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Stereodefined Fluorinated Tetrasubstituted Olefins by Catalytic Cross-Metathesis

Project description

Stereoretentive cross-metathesis: a route to innovative pharmaceuticals

Olefin metathesis is an important reaction in pharmaceutical discovery and development in which the constituents of olefins, which contain carbon-carbon double bonds, are substituted to form new compounds. So-called tetra-substituted olefins with a fluorine atom and/or polyfluoroalkyl moiety substitution are highly sought after, as are ways to produce specific conformational preferences (stereocontrol). Existing methods to achieve such results are inadequate. With the support of the Marie Skłodowska-Curie Actions programme, the FLUORMET project aims to develop new catalysts to promote the formation of stereodefined tetrasubstituted fluoro-alkenes by stereoretentive cross-metathesis. They will be used to synthesise fluorinated analogues of natural products and modify important drugs to achieve superior bioactivity or new activity in a different therapeutic area.

Objective

Practical strategies that provide facile access to tetrasubstituted olefins bearing a fluorine atom and/or a polyfluoroalkyl moiety are crucial to drug discovery and development and are therefore in high demand. Equally important and sought-after are reliable and stereocontrolled methods for modifying such alkenes. Nonetheless, such methods are scarce, and those available are severely limited in scope.
In this context, catalytic olefin metathesis offers a unique disconnection to access modifiable tetrasubstituted alkenes in either stereoisomeric form. Still, there are no more than a handful of such reactions, with all ring-closing metathesis (RCM) processes affording a cyclic alkene bearing two methyl groups. There is only a single reported example of a cross-metathesis (CM) reaction that affords a tetrasubstituted olefin as a stereoisomeric mixture.
Inspired by recent progress by the host group, we will develop new cyclic alkylidene catalysts that are designed to promote formation of stereodefined tetrasubstituted fluoro-alkenes by stereoretentive CM. The substrates will be readily available trisubstituted olefins and commercially available F/F3C-substituted alkenes. The products will be value-added tetrasubstituted olefins bearing a F/F3C moiety as well as a modifiable C–Cl or C–Br bond. The method will be applied to the synthesis of fluorinated analogues of natural products such as fluoro-pateamine A.
Another key aspect will be application to the modification of important drugs. Our goal will be to utilize the new catalytic chemistry to generate analogues that might exhibit superior bioactivity, or be active in a different disease area. We will transform entecavir or barmumycin to their polyhalogenated analogues, which will be tested for in vitro bioactivity through collaboration with experts. The conversion of readily accessible olefins into their polyfluorinated, tetrasubstituted analogs holds considerable and as-of-yet untapped promise for drug discovery.

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HORIZON-TMA-MSCA-PF-EF - HORIZON TMA MSCA Postdoctoral Fellowships - European Fellowships

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(opens in new window) HORIZON-MSCA-2023-PF-01

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Coordinator

UNIVERSITE DE STRASBOURG
Net EU contribution

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€ 195 914,88
Address
RUE BLAISE PASCAL 4
67081 STRASBOURG
France

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Activity type
Higher or Secondary Education Establishments
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Total cost

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