Ruthenium complexes of chiral tridentate ligands: a new class of catalyst for asymmetric ketone and imine hydrogenation.

手性三齿配体的钌配合物：一类新型不对称酮和亚胺氢化催化剂。

• 批准号: EP/F030576/1
• 负责人: Matthew Clarke
• 金额: $ 31.29万
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2007
• 资助国家: 英国
• 起止时间: 2007 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FF030576%2F1
• 关键词: Ruthenium; complexes; chiral; tridentate; ligands

A catalyst allows the rate of a chemical reaction to be accelerated enormously, without the catalyst itself being used up in the reaction. Homogeneous catalysts play an ever-increasing role in industrial chemical synthesis. The demand for chemical processes to be less harmful to the environment has increased the importance of reactions that utilise tiny amounts of catalyst to promote clean, efficient reactions between two chemicals that do not normally react with each other at a measurable rate. One of the most important examples is catalytic reduction of a class of chemicals called carbonyl compounds to alcohols. Alcohols are one of the most important ingredients for drugs, flavours, fragrances and plastics. There are a number of methods to do this transformation, but most generate waste. More desirable from an economic and ecological point of view is to use a catalyst and molecular hydrogen to accomplish this task, since no waste would be formed. This has been achieved for certain classes of carbonyl compound. However, there are many classes that are not efficiently 'hydrogenated' using the current state of the art catalysts. This research project aims to develop a new type of hydrogenation catalyst that is based on ruthenium metal compounds modified with an (optically pure) ligand containing phosphorus and nitrogen atoms. The new catalysts will efficiently hydrogenate ketones to alcohols. Some alcohols exist as two mirror image structures (optical isomers),related like your left and right hands, and despite sharing the same chemical composition, each mirror image has very different biological properties. There is therefore a massive research effort aimed at producing optically active alcohols as single optical isomers for the pharmaceutical industry. It is desirable that the methods used to prepare the single optical isomer alcohols use clean catalytic chemistry due to the environmental issues raised above. This project aims to develop catalysts that can cleanly hydrogenate carbonyl compounds that are currently difficult to reduce, and to do so in a way that makes a single optical isomer. The research could lead to new alcohols products being efficiently prepared for the first time, and could lead onto commercial applications in the future.

催化剂可以大大加快化学反应的速度，而催化剂本身在反应中不会被耗尽。均相催化剂在工业化学合成中发挥着越来越重要的作用。对化学过程对环境危害较小的需求增加了利用微量催化剂促进两种化学品之间清洁，有效反应的重要性，这些化学品通常不会以可测量的速率相互反应。最重要的例子之一是将一类称为羰基化合物的化学物质催化还原为醇。酒精是药物、调味品、香料和塑料的最重要成分之一。有许多方法可以进行这种转化，但大多数都会产生废物。从经济和生态的角度来看，更理想的是使用催化剂和分子氢来完成这一任务，因为不会形成废物。对于某些类别的羰基化合物，这已经实现。然而，有许多种类的催化剂使用现有技术催化剂不能有效地“氢化”。该研究项目旨在开发一种新型加氢催化剂，该催化剂基于钌金属化合物，并用含有磷和氮原子的（光学纯）配体进行改性。这种新的催化剂能有效地将酮转化为醇。一些醇以两种镜像结构（光学异构体）存在，就像你的左手和右手一样相关，尽管有相同的化学成分，但每个镜像都有非常不同的生物学特性。因此，有大量的研究工作，旨在生产光学活性醇作为单一的光学异构体，用于制药工业。由于上述环境问题，期望用于制备单一光学异构体醇的方法使用清洁的催化化学。该项目旨在开发催化剂，可以清洁地还原目前难以还原的羰基化合物，并以产生单一光学异构体的方式进行。这项研究可能导致新的醇类产品首次被有效地制备，并可能在未来进入商业应用。

项目成果

On the NH effect in ruthenium-catalysed hydrogenation of ketones: rational design of phosphine-amino-alcohol ligands for asymmetric hydrogenation of ketones.

• DOI: 10.1002/chem.201000790
• 发表时间: 2010-07
• 期刊: Chemistry
• 作者: S. Phillips;J. Fuentes;M. Clarke

Exploring the role of phosphorus substituents on the enantioselectivity of Ru-catalysed ketone hydrogenation using tridentate phosphine-diamine ligands

• DOI: 10.1039/c1cy00253h
• 发表时间: 2011-10
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: S. Phillips;Kristian H. O. Andersson;N. Kann;Michael T Kuntz;P. Wawrzyniak;M. Clarke

New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones.

新型膦-二胺和膦-氨基-醇三齿配体，用于钌催化酮的对映选择性氢化，以及通过氰基酮的不对称还原实现简洁的内酯合成。

• DOI: 10.1186/1752-153x-6-151
• 发表时间: 2012
• 期刊: Chemistry Central journal
• 作者: Fuentes JA

Enantioselective hydrogenation and transfer hydrogenation of bulky ketones catalysed by a ruthenium complex of a chiral tridentate ligand.

• DOI: 10.1002/chem.200801929
• 发表时间: 2009-01
• 期刊: Chemistry
• 作者: M. Díaz-Valenzuela;Scott D Phillips;Marcia B France;Mary E. Gunn;Matthew L. Clarke