able to catalyze the transformation with excellent enantioselectivities. Moreover, stereoselective routes for the synthesis of monoprotected vicinal diols and hydroxyketones were found. In addition, short routes for the direct preparation of enantiomerically pure epoxides and 1,2-amino alcohols are presented. The direct catalytic alpha-oxidation is also a novel route for the stereoselective preparation of beta-adrenoreceptor antagonists.

Authors+Show Affiliations

Córdova A
Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm, Sweden. acordova@organ.su.se
Sundén H
No affiliation info available
Bøgevig A
No affiliation info available
Johansson M
No affiliation info available
Himo F
No affiliation info available

MeSH

AlcoholsAldehydesAmino AcidsAmino AlcoholsCatalysisKetonesModels, MolecularMolecular ConformationMolecular StructureOxidation-ReductionProlineStereoisomerism

Pub Type(s)

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

Language

eng

PubMed ID

15281151

Citation

Córdova, Armando, et al. "The Direct Catalytic Asymmetric Alpha-aminooxylation Reaction: Development of Stereoselective Routes to 1,2-diols and 1,2-amino Alcohols and Density Functional Calculations." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 10, no. 15, 2004, pp. 3673-84.
Córdova A, Sundén H, Bøgevig A, et al. The direct catalytic asymmetric alpha-aminooxylation reaction: development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations. Chemistry. 2004;10(15):3673-84.
Córdova, A., Sundén, H., Bøgevig, A., Johansson, M., & Himo, F. (2004). The direct catalytic asymmetric alpha-aminooxylation reaction: development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations. Chemistry (Weinheim an Der Bergstrasse, Germany), 10(15), 3673-84.
Córdova A, et al. The Direct Catalytic Asymmetric Alpha-aminooxylation Reaction: Development of Stereoselective Routes to 1,2-diols and 1,2-amino Alcohols and Density Functional Calculations. Chemistry. 2004 Aug 6;10(15):3673-84. PubMed PMID: 15281151.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - The direct catalytic asymmetric alpha-aminooxylation reaction: development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations. AU - Córdova,Armando, AU - Sundén,Henrik, AU - Bøgevig,Anders, AU - Johansson,Mikael, AU - Himo,Fahmi, PY - 2004/7/29/pubmed PY - 2005/10/14/medline PY - 2004/7/29/entrez SP - 3673 EP - 84 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 10 IS - 15 N2 - Proline-catalyzed direct asymmetric alpha-aminooxylation of ketones and aldehydes is described. The proline-catalyzed reactions between unmodified ketones or aldehydes and nitrosobenzene proceeded with excellent diastereo- and enantioselectivities. In all cases tested, the corresponding products were isolated with >95 % ees. Methyl alkyl ketones were regiospecifically oxidized at the methylene carbon atom to afford enantiomerically pure alpha-aminooxylated ketones. In addition, cyclic ketones could be alpha,alpha'-dioxidized with remarkably high selectivity, furnishing the corresponding diaminooxylated ketones with >99 % ees. The reaction mechanism of the proline-catalyzed direct asymmetric alpha-aminooxylation was investigated, and we performed density functional theory (DFT) calculations in order to investigate the nature of the plausible transition states further. We also screened other organocatalysts for the asymmetric alpha-oxidation reaction and found that several proline derivatives were also able to catalyze the transformation with excellent enantioselectivities. Moreover, stereoselective routes for the synthesis of monoprotected vicinal diols and hydroxyketones were found. In addition, short routes for the direct preparation of enantiomerically pure epoxides and 1,2-amino alcohols are presented. The direct catalytic alpha-oxidation is also a novel route for the stereoselective preparation of beta-adrenoreceptor antagonists. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/15281151/The_direct_catalytic_asymmetric_alpha_aminooxylation_reaction:_development_of_stereoselective_routes_to_12_diols_and_12_amino_alcohols_and_density_functional_calculations_ DB - PRIME DP - Unbound Medicine ER -