Modular Helicenoid Lewis Base Catalysts Applied to Modern Synthesis and Materials

The property of handedness is of extreme importance in chemistry because this property controls so many aspects of life, both inside ourselves and the world around ourselves. The shapes of molecules act in a similar fashion to the human hand: you will struggle to properly fit a left hand into a right handed glove. This handedness of molecules has profound effects on their biological activity. Therefore, being able to control the handedness of synthesised compounds is critical to the function of these products. One way to accomplish this is by using catalysts that possess one-sense of handedness. An area of increasing relevance to chemistry, and society beyond the world of chemical research, is organocatalysis where small organic molecules, as opposed to transition metals, catalyse the formation of useful handed molecules.

Nature constructs many structures which are based upon a helical shape, from the large (e.g. hurricanes) to the very small (our genetic DNA). These structures are chiral by virtue of being helical, that is, they are "handed." This proposal concerns the development of much improved, powerful helical organic catalysts. We wish to use these to control the handedness when forming products with a specific sense of handedness or when performing polymerisations. This project will examine the development of new reactions and the formation of "handed" polymers, with progress in these areas likely to be of significant benefit to science and society.

In particular, the polymers we wish to examine may have a large impact on all of our lives. We will seek to use our catalysts to make polymers, made from materials sourced from almonds, which will have properties similar to polystyrene. This has significance as polystyrene is a non-biodegradable material filling global land fill sites. We all see a lot of polystyrene on a day-to-day basis... the mountain of "coffee cups" rises and rises in land fill contexts. The polymers we will synthesise will be biodegradable, so will compost quite happily yet our catalyst will help us keep the desirable mechanical properties of polystyrene.

Taken together, this project will make strides in new catalyst design, reaction development and searching for new "green" polymers to replace an evasive, taken for granted polymer.

A number of key stakeholders are envisaged to directly benefit from this work.

1) Direct scientific communities i.e. that of organic synthesis and polymer material will benefit from the disclosure of the new and active catalyst structures and the stereocontrolled entry to polyester polymers as described in the proposal. Concomitantly with these beneficiaries, there will be benefit accrued at The University of Bath through this work i.e. the research groups of Carbery and Davidson. These groups will benefit from the reported findings with respect to international standing, the future raising of funding and commercialisation of catalysts and materials. Indeed, this last issue will offer the University an opportunity to direct to some extent through commercialisation of this research and its findings.

2) Scientists working in the applied scientific industries e.g. pharmaceuticals and polymer materials will benefit from this work. Once reported to the greater scientific community, the findings will hopefully form the basis of commercial collaboration with these industries. The use of the catalysts for the kinetic resolution of amines and dynamic kinetic resolutions discussed in the proposal will be a highly desirable entry to valuable synthetic building blocks.

3) We believe in the long run that society will benefit from this work. More specifically, the development of sustainable equivalents of polystyrene will revolutionise the environmental problem of polystyrene accumulation in the environment. Polystyrene is a very widely used polymeric material, however, this polymer is ultimately sourced form petrochemical-derived monomers i.e. styrene. This project will develop stereochemically well-defined polymers which mimic polystyrene. We will therefore begin a reversal in the dependence on petrochemical material sin in day-to-day society.