Nucleophilic addition of nitrones to ketones: development of a new catalytic asymmetric nitrone-aldol reaction.
Chemistry. 2002 Dec 16; 8(24):5652-61.C

Abstract

A new organic reaction has been discovered in which nitrones react with carbonyl compounds in an aldoltype reaction to give functionalized beta-hydroxynitrones. The alpha-carbon atom of the nitrone undergoes a nucleophilic addition reaction to electron-deficient ketones, such as alpha-ketoesters, alpha,beta-diketones, and trifluoromethyl ketones, to afford the products in moderate to good yields. The scope and potential of the reaction have been investigated and developed. The reaction can also be catalyzed by secondary amines. The use of chiral cyclic amines, such as L-proline leads to optically active beta-hydroxynitrones in moderate yield and with moderate to high enantiomeric excess. The reaction mechanism was studied by kinetic measurements, intermediate and product analysis, and determination of the absolute configuration of the product; based on these investigations a mechanism for the new reaction is proposed.

Authors+Show Affiliations

Bøgevig A

Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark.

Gothelf KV

No affiliation info available

Jørgensen KA

No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

12693046

Citation

Bøgevig, Anders, et al. "Nucleophilic Addition of Nitrones to Ketones: Development of a New Catalytic Asymmetric Nitrone-aldol Reaction." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 8, no. 24, 2002, pp. 5652-61.

Bøgevig A, Gothelf KV, Jørgensen KA. Nucleophilic addition of nitrones to ketones: development of a new catalytic asymmetric nitrone-aldol reaction. Chemistry. 2002;8(24):5652-61.

Bøgevig, A., Gothelf, K. V., & Jørgensen, K. A. (2002). Nucleophilic addition of nitrones to ketones: development of a new catalytic asymmetric nitrone-aldol reaction. Chemistry (Weinheim an Der Bergstrasse, Germany), 8(24), 5652-61.

Bøgevig A, Gothelf KV, Jørgensen KA. Nucleophilic Addition of Nitrones to Ketones: Development of a New Catalytic Asymmetric Nitrone-aldol Reaction. Chemistry. 2002 Dec 16;8(24):5652-61. PubMed PMID: 12693046.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Nucleophilic addition of nitrones to ketones: development of a new catalytic asymmetric nitrone-aldol reaction. AU - Bøgevig,Anders, AU - Gothelf,Kurt V, AU - Jørgensen,Karl Anker, PY - 2003/4/16/pubmed PY - 2003/4/16/medline PY - 2003/4/16/entrez SP - 5652 EP - 61 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 8 IS - 24 N2 - A new organic reaction has been discovered in which nitrones react with carbonyl compounds in an aldoltype reaction to give functionalized beta-hydroxynitrones. The alpha-carbon atom of the nitrone undergoes a nucleophilic addition reaction to electron-deficient ketones, such as alpha-ketoesters, alpha,beta-diketones, and trifluoromethyl ketones, to afford the products in moderate to good yields. The scope and potential of the reaction have been investigated and developed. The reaction can also be catalyzed by secondary amines. The use of chiral cyclic amines, such as L-proline leads to optically active beta-hydroxynitrones in moderate yield and with moderate to high enantiomeric excess. The reaction mechanism was studied by kinetic measurements, intermediate and product analysis, and determination of the absolute configuration of the product; based on these investigations a mechanism for the new reaction is proposed. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/12693046/Nucleophilic_addition_of_nitrones_to_ketones:_development_of_a_new_catalytic_asymmetric_nitrone_aldol_reaction_ DB - PRIME DP - Unbound Medicine ER -

Tags

Nucleophilic addition of nitrones to ketones: development of a new catalytic asymmetric nitrone-aldol reaction.Chemistry. 2002 Dec 16; 8(24):5652-61.C