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Vers la synthèse totale de la paulitine. Etude de nouvelles réactions de métathèse.

Abstract : THE AIM OF THIS WORK WAS INITIALLY THE TOTAL SYNTHESIS OF PAULITINE. THE RESULTS OBTAINED LEAD US TO STUDY THE ENYNE-METATHESIS MECHANISM IN MORE DETAIL, IN ORDER TO OBTAIN THE A-B BICYCLE OF THE TARGET MOLECULE. IT WAS THEN HIGHLIGHTED THAT, FOR ENYNES WITH A TERMINAL ALKYNE AND AN OXYGEN ATOM AT THE PROPARGYLIC POSITION, THE RUTHENIUM CARBENE FIRST ! