Objective
Research objectives and content
The Gibson group have recently discovered a method for converting metal-carbonyl ligands M-CO into metal-isonitrile ligands M-CNR which circumvents the use of the maladorous and toxic isonitriles themselves. The method readily generates non-racemic chiral isonitrile ligands, a class of ligand which has been overlooked in asymmetric catalysis to date. This method uses phosphoramidates, which are easily prepared from amines in one step; reaction of the anion of this phosphite with iron pentacarbonyl, for example, gives the corresponding mono isonitrile complex (phosphinimines are known to undergo a similar reaction to this one. However, they are hygroscopic and air sensitive. Futhermore, this chemistry has been focussed mainly on creating relatively simple well-established isonitrile ligands). We thus want to define the scope of this phosphoramidate reaction and apply it to chemistry of academic and commercial significance. We propose herein to focus our attention on using chiral amines to generate chiral isonitriles as these constitute a very rare class of chiral ligand. We envisage three quite different approaches to prepare these new isonitrile complexes: i) the decarbonylation approach; ii) the halide extraction approach, and iii) the protonation approach. Moreover, we propose to direct our effort towards metal complexes that may be expected to have catalytic activity so that we will be able to assess the effectiveness of chiral isonitrile ligands in asymmetric catalysis. The research objective is to analyze the properties of non-racemic chiral isonitrile ligands and their potential in asymmetric catalysis by synthesizing complexes which are predicted to have Lewis acid activity and then examining the effectiveness of the asymmetric environment created by the isonitrile ligands using assays based on three synthetically important reactions. A successful outcome to the proposed project will a) demonstrate the scope and limitations of the new method of making isonitrile ligands, b) illustrate how the unique steric and electronic properties of isonitrile ligands may be used to create an asymmetric environnent around a transition metal, and c) produce fundamentally new enatioselective catalysts for three synthetically important organic reactions: the Diels-Alder reaction, the hetero Diels-Alder reaction and the Mukaiyama aldol reaction. In view of the high levels of interest in asymmetric catalysis in academia and industry, I anticipate that this new approach to an asymmetric environnent and the new generated catalysts will be of interest and use to both these communities.
Training content (objective, benefit and expected impact)
The results of these investigations will be disseminated by publication of papers in internationally recognised journals, presentation of seminars at UK fine chemical companies and universities and presentation of lectures at international and UK conferences.
Links with industry / industrial relevance (22)
All avenues for commercial exploitation of new catalysts will be actively explored. These will include discussions with Imperial College's wholly-owned company for the exploitation of inventions, IMPEL. The Gibson group has always had strong connections with UK industry. At present, joint projects with British Biotechnology, Chiroscience, The James Black Foundation, SmithKline Beecham Pharmaceuticals and Zeneca Pharmaceuticals are in place.
Fields of science (EuroSciVoc)
CORDIS classifies projects with EuroSciVoc, a multilingual taxonomy of fields of science, through a semi-automatic process based on NLP techniques. See: The European Science Vocabulary.
CORDIS classifies projects with EuroSciVoc, a multilingual taxonomy of fields of science, through a semi-automatic process based on NLP techniques. See: The European Science Vocabulary.
- natural sciences chemical sciences organic chemistry organic reactions
- medical and health sciences basic medicine pharmacology and pharmacy pharmaceutical drugs
- natural sciences chemical sciences catalysis
- natural sciences chemical sciences organic chemistry amines
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Coordinator
LONDON
United Kingdom
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