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複素環系不斉補助剤を基盤とした精密な不斉制御空間の構築と不斉触媒反応への展開

基于杂环不对称助剂的精确不对称控制空间的构建及其在不对称催化反应中的应用

基本信息

批准号：
10470471
负责人：
KUNIEDA Takehisa
金额：
$ 7.42万
依托单位：
Kumamoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

The aim of this research is to establish the methodology for i) simple preparation of tricyclic 2-oxazolidinones and 2-imidazolidinones with conformational rigidity and steric congestion as extremely powerful chiral auxiliaries by catalytic resolution, and ii) excellent asymmetric reactions with bicyclic 2-amino alcohols and 1,2-diamines derived from the above tricyclic compounds.1. Easy access to highly efficient chiral auxiliaries by kinetic resolution :The optically active "roofed" 2-oxazolidinones and 2-imidazolidinones were readily obtained from kinetic resolution with oxazaborolidine catalysts, which is an alternative method for optical resolution with "MAC-acid" (2-exo-methoxy-1-apocamphanecarboxylic acid).2. Development of highly efficient chiral auxiliaries :Diastereoselectivity which is induced by the use of 2-imidazolidinone auxiliaries is greatly dependent on the N-substituents of the heterocycles, among which the bulky arenesulfonyl group is the moiety of choice. Reactions of this type afford an excellent level of diastereoselection in the methylation of N'-butyryl-2-imidazolidinones via the metal enolates.3. Development of highly efficient chiral amino alcohols :(1) chiral ligands : The chiral cis-2-aminoalcohols derived from ring-opening of the above tricyclic 2-oxazolidinones played a promising role in performing the high level of catalytic chiral discrimination (asymmetrization of meso-1,3-diacetyl-2-imidazolidinones).(2) chiral reactants : The alkoxide of the sterically congested 2-aminoalcohols served well as chiral discriminating agents for highly efficient dissymmetrization of meso-1,3-diacetyl-2-imidazolidinones.(3) C_2-symmetrical bis (oxazoline) ligands : The use of sterically congested C_2-symmetrical bis (oxazoline) ligands derived from the above amino alcohols provided the unexpected enantioselection for aldol reactions catalyzed by the Cu (II) complexes, which was an important findings for a design of new chiral synthetic processes.

本研究的目的是建立一种简单的制备具有构象刚性和空间拥挤的三环2-恶唑烷酮和2-咪唑烷酮的催化拆分方法，以及与由上述三环化合物衍生的双环2-氨基醇和1，2-二胺的优异的不对称反应。通过动力学拆分容易获得高效的手性助剂：通过使用恶唑硼烷催化剂的动力学拆分容易获得光学活性的“屋顶”2-恶唑烷酮和2-咪唑烷酮，这是“MAC-酸”（2-exo-methoxy-1-apocamphanecarboxylic acid）光学拆分的替代方法。高效手性助剂的开发：2-咪唑啉酮类助剂的非对映选择性很大程度上取决于杂环的N-取代基，其中大体积的芳烃磺酰基是选择的部分。这种类型的反应在经由金属烯醇化物的N '-丁酰基-2-咪唑烷酮的甲基化中提供了优异水平的非对映选择性。高效手性氨基醇的开发：（1）手性配体：由上述三环2-恶唑烷酮开环得到的手性顺式-2-氨基醇在高水平的催化手性识别（meso-1，3-二乙酰基-2-咪唑烷酮的不对称化反应）中发挥了很好的作用。(2)手性反应物：空间拥挤的2-氨基醇的醇盐可作为手性识别剂用于meso-1，3-二乙酰基-2-咪唑烷酮的高效不对称化反应。(3)C_2-对称双恶唑啉配体：利用上述氨基醇衍生的空间拥挤的C_2-对称双恶唑啉配体，在Cu（II）配合物催化的Aldol反应中提供了出乎意料的对映体选择性，这对于设计新的手性合成方法是一个重要的发现。