Nishiyama Hisao, Ito Jun-Ichi
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan.
Chem Rec. 2007;7(3):159-66. doi: 10.1002/tcr.20114.
Molecular catalysts for organic synthesis should be constructed to be tailored to target reactions and their desirable conditions. In our search for them, we have studied new types of transition metal molecular catalysts dressed with a tridentate N,C,N modular ligand, which consists of a C2-symmetric side-by-side phenyl group with chiral bis(oxazolinyl) substituents. The ligand, 2,6-bis(oxazolinyl)phenyl abbreviated as Phebox, can connect covalently to transition metals by the central carbon atom. Here, we review our recent work on the chemistry of Phebox and its metal complexes, including preparation, structural analysis, asymmetric Lewis acid catalysis, asymmetric hydrosilylation, asymmetric conjugate reduction, asymmetric reductive aldol reaction, and organometallic reactions.
用于有机合成的分子催化剂应设计成适合目标反应及其所需条件。在寻找这类催化剂的过程中,我们研究了新型过渡金属分子催化剂,其配备了三齿N,C,N模块化配体,该配体由带有手性双(恶唑啉基)取代基的C2对称并排苯基组成。配体2,6-双(恶唑啉基)苯基简称为Phebox,可通过中心碳原子与过渡金属共价连接。在此,我们综述了我们最近关于Phebox及其金属配合物化学的研究工作,包括制备、结构分析、不对称路易斯酸催化、不对称硅氢化、不对称共轭还原、不对称还原羟醛反应和有机金属反应。