Bøgevig Anders, Gothelf Kurt V, Jørgensen Karl Anker
Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark.
Chemistry. 2002 Dec 16;8(24):5652-61. doi: 10.1002/1521-3765(20021216)8:24<5652::AID-CHEM5652>3.0.CO;2-J.
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.
人们发现了一种新的有机反应，其中硝酮在醛醇型反应中与羰基化合物反应生成官能化的β-羟基硝酮。硝酮的α-碳原子与缺电子酮，如α-酮酯、α,β-二酮和三氟甲基酮发生亲核加成反应，以中等至良好的产率得到产物。该反应的范围和潜力已得到研究和拓展。该反应也可由仲胺催化。使用手性环状胺，如L-脯氨酸，可中等产率且中等至高对映体过量地得到光学活性的β-羟基硝酮。通过动力学测量、中间体和产物分析以及产物绝对构型的测定对反应机理进行了研究；基于这些研究提出了该新反应的机理。
