Stereocontrol utilizing intermolecular interaction

利用分子间相互作用的立体控制

基本信息

批准号：
10208214
负责人：
KATSUKI Tsutomu
金额：
$ 44.48万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas (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

Dynamic control of intermolecular interaction is indispensable for achieving highly stereocontrolled reactions. We have developed various new stereocontrolled reactions on the basis of new knowledge on the factors controlling intermolecular reactions.(1) Study with metallosalen complexesThe X-ray structural analysis of metallosalen complexes clarified that conformation of the salen ligands is strongly influenced by weak-bond interactions such as OH-π and CH-π interactions and by the presence or absence of a donor ligand. With this knowledge, highly cis- and enantio-selective cyclopropanation was achieved for the first time. Furthermore, new type of asymmetric catalysts activated by photo-irradiation were introduced and, with these complexes, catalytic asymmetric oxidation using molecular oxygen as the terminal oxidant was developed.(2) New methodologies for acyclic stereocontrolStereospecific and regioselective epoxide-ring opening using new aluminum and borane reagents enabled efficie … More nt construction of consecutive asymmetric centers. High efficient construction of chiral quaternary carbons was also developed. With these reactions as key steps, various natural products of complex architectures were synthesized in a highly straightforward manner.(3) Asymmetric induction based on dynamic chirality of enolate structureDirect α-alkylation of optically active α-amino acids was achieved in an enantiospecific manner in the absence of any external chiral sources. Newly introduced nucleophylic catalyst bearing p-aminopyridine moiety enabled highly enantiomer-differentiating acylation. The origin for the observed selectivity was attributed to enantiomer-selective acceleration.(4) Transition metal catalysts in stereoselective carbohydrate synthesisVarious carbohydrate derivatives were synthesized efficiently from protected and unprotected glucals by using transition metal catalysts.(5) Desymmetrization of meso-diols and memory of chirality in carbenium ionAsymmetric desymmetrization of meso-diols was achieved efficiently by mono-acylation using chiral binaphthyltin dibromide as a catalyst. Optically acive α-amino acids were converted into optically active aminals via the corresponding acylinium ions in the absence of any external chiral sources. These results disclosed that memory of chirality can be observed in the reactions proceeding through a carbenium intermediate. Less

分子间相互作用的动态控制对于实现高度立体控制的反应是必不可少的。 We have developed various new stereocontrolled reactions on the basis of new knowledge on the factors controlling intermolecular reactions.(1) Study with metallosalen complexesThe X-ray structural analysis of metallosalen complexes clarified that conference of the salen ligands is strongly influenced by weak-bond interactions such as OH-π and CH-π interactions and by the presence or absence of a donor ligand.有了这些知识，首次实现了高度的顺式和对映选择性环丙烷化。此外，引入了通过光辐射激活的新型不对称催化剂，并且，使用这些复合物，使用分子氧作为末端氧化物的催化不对称氧化。（2）使用新方法使用新方法，用于使用新的构造构造和调节性构造效应的新方法……连续的不对称中心。还开发了高效的手性季四元碳。将这些反应作为关键步骤，复杂体系结构的各种天然产物以高度直接的方式合成。（3）基于烯丙基活性α-氨基酸的动态性手性的不对称诱导是在不存在任何外部chiriral源源的情况下以对照源性的方式实现了光学活性α-氨基酸的。新引入了带有p-氨基吡啶部分的核物理催化剂，使高度差异化的酰化能力。观察到的选择性的起源归因于促进者选择性加速度。（4）通过使用过渡金属催化剂（5）的旋转金属催化剂（5），通过受保护和未经保护的淋巴结有效地合成了立体选择性的碳含碳含量合成的碳含量碳水化合物衍生物的过渡金属催化剂。（5）。使用手性双氨基蛋白二溴化物作为催化剂，通过单次筛分有效地实现了中二醇的离子化对称性对称性化。在没有任何外部手性源的情况下，通过相应的酰基酰基离子将光学上的α-氨基酸转化为光学活性臂。这些结果揭示了手性记忆可以在通过碳中间的反应中观察到。较少的