Led by Professor Matthew Davidson, University of Bath
The development of new sustainable catalyst technologies for organic transformations and their successful implementation across the chemicals sector is perhaps the most important factor in ensuring the future prosperity of a key component of the UK’s manufacturing base. Organic transformations are central to the manufacture of bulk and fine chemicals, pharmaceuticals and polymers; and it is essential that new fundamental research be initiated so that the UK maintains a strong internationally competitive position.
The Chemical Transformations theme aims to promote the prosperity of the UK manufacturing base in fine and bulk chemicals, polymers and pharmaceuticals
There are four new chemical Transformations projects projects currently running replacing the initial exemplary projects. There are also two core Initial Projects that are still running in this theme. More details of the projects can be found below
- Catalysis in Confined Environments: Well–Defined TM–Catalysts@MOF
To develop methodologies for the synthesis of encapsulated catalysts in platform Metal Organic Frameworks with the focus on adding value to hydrocarbon feedstocks will be developed. This will provide a step–change in the implementation of well–defined TM–catalysts@MOF in catalysis, offering a unique platform upon which to exploit this technology further.
- Comparing Homogeneous and Heterogeneous Catalysts For Selective Polymerisations
Selectivity is one of the most important challenges facing polymer science: the ability to control and select particular monomers from mixtures remains an un-solved problem for the field but an urgent requirement for the development of future materials.
In contrast, Nature exerts exquisite sequence selectivity in biopolymers which, in part, controls their myriad of biological roles and functions. Our proposal is to develop and understand a new catalytic means to control sequence selectivity, using mixtures of monomers so as to prepare highly controlled polymeric materials (ABCDEF…type) suitable for applications spanning medicine, engineering materials, and advanced plastics. We will accomplish this by developing and comparing new multi-metallic homogeneous and heterogeneous catalysts
Co Funded with Design
Prof Charlotte Williams
Dr Robert Raja
- Ionic Liquid-Metal Oxide Composite Catalysts for Beckmann Rearrangement
This project combines UK expertise that is world leading in solid acids, ionic liquids and X-ray techniques to design new heterogeneous acid catalysts for the cleaner preparation of lactams. Lactams are intermediates in the synthesis of nylons such as nylon 6.
- A Collaborative Mechanistic Approach to Paramagnetic Iron Catalysis.
Platinum Group Metal (PGM)-based homogeneous catalysts are ubiquitous in synthetic organic transformations. These PGM-based catalysts have many attractions: they are usually easy to handle; tolerant of functional groups and reaction media and active in a wide variety of processes. However, the continued use of PGMs in pharmaceutical, fine chemical, agrochemical and related sectors is ultimately limited by (a) very high (and volatile) cost, (b) toxicity and (c) sustainability issues. The hunt is on to replace homogeneous catalysts based on PGMs with those formed from so-called Earth-Abundant Metals (EAMs), with iron being a particularly promising candidate in many instances. This is because iron is cheap, enormously abundant and has relatively low toxicity and environmental impact. Accordingly replacing PGMs with iron in catalysts for a variety of transformations is an extremely topical area of research.
Professor Robin Bedford (Bristol)
Dr Antonis Messinis
- Activation and Reaction of sp3 Centres
continuing Core project in the Initial Exemplar Projects that started in 2014
The project involves a collaboration of academics that are internationally recognised for their work in chemo- and bio- catalytic hydrogen transfer reactions and mechanism, together with representatives of key Pharma, Agrochem and Fine Chemical end-user companies. There are links we wish to exploit with other sub-projects: support from Catalyst Design in modelling ligand/metal/substrate/product interactions and catalytic cycles; other projects within Chemical Transformations such as Biocatalysis for High Value Transformations and Catalysis within Confined Environments (cf. our use of immobilised and encapsulated catalysts).1 There is a link with Energy Catalysis through our transformations involving low energy redox reactions for low energy processing; the catalysts will generate hydrogen from formic acid and C1-C3 alcohols.2 The project also has synergies with Environmental Catalysis, indeed the collaborating companies demand this, for example: improved atom efficiency of catalytic hydrogen transfer over traditional reduction and oxidation reagents (eg NaBH4, Swern); the catalysts work in sustainable solvents and would be expected to do so here;3 the methodology we develop should be applicable to renewable starting materials to enable green chemistry methods for making heterocycles (eg use of glycols, hydroxy and amino acids). A key aspect of this project is to develop industrially useful methods which necessitate efficient catalytic processes
Prof Jon Williams and
Prof John Blacker
- Biocatalysis for High Value Transformations that Chemical Catalysis Struggles To Perform
Continuing Core project from the initial Exemplar Projects
This s project will have huge breadth as a function of its use of exploitation and design of biological catalysis for application to unique transformations. It will encompass use of natural and unnatural moieties and so bridge the gap between homo and bio.
