Self-assembly of asymmetric catalysts

Lead Research Organisation: University of St Andrews
Department Name: Chemistry

Abstract

Homogeneous catalysis plays an ever-increasing role in chemical synthesis. A catalyst allows the rate of a chemical reaction to be accelerated enormously, without the catalyst itself being used up in the reaction. 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. An important challenge in homogeneous catalysis is being able to control selectivity while retaining high catalytic activity. Many important drug and agro- chemicals exist as two mirror image structures called optical isomers that are related like your left and right hands, and despite sharing the same chemical composition, each mirror image has very different biological properties (New drugs that exist as optical isomers are now required to be prepared as a single optical isomer). There is therefore a massive research effort aimed at producing optically active compounds as single optical isomers for the pharmaceutical industry, with catalytic methods being potentially more efficient and less harmful to the environment. However, one of the big problems that prevents wider application of catalytic methods is the vast amount of time and money required to find the perfect catalyst for the specific reaction being studied. Many catalysts are difficult to make, and a catalyst that is good for one group of reactants is often hopeless for another. There is now massive interest in methodology that allows a large number of catalysts to be prepared rapidly. This programme has the ambitious aim of developing a new approach to solving this problem. The preparation of catalysts that can be changed by binding to a large collection of complementary additives in an instantaneous reaction that uses hydrogen bonding to hold the molecules together (Hydrogen bonds are the bonds that hold DNA together, and are formed very rapidly without any chemical reagents or intervention). If the project is fully successful, the time taken to find the perfect catalyst will be reduced dramatically, and chemists will have something analagous to a skeleton key for unlocking every door: a toolbox of catalysts that can be adjusted to every set of reactants that might be used. The project will involve detailed work on the mechanism of the self-asembly process, evaluating the strength of the hydrogen bonds and the conditions under which they are able to form. Using this approach some new development in currently challenging but important catalytic reactions should be possible
 
Description This project aimed to understand the remarkable self-assembling catalysts we had discovered. The mechanistic study was rather challenging and actually involved us having to redesign a new catalyst system that was more amenable for study. this was achieved and a paper that described the exact function of the two-component catalysts was published. A surprising observation made here led us to extrapolate a mechanstic feature in our catalysts to other systems more widely applied that show some similar features. Following on from our first report on such systems, the use of self-assembled organocatalysts is now quite a widespread niche topic. We actually moved on to consider transition metal catalysts that could also assemble with a rationally designed co-catalyst to deliver a catalyst with enhanced features. Some interesting proof of concepts were established regarding the design of catalysts that are programmed to bind either additives or recognise a secondary binding site on the substrate. Some rather unusual ligands and metal complexes were also successfully synthesised. Attempts to tune these up into genuinely useful processes are still being pursued. Some other speculative studies on activation C-H bonds selectively were less successful. A side effect of these studies was contributing either key intermediates or key information to other projects in catalysis we have been studying, so these reports are also linked here. Overall, this study helped provide a solid foundation for an approach that quite a few chemists now find appealing. It also scoped out what might be achieved with transition metal complexes with bifunctional and trifunctional ligands, solved synthetic challenges in their synthesis, and studied a range of potentially important catalytic protocols.
Exploitation Route Our findings are being used by other academics interested in self-assembly of catalysts. Even the very specific specialised topic we studied for the first time represents a bit of a mini-field, with a significant number of the 150 or so papers that cite our first paper referring to it was starting point for this area. It is still too early to predict whether all that activity will genuinely have a direct impact outside chemical research, and we therefore moved towards optics of more immediate potential societal impact. It is fair to link a topic of current study in my group on self-assembled heterogeneous catalysts as arising from me spending time thinking about self assembly of catalysts during this grant. I believe the way this alternative direction may become more directly useful.
Sectors Chemicals,Manufacturing, including Industrial Biotechology