Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai, 980-8578, Japan.
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai, 980-8578, Japan.
Chemistry. 2018 Sep 6;24(50):13110-13113. doi: 10.1002/chem.201803218. Epub 2018 Aug 13.
An organocatalytic arylation of α-ketoesters was developed on the basis of umpolung strategy. Phosphazene P2-tBu efficiently catalyzes the three-component coupling reaction of α-ketoesters, a silylated secondary phosphite, and electron-deficient fluoroarenes to provide α-hydroxyester derivatives possessing an electron-deficient aryl group at the α-position. The reaction involves the catalytic generation of α-oxygenated ester enolates from α-ketoesters through the [1,2]-phospha-Brook rearrangement followed by the S Ar reaction.
基于反转策略，开发了一种α-酮酯的有机催化芳基化反应。磷杂环戊二烯 P2-tBu 有效地催化了α-酮酯、硅化的二级膦酸酯和缺电子的氟代芳烃的三组分偶联反应，生成了在α-位具有缺电子芳基的α-羟基酯衍生物。该反应涉及通过[1,2]-磷杂-Brook 重排从α-酮酯中催化生成α-氧代酯烯醇盐，然后进行 S Ar 反应。
