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.

这项研究的目的是建立i）i）简单制备三环2-恶唑烷酮和2-咪唑替奈酮，具有构象刚性和空间充血作为催化分辨率极有强大的手性辅助因素，以及II）与Bbicyclic 2-氨基醇醇和1,2-Diaim的极好的不对称反应。通过动力学分辨率轻松获取高效的手性辅助机：可轻松地从动力学分辨率中获得了使用黄选择性方法的催化剂，可以从动力学分辨率中获得，这是使用“ Mac-acid”（2-execoCARCARCARCARCAR）的替代方法。高效的手性辅助机构的发展：使用2-咪唑二唑酮辅助剂引起的非映选择性在很大程度上取决于杂环的N-阳离子，其中笨重的领域是繁殖的占选择组的基础。这种类型的反应在N'-Butyryl-2-二氨基二唑啉酮的甲基化中提供了极好的非对映选择水平。3。高效的手性氨基醇的发展：（1）手性配体：通过上述三环2-恶唑烷酮的环的开环得出的手性顺式氨基醇在催化性手性辨别力（高水平的催化水平）（在催化性的高水平）中起着有前途的作用（在催化性手续的高水平中（2）中性反应：2-3-3-3-3-二氨酸-2-二氨基-2-iridiDiDiDiDiDiDiDIDIDIDIDIIDINIDIDINIDIDINIDINIDIDIDINIDIIDINDIDIDIDIIDINIDINIDIDINIDIDIDIIDINIDIDINIDIDINIDIDIDIDIDIDIIDIDINIDIDIINSIDIN。在空地上充血的2-氨基醇的烷氧气很好地用作歧视剂，可高效地对中等1,3-二乙酰基-2-米达唑烷酮。上面的氨基醇为Cu（II）配合物催化的藻反应提供了意外的对映射，这是设计新手性合成过程的重要发现。