Objetivo This project aims to develop new asymmetric catalysts for carbon-carbon bond forming reactions. The catalysts will be designed around the simultaneous use of two different metals to bind and activate both components of the reaction at the same time. This will result not only in increased activity, but also in high levels of asymmetric induction due to the highly pre-organised nature of the transition state. The hetero-bimetallic catalysts prepared in this project are anticipated to be superior to existing mono-metallic catalysts for reactions which are known to be susceptible to asymmetric catalysis, but more importantly are also expected to be capable of catalysing reactions for which no asymmetric catalyst is currently available. The three applicants have been collaborating together in the area of asymmetric catalysis for the last ten years and have extensive preliminary results in the areas of asymmetric cyanohydrin synthesis and asymmetric phase-transfer catalysis to support the hypothesis of the proposal. The previous collaborative work of the applicants has been recognised as world leading by the European Commission through the award of the 2001 Descartes prize to a consortium including all three of the current applicants. In the currently proposed work, we will prepare new polydentate chiral ligands which are specifically designed to coordinate to two different metals. This is different to our previous work where the ligands were not designed to coordinate to two metals, and bimetallic complexes formed by accident. Clearly if the ligands are designed to complex to two different metals then the probability of them doing so will be greatly increased. The new ligands will be complexed to transition metals, main group metals and lanthanides and the resulting bimetallic complexes fully characterised using both NMR and X-ray crystallographic techniques as appropriate. They will then be tested for catalytic activity in a wide range of important carbon-carbon bond forming reactions including: addition of various nucleophiles to aldehydes, ketones and imines; Darzens condensations; reductive couplings of aldehydes and imines; and Diels-Alder reactions. The enantiomeric excess of the products will be determined by chiral-NMR methods, chiral GC or chiral HPLC as appropriate, and evidence for the catalytic activity being based on heterobimetallic catalysis will be obtained from a study of non-linear effects and variation of the catalyst structure. This project will therefore result in the development of novel asymmetric catalysts which can be used by industrial and academic chemists in the synthesis of pharmaceuticals, agrochemicals, and other important commodities where the chirality of the product is critical for the activity of the product. The project will also demonstrate the concept of using heterobimetallic complexes as catalysts. Palabras clave Co-ordination & Organometallic Chemistry Homogeneous Catalysis Synthesis & Growth Programa(s) IC-INTAS - International Association for the promotion of cooperation with scientists from the independent states of the former Soviet Union (INTAS), 1993- Tema(s) Data not available Convocatoria de propuestas Data not available Régimen de financiación Data not available Coordinador UNIVERSITY OF NEWCASTLE UPON TYNE Aportación de la UE Sin datos Dirección BEDSON BUILDING NEWCASTLE UPON TYNE Reino Unido Ver en el mapa Coste total Sin datos Participantes (2) Ordenar alfabéticamente Ordenar por aportación de la UE Ampliar todo Contraer todo NESMEYANOV INSTITUTE OF ORGANOELEMENT COMPOUNDS Rusia Aportación de la UE Sin datos Dirección VAVILOV STREET, 28 MOSCOW Ver en el mapa Coste total Sin datos UNIVERSITÉ DE PARIS-SUD Francia Aportación de la UE Sin datos Dirección ORSAY Ver en el mapa Coste total Sin datos
