氢键导向的不对称氢甲酰化反应研究

项目名称： 氢键导向的不对称氢甲酰化反应研究

项目编号： No.21302116

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 汤卫军

作者单位： 陕西师范大学

项目金额： 25万元

中文摘要： 将烯烃氢甲酰化得到醛是一个非常重要并广泛被工业化生产的催化反应。其中最为重要的是不对称氢甲酰化反应，该反应可以从廉价的烯一步合成具有重要应用价值的光活性醛，具有广阔的商业价值和应用前景，特别是功能化烯烃的不对称氢甲酰化，其产物衍生物如手性氨基醇，手性二醇，手性二胺，手性氨基酸或酯等是重要活性化合物的结构单元。然而，针对官能化烯烃的研究还很处于初步发展阶段，可能原因在于其官能团参与金属的配位，导致催化剂失活。在基于前续研究基础上，本项目拟结合有机催化剂和金属催化剂，通过分子氢键来导向金属催化剂，以期应用于具有功能化烯类底物的不对称氢甲酰化反应，通过分子氢键类型，手性匹配原则，以及优化配体空间结构和电子效应，以期能找到高效，高立体选择性和高区域选择性的催化体系，在此研究的基础上，阐明反应机理，为进一步开发和设计有效的不仅能应用于不对称氢甲酰化反应，而且还能有效催化其他反应的催化剂提供理论依据。

中文关键词： 氢化还原；手性氨基酸；四氢喹啉；酮酯还原；钴催化氢化

英文摘要： The preparation of aldehydes by catalytic hydorformylation of olefins is a very important reaction, which has been applied widely in industry.Of particular importance is the asymmetric hydroformylation (AHF), which allows the transforamtion of cheap olefins into optically active aldehydes in one single step.In particular, AHF of functionalized olefins leads to the production of highly valuable multifunctional products, such as chiral amino alcohols, chiral diols, chiral amines, and amino acids/esters,which are important building blocks for many active compounds. However, it is still in its developing stage, it might be due to the coodination of functional groups to metal catalyst, which leads to its inactive. Based on previous research, this project will focus on the AHF of selected functionalized olefins catalyzed by metal catalysts and organocatalysts, which will be combined together with the catalysis and asymmetric induction directed by hydrogen bonding between the substrates and catalysts. It is expected to deliver novel, highly efficient,enantioselective and regioselective catalytic systems for AHF taking advantage of hydrogen bonding, chiral matching,structures and electronic effects.Furthermore,by elucidating the mechanism, the project will give a theoretic foundation for developing highly efficient cata

英文关键词： hydrogenation reduction；chiral amino acid；tetrahydroquinolines；reduction of ketoester；cobalt catalyzed hydrogenation