- Metal-Organic and Organocatalytic Methods for Stereocontrolled Activated Monomer Catalysis
- A Multi-tool Approach to Unravel the Modus Operandi of Olefin OligomerisationCatalysts
Catalyst characterisation under true operating conditions will underpin a fundamental understanding of the nature of the active species present upon activation of the procatalyst and after introduction of the substrate. While this project will initially focus on chromiumbased ethylene oligomerisation, a reaction that is of significant industrial interest, the project can be extended to other oligomerisation or polymerisation catalyst systems and to other catalytic processes. Specific chromiumbased catalysts that will be investigated are well established and highly tuneable systems containing bis(benzimidazole)methylamine (BIMA), bis(phosphino)amine (PNP), and bis(thiolate)amine (SNS) ligands. Judicious choice of the ligands will enable the generation of systems with moderate activities, not to fill the spectroscopic cells with product too quickly. The important questions that will be addressed are: the oxidation state of the active species before/after introduction of ethylene; the immediate coordination environment at the chromium centre in the active catalyst; the nature of the deactivated catalyst; the origins of catalyst deactivation and whether distinctly different chromium species can be identified as being responsible for selective oligomerisation and polymer by-product formation.
Dr. George Britovsek
- CarboCat: Ligand Design for Enhanced Proton Transfer in Homogeneous Alkene and Alkyne Alkoxycarbonylation – Understanding and Application
This challenging project seeks to open up and extend the scope of the potentially synthetically versatile alkene/alkyne alkoxycarbonylation reactions for the preparation of valuable commodity and higher-value fine chemical intermediates, something of broad commercial interest.
The work will involve a combination of ligand design/synthesis, molecular catalyst screening, computational modelling, kinetic studies, and in situ spectroscopic investigations (HP-IR and XAS), with with primary focus on establishing catalyst action and structure/performance correlations.
This research project is a close collaboration between Durham University (Drs Phil Dyer and Simon Beaumont), University of St. Andrews (Dr Matt Clarke and Prof. Michael Buehl), and the University of Manchester (Prof. Richard Layfield).
Philip W. Dyer
- Biocatalysis for High Value Transformations that Chemical Catalysis Struggles to Perform
Continuing Core project from the initial Exemplar Projects
This project will have huge breadth as a function of its use of exploitation and design of biological catalysis for application to unique transformations. It will encompass use of natural and unnatural moieties and so bridge the gap between homo and bio.
The directing abilities of enzymes are underutilized for efficient synthesis. This project will greatly expand heterocycle transferases using unnatural substrates of high “chemical value” (bioactivity, step efficiency, utility). Novel biocatalytic cascades will be developed to transform low-value chemicals into advanced intermediates and complex products using reactivity and selectivity motifs unmatched by traditional chemical synthesis.
Previously mastered techniques in GT handling as well as high-throughput expression/purification can rapidly generate screening-level quantities of hundreds of potential biocatalysts. A panel of natural and “chemically enhanced” substrates will provide a biocatalytic map to high-value activities.
GT activities will be combined with one of Nature’s most powerful tools, P450 enzymes, which oxidize bare C-H bonds to hydroxyl functionalities. Such a sequence will generate GT substrates in situ, creating a potential tandem enzymatic “C-H heterocycle functionalization” sequence. The control of biocatalytic oxidative functionalization is key for efficient conversion of abundant biomass feedstocks to valuable products.
Benjamin G. Davis/ Matthew G. Davidson
- Frustrated Lewis Pairs for Metal-Free Catalysis of Hydrogenation and Dehydrogenation Processes
In 1923 Gilbert N. Lewis defined acids as electron pair acceptors and bases as electron pair donors.1 In most cases the two classes of compound combine to give acid/base adducts through coordinate bond formation. Frustrated Lewis pairs (FLPs) – in which steric constraints prevent such bond formation – were described conceptually as far back as 1942,2 but have emerged as a new paradigm for small molecule capture and activation following a landmark report by Stephan and co-workers in 2006.3 These systems have been exploited in ‘metal-free’ catalysis such as FLP-catalysed (asymmetric) hydrogenation chemistry, which relies on the ability of the phosphonium hydroborate ([R3PH]+[HBArF3]-) derived from H2 cleavage to sequentially transfer H+/H- to unsaturated substrates such as imines.4 Such processes avoid the use of expensive and toxic heavy later transition (‘Noble’) metals leading to improved cost/sustainability associated with green chemical processes.
Given the highly promising preliminary work in the hydroboration of unsaturated substrates, we target the catalytic conversion of CO2 to formate/methoxy derivatives, which is relevant to both the environmental and energy themes. Optimizating this transformation, and the demonstration of catalytic Si-N dehydrocoupling are key targets for this project. We anticipate additional collaborations in cascade C-H activation CO2 coupling chemistry (environmental theme) and applications of non-natural FLPs in proteins (biocatalysis theme).
Paul Kamer / Simon Aldridge
- Hydrogenation of Organic Compounds: Electrochemical Intervention to Optimized Catalysts
This project seeks to develop a detailed understanding of platinum-based heterogeneous catalysts used for the hydrogenation of organic compounds, with the aim of improving catalyst usage and enhancing catalyst design. We advocate electrochemistry to solve key problems pertaining to heterogeneous chemical catalysis. Together with a wide range of structural and spectroscopic probes, this multifaceted project will enable the development of new catalysts that will be assessed for hydrogenation reactions.
Initial projects were focused on
i)Enhancing selectivity and sustainability of existing processes,
ii) Pharmaceutical process chemistry; synthesis gas conversion; renewable polymers, iii) New catalytic approaches to transformations including Catalysis in confined environments; transition metal free catalysis; biocatalysis for new chemical transformations and
iv) Combination of biocatalysis, homogeneous and heterogeneous, organo- and metal-based catalysis
Information on the initially projects can be found by clinking on the link