仲醇的氧化动力学拆分

Oxidative Kinetic Resolution of Secondary Alcohols

光学活性仲醇是非常重要的合成多种具有药物和生物活性化合物的原料和关键中间体,它们可通过外消旋仲醇的氧化动力学拆分获得。本文按氧化剂和手性催化剂的类别分类综述了近年来通过氧化动力学拆分获得光学活性仲醇方法的进展,并对一些方法的机理进行了描述。对以(-)-金雀花碱-钯(Ⅱ)、金雀花碱类似物-钯(Ⅱ)、N-杂环卡宾(NHC)-钯(Ⅱ)、手性双官能团-铱配合物以及手性(ON)-钌(salen)配合物催化的分子氧为氧化剂的仲醇的氧化动力学拆分进行了充分讨论。此外,还讨论了手性salen-锰(Ⅲ)催化二乙酰基碘苯以及通过不对称氢转移的方法对仲醇的氧化动力拆分。可以发现,(-)-金雀花碱-钯(Ⅱ)-分子氧体系在目前所有仲醇氧化动力学拆分体系中表现最佳。用于仲醇氧化动力学拆分的高效体系仍有待进一步开发。

Optically active alcohols are extremely important starting materials and key intermediates for the synthesis of pharmaceutically and biologically active compounds. They can be obtained by oxidative kinetic resolution of racemic alcohols. In this review the recent progress in the oxidative kinetic resolution of secondary alcohols is discussed according to the kind of the oxidants and chiral catalysts. In addition, the mechanisms of some methods for the resolution of secondary alcohols are also discussed. The oxidative kinetic resolution of secondary alcohols using （ - ） -sparteine-Pd （ I1 ）, sparteine analogues-Pd （ 11 ）, N-heterocyclic carbine （ NHC ）-Pd （ 11 ） , chiral difunctional-Ir complexes and chiral （ON）-Ru （salen） complexes as catalyst systems respectively, and molecular oxygen as terminal oxidant are fully discussed. Besides, the resolution of secondary alcohols with chiral salen-Mn（ Ill ） complex as catalyst and （diacetoxyiodo）benzene as terminal oxidant, and by the means of asymmetric transfer hydrogenation are also discussed. It is found that （ - ）-sparteine-Pd（ 11 ）-02 is the best among all the systems employed in the oxidative kinetic resolution of secondary alcohols. The novel system with high performance in the oxidative kinetic resolution of secondary alcohols need to be developed.