Acyclic stereoselection using 1, 2-diastereoselective induction reactions

我们发现，用Sharpless试剂对具有杂原子取代基的烯丙醇进行动力学拆分，两种对映体的速率差别很大。我们还发现2-呋喃醇和2-噻吩醇的动力学拆分也进行得很有效，从而分别为制备同手性2-呋喃醇和2-噻吩醇提供了一种通用方法。我们已经掌握了这些仲醇的高效制备方法，通过1,2-非对映选择性诱导反应和利用杂原子取代基、呋喃基和噻基部分的反应活性，致力于将这些仲醇用于制备天然产物和重要的生物合成中间体。结果，我们成功地以手性形式制备了-羟基羧酸、乙烯环氧化物、1-乙烯基-1,2-二醇、- -二氧基醛和-内酯。

We have found that the kinetic resolution of allylic alcohols possessing a heteroatom substituent at gamma-position by using the Sharpless reagent proceeds with very large rate differences for the two enantismers. We also found that the kinetic resolution of 2-furanyl alcohols and 2-thienyl alcohols also proceeds efficiently thus providing a general method for preparation of homochiral 2-furanyl alcohols and 2-thienyl alcohols, respectively.With highly efficient method for preparation of these secondary alcohols in hand, we have devoted our efforts to use these alcohols for preparation of natural products and important intermediates for synthesis of biological importance by using 1,2-diastereoselective induction reactions and use of the reactivity of the heteroatom substituents, and furyl and thienyl moiety. As a result, we have succeeded to prepare alpha-hydroxy carboxylic acids, vinyl epoxides, 1-vinyl-1,2-diols, alpha,beta-dialkoxy aldehydes, and gamma-lactones in chiral forms.