Chiral N-Heterocyclic Carbene Catalyzed, Enantioselective Oxodiene Diels−Alder Reactions with Low Catalyst Loadings

Chiral N-Heterocyclic Carbene Catalyzed, Enantioselective Oxodiene Diels−Alder Reactions with Low Catalyst Loadings

Chiral N-heterocyclic carbene (NHC) catalyzed redox reactions of racemic α-chloroaldehydes lead to the generation of chiral enolates suitable for highly enantioselective inverse-electron-demand 1-oxodiene Diels−Alder reactions. Significantly, these reactions proceed under mild, operationally friendl...

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Bibliographic Details
Published in:Journal of the American Chemical Society Vol. 128; no. 47; pp. 15088 - 15089
Main Authors: He, Ming, Uc, Gerson J, Bode, Jeffrey W
Format: Journal Article
Language:English
Published: Washington, DC American Chemical Society 29-11-2006
Subjects:
Aldehydes - chemistry
Alkenes - chemistry
Catalysis
Catalysts: preparations and properties
Chemistry
Exact sciences and technology
General and physical chemistry
Heterocyclic Compounds - chemistry
Hydrocarbons - chemistry
Ketones - chemistry
Lactones - chemical synthesis
Methane - analogs & derivatives
Methane - chemistry
Stereoisomerism
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
Carbene
Catalytic reaction
Enantioselectivity
Nitrogen heterocycle
Organic free biradical
Diels Alder addition
Chiral compound
Catalyst
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Summary:Chiral N-heterocyclic carbene (NHC) catalyzed redox reactions of racemic α-chloroaldehydes lead to the generation of chiral enolates suitable for highly enantioselective inverse-electron-demand 1-oxodiene Diels−Alder reactions. Significantly, these reactions proceed under mild, operationally friendly reaction conditions (EtOAc, room temperature, 2−8 h) using less than 1 mol % of a chiral N-mesityl triazolium salt as the precatalyst. A broad array of densely functionalized dihydropyran-2-ones bearing either aliphatic or aromatic substiutents are formed in excellent yields and exceptional enantioselectivities from readily available reactants. Stereochemical mismatching between the racemic starting materials and the chiral catalyst is avoided by rapid epimerization of the chloroaldehydes under the reaction conditions.
Bibliography:istex:F77F8E8ED31928E4F8EF6D47E50548A14437B412
ark:/67375/TPS-7GZD4Z6B-T
ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:0002-7863
1520-5126
DOI:10.1021/ja066380r