Development of New Lewis Acid Catalysts based on Late-Transition Metal Complexes

基于后过渡金属配合物的新型路易斯酸催化剂的开发

• 批准号: 12450361
• 负责人: NISHIYAMA Hisao
• 金额: $ 8.96万
• 依托单位: Nagoya University (2002)Toyohashi University of Technology (2000-2001)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450361/
• 关键词: Lewis Acid; Asymmetric Synthesis; Oxazoline; aqueous system; Rhodium; 1,3-dipolar; 遷移金属触媒; オキケゾリン; 水; 1、3-双極付加; アルドール反応; 触媒; 水素触媒; ビスオキサゾリン; 白金; 不斉; ルイス酸触媒; 遷移金属錯体; 環境調和型; 水和錯体

In order to develop a new class of Lewis acid catalysts, complexes of late-transition metals have been investigated including chiral skeleton on the binding oragnic parts. The new complexes have been characterized by NMR and X-ray analysis. The catalysts have also designed to have some profiles, such as water tolerable and recyclable.We have developed new type of ligands including chiral oxazoline-pyridine derivatives, bis(oxazolinyl)pyridines, bis(oxazolinyl)phenyl, and bis(oxazolinyl)xantenes, which were derived from optically active beta-aminoalcohols. We have determined structures of several rhodium, ruthenium, platinum, and palladium complexes with oxazoline skeletons by X-ray analysis. Espetially, Phebox-Rh complexes exhibited catalytic activity as Lewis acids to promote Diels-Alder reaction, hetero-Diesl-Alder reaction, and aldol reactions giving higher enantioselectivities. The catalyst shows the activity in aqueous media.

为了开发一类新型的Lewis酸催化剂，我们研究了后过渡金属络合物，包括有机键合部分的手性骨架。用核磁共振和X-射线分析对新化合物进行了表征。我们还开发了新型的配体，包括手性恶唑啉-吡啶衍生物、双(恶唑啉)吡啶、双(恶唑啉)苯基和双(恶唑啉)苍耳烷，它们都是由光学活性的β-氨基醇衍生而来的。我们用X-射线分析确定了几种含恶唑啉骨架的Rh、Ru、Pd、铂配合物的结构。特别是，Phebox-Rh络合物表现出作为Lewis酸的催化活性，能够促进Diels-Alder反应、杂化Diesl-Alder反应和Aldol反应，具有较高的对映选择性。该催化剂在水介质中表现出良好的催化活性。