Acyclic stereoselection using 1, 2-diastereoselective induction reactions

使用 1, 2-非对映选择性诱导反应进行非环状立体选择

• 批准号: 62550623
• 负责人: SATO Fumie
• 金额: $ 1.6万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550623/
• 关键词: Sharpless reagent; allylic alcohols; furanyl alcohols; thienyl alcohols; 1, 2-diastereoselective; 不斉酸化; 1、2-不斉誘導; 生理活性化合物; 不斉合成; エノラ-ト; プロピオン酸エステル; 4級炭素; アミノアルコール; α-N、N-ジベンジルアミノフロパナール; 1、2-不斉誘導反応; 1, 2不斉誘導反応; 不斉エポキシ化反応; 1, 2-ジオール; β-アミノ

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.

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。

项目成果

T.Ito,S.Okamoto,and F.Sato: "Practical Method for Synthesis of Optically Pure Propargylic Alcohols" Tetrahedron Letters. 30. 7083-7086 (1989)

T.Ito、S.Okamoto 和 F.Sato：“合成光学纯丙炔醇的实用方法”四面体快报。

Y.Kitano,M.Kusakabe,Y.Kobayashi and F.Sato: "Preparation of Optically Active 2-Thienylcarbio'ls by Kinetic Resolution Using the Sharpless Reagent" Jouranal of Organic Chemistry. 54. 994-996 (1989)

Y.Kitano、M.Kusakabe、Y.Kobayashi 和 F.Sato：“使用 Sharpless 试剂通过动力学拆分制备光学活性 2-Thienylcarbiols”有机化学杂志。

M.Kusakabe,H.Kato and F.Sato: "A Practical Synthesis of Several Polyhydroxylated Chiral Building Blocks" Chemistry Letters. 2163-2166 (1987)

M.Kusakabe、H.Kato 和 F.Sato：“几种多羟基化手性构件的实用合成”化学快报。

M. Kusakabe, Y. Kitano, Y. Kobayashi, and F. Sato: "Preparation of Optically Active 2-Furylcarbinols by Kinetic Resolution Using the Sharpless Reagent and Their Application in Organic Synthesis" J. Org. Chem., 54, 2085-2091 (1989).

M. Kusakabe、Y. Kitano、Y. Kobayashi 和 F. Sato：“使用 Sharpless 试剂通过动力学拆分制备光学活性 2-呋喃基甲醇及其在有机合成中的应用”J. Org。

Y. Kobayashi, M. Kusakabe, Y. Kitano, and F. Sato: "Preparation of Optically Active 2-Furylcarbinols by Kinetic Resolution Using the Sharpless Reagent" J. Org. Chem., 53, 1586-1587 (1988).

Y. Kobayashi、M. Kusakabe、Y. Kitano 和 F. Sato：“使用 Sharpless 试剂通过动力学拆分制备光学活性 2-呋喃基甲醇”J. Org。