Kobbelgaard Sara, Brandes Sebastian, Jørgensen Karl Anker
The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark.
Chemistry. 2008;14(5):1464-71. doi: 10.1002/chem.200701729.
The first organocatalysed enantioselective [1,3]-sigmatropic O- to N-rearrangement reactions are presented. The reactions take place under regio- and enantioselective control, and are catalysed by cinchona alkaloids. Two reactions have been developed the first one is the rearrangement of imidates to amides, while the other rearrangement occurs from carbamates to amines via a decarboxylation. Both transformations give nitrogen protected beta-amino acid derivatives as the product. These novel asymmetric organocatalysed [1,3]-sigmatropic O- to N-rearrangement reactions provide a reliable and efficient synthetic method for obtaining enantioenriched beta-amino acid derivates in good yield from racemic starting materials.
首次报道了有机催化的对映选择性[1,3]-σ迁移O到N的重排反应。这些反应在区域和对映选择性控制下进行，由金鸡纳生物碱催化。已开发出两种反应，第一种是亚氨酸酯重排为酰胺，而另一种重排是通过脱羧作用使氨基甲酸酯转化为胺。两种转化均以氮保护的β-氨基酸衍生物为产物。这些新型的不对称有机催化[1,3]-σ迁移O到N的重排反应提供了一种可靠且高效的合成方法，可从外消旋原料以良好的产率获得对映体富集的β-氨基酸衍生物。
