Organocatalytic Arylation of α-Ketoesters Based on Umpolung Strategy: Phosphazene-Catalyzed S<sub>N</sub>
Ar Reaction Utilizing [1,2]-Phospha-Brook Rearrangement
作者:Azusa Kondoh、Takuma Aoki、Masahiro Terada
DOI:10.1002/chem.201803218
日期:2018.9.6
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 SNAr reaction.
α-酮酸酯的有机催化芳基化反应是基于umpolung策略开发的。磷腈P2- t Bu有效催化α-酮酸酯,甲硅烷基化的亚磷酸酯和缺电子的氟代芳烃的三组分偶联反应,从而提供在α-位置具有缺电子的芳基的α-羟基酯衍生物。该反应涉及通过[1,2]-磷-布鲁克重排反应,由α-酮酸酯催化生成α-氧化酯烯酸酯,然后进行S N Ar反应。