Trost Barry M, Richardson Jeffery, Yong Kelvin
Department of Chemistry, Stanford University, California 94305-5080, USA.
J Am Chem Soc. 2006 Mar 1;128(8):2540-1. doi: 10.1021/ja057163d.
The palladium-catalyzed oxidation of allylic esters and carbonates using a novel potassium nitronate has been developed. This method is highly chemoselective, leaving other esters, alcohols, thioethers, and amines undisturbed. The oxidation can be operated in two modes: an achiral mode, using either PPh3 or rac-2 as ligand, or a chiral and highly enantioselective mode, using 2 as ligand. The oxidative enantioselective desymmetrization of meso bis-esters provides a significantly shorter method to arrive at commonly used synthetic intermediates compared to other strategies. Highly efficient kinetic resolution is also possible using this methodology.
已开发出一种使用新型硝酮钾对烯丙基酯和碳酸酯进行钯催化氧化的方法。该方法具有高度的化学选择性,不会影响其他酯、醇、硫醚和胺。氧化反应可以两种模式进行:非手性模式,使用三苯基膦(PPh3)或外消旋-2作为配体;或手性且高度对映选择性模式,使用2作为配体。与其他策略相比,内消旋双酯的氧化对映选择性去对称化提供了一种显著更短的方法来获得常用的合成中间体。使用这种方法也可以实现高效的动力学拆分。