Chiral 3d-transition metal catalysts on the basis of novel tetradentate bis(iminoalkoxid) ligands and their investigation in the asymmetric catalysis of multiple bond transformations (epoxidation, alkynylation of ketones)

基于新型四齿双(亚氨基醇盐)配体的手性3d-过渡金属催化剂及其在多键转化（酮的环氧化、炔基化）不对称催化中的研究

• 批准号: 214588454
• 负责人: Dr. Paul Benndorf
• 金额: --
• 依托单位: Institut für Anorganische Chemie (aoc)
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2012-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/214588454?language=en
• 关键词: Chiral; 3d; transition; metal; catalysts

For the pharmaceutical industry, it is of great interest to obtain enantiomerically pure products, since normally only one enantiomer shows the corresponding pharmacological effect. Accordingly, the enantioselective synthesis of chiral molecules is subject of intense research. One way to accomplish this is through the use of chiral catalysts. With them it is possible to perform atom efficient synthesis and thus avoid waste. This is both economically and ecologically wise.Therefore, asymmetric catalysts with novel chiral, tetradentate bis(iminoalcohol) ligands should be developed in this research project. Initially, different complexes with 3d transition metals (titanium, chromium, manganese, iron, copper, zinc) should be synthesized. In addition the synthesis of bimetallic complexes should be tried, since these could have better catalytic properties due to cooperative effects. The properties of the complexes should be tested in the asymmetric catalysis of multiple bond transformations (epoxidation, alkynylation of ketones). By varying the substituents of the ligand, the catalysts should get optimized to achieve high enantiomeric excesses. Overall, an inexpensive and highly variable, chiral ligand system should be developed that is easy to synthesize and its complexes are able to compete in catalysis with the established salen complexes.

对于制药工业来说，获得对映体纯的产品非常有意义，因为通常只有一种对映体显示出相应的药理作用。因此，手性分子的对映选择性合成是深入研究的主题。实现这一目标的一种方法是使用手性催化剂。有了它们，就可以进行原子有效的合成，从而避免浪费。这既经济又环保。因此，本研究项目应开发具有新型手性四齿双（亚氨基醇）配体的不对称催化剂。最初，应合成具有 3d 过渡金属（钛、铬、锰、铁、铜、锌）的不同络合物。此外，还应该尝试合成双金属配合物，因为它们可以通过协同效应具有更好的催化性能。配合物的性质应在多键转化（酮的环氧化、炔基化）的不对称催化中进行测试。通过改变配体的取代基，应优化催化剂以实现高对映体过量。总的来说，应该开发一种廉价且高度可变的手性配体系统，该系统易于合成，并且其配合物能够在催化作用上与已建立的萨伦配合物竞争。

项目成果

Metal/bromide autoxidation of triglycerides for the preparation of FAMES to improve the cold-flow characteristics of biodiesel

金属/溴化物自氧化甘油三酯制备FAMES以改善生物柴油的冷流特性

• DOI: 10.1016/j.cattod.2014.02.041
• 发表时间: 2014
• 期刊: Catalysis Today
• 影响因子: 5.3
• 作者: P. Phung;W. N. Rowlands;A. Thiyakesan;P. Benndorf;A. F. Masters;T. Maschmeyer
• 通讯作者: T. Maschmeyer