Objetivo This project is a development of a successful, recently completed, earlier INTAS programme which has been expanded to now involve eight research teams, four from NIS and four from the INTAS countries. The project is broken into six main tasks each of which often involves a number of sub-tasks. Each of the main tasks will be carried out in a collaborative manner involving at least two of the research teams and in many cases four teams.This will be achieved through a combination of(i) sub-tasks carried out by a single team and coordinated within the total task and;(ii) a heavy emphasis on the exchange of students for extended periods.Such exchanges were key to the outputs of the earlier project by way of scientific papers in International Journals, posters and conference presentations.The key target of the proposal is to apply metal mediated reactions in the development of new synthetic procedures and to apply these to the synthesis of biologically active molecules and, in particular, to those containing three member rings. Such molecules are known to control a very wide variety of key transformations in nature and are key targets for the pharmaceutical industry. The proposal will cover a number of aspects of metal mediated reactions, involving e.g. lithium and transition metals, but will have a high emphasis on the recent rapid developments in titanium chemistry, many of which are exemplified in the direct conversion of esters into cyclopropanols on reaction with an organomagnesium reagent and titanium isopropoxide (the Kulinkovich reaction).The primary targets of this proposal are as follows:(i)The study of isoxazolones as substrates in the Kulinkovich reaction, in order to develop simple routes to novel heterocycles;(ii)The stereoselective preparation of functionalized alkenes by titanium-mediated carbon-carbon forming reactions of Grignard reagents with allylic alcohols and related compounds. The procedures developed will be to apply to directed synthesis of natural compounds, in particularly to the efficient syntheses of important insect pheromones;(iii)The exploitation of a related reaction, the generation of cyclopropyl radicals from dibromocyclopropanes by reaction with an alkyl magnesium halide and titanium isopropoxide, in particular in intramolecular cyclisations leading to carbocycles and heterocycles containing a bicyclo[3.1.0]hexane skeleton. In order fully to exploit this chemistry, new methods for the introduction of functionality into simple enantiomerically pure cyclopropanes using chromium mediated oxidation will be examined;(iv)Cyclopropanes are responsible for enzyme inhibitions, phytotoxicity, insecticidal, antifungal, herbicidal and plant growth regulatory activities as well as for antibiotic, antimicrobial, antitumoral, antibacterial, antiviral and neurochemical potencies. New methods for the construction of functionally substituted cyclopropanes are of significant interest. The proposal will explore the synthesis of a variety of such important species using low valent titanium chemistry.A related objective will be to approach a fundamental problem of organic synthesis - the development of effective procedures for the synthesis of strained organic compounds containing unusual combinations of structural units. New methods of synthesis of highly strained fused and bridged carbo- and heterocycles will be developed based on a metal mediated methodology. The proposed strategy will affect in one synthetic step a sequence of reactions: for instance the Kulinkovich reaction, which is followed by transformation into high strained molecules. The domino process may also involve consecutive carbene generation, ylide generation, and intramolecular cycloaddition of the ylide to a dipolarophile fragment in the same substrate. Carbenes will be generated from diazocompounds or cyclopropenes in reactions catalysed by transition metals. In a related task the generation of carbenes in the presence of organometallic species, the formation of ylides and the modification of their subsequent reactions will be examined in order to exploit further the chemistry of terpenes, which form a key part of the 'chiral pool'. 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) 3 - Chemistry OPEN - OPEN Call Convocatoria de propuestas Data not available Régimen de financiación Data not available Coordinador University of Wales, Bangor Aportación de la UE Sin datos Dirección Deniol Road LL57 2UW Bangor, Gwynedd Reino Unido Ver en el mapa Coste total Sin datos Participantes (7) Ordenar alfabéticamente Ordenar por aportación de la UE Ampliar todo Contraer todo Belarussian State University Bielorrusia Aportación de la UE Sin datos Dirección Fr. Skaryny Avenue, 4 220050 Minsk Ver en el mapa Coste total Sin datos Georg-August-University of Goettingen Alemania Aportación de la UE Sin datos Dirección Tammannstrasse 2 37077 Göttingen Ver en el mapa Coste total Sin datos Kazan Medical State University Rusia Aportación de la UE Sin datos Dirección 49 Butlerov Street 420012 Kazan Ver en el mapa Coste total Sin datos M.V. Lomonosov Moscow State University Rusia Aportación de la UE Sin datos Dirección Vorobjevy Gory 119899 Moscow Ver en el mapa Coste total Sin datos St. Petersburg State University Rusia Aportación de la UE Sin datos Dirección Universitetskii prospekt 2 198904 St. Petersburg Ver en el mapa Coste total Sin datos Universita di Firenze Italia Aportación de la UE Sin datos Dirección Via Caponi 9 50121 Firenze Ver en el mapa Coste total Sin datos Université de Paris Sud Francia Aportación de la UE Sin datos Dirección 91405 Orsay Cedex Ver en el mapa Coste total Sin datos
