Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl. 2020 Apr 27;59(18):7261-7265. doi: 10.1002/anie.202001258. Epub 2020 Mar 9.
We report the first examples of catalytic enantioselective benzilic ester rearrangement reaction. In the presence of a catalytic amount of Cu(OTf) and a chiral box ligand under mild conditions, reaction of 2,3-diketoesters with alcohols afforded structurally diverse α-aryl(alkyl) substituted-α-hydroxy malonates (tartronic esters) in good to excellent yields with high enantioselectivities. Preliminary mechanistic studies indicated that hemiketalization, rather than the dynamic kinetic resolution of hemiketal, was the enantiodetermining step under our reaction conditions.
我们报告了首例催化对映选择性安息香酯重排反应的实例。在温和条件下，使用催化量的 Cu(OTf) 和手性盒配体，2,3-二酮酯与醇反应以高对映选择性得到结构多样的α-芳基（烷基）取代-α-羟基丙二酸酯（塔伦酯），产率良好至优秀。初步的机理研究表明，在我们的反应条件下，半缩酮化而不是半缩酮的动态动力学拆分是决定对映体的步骤。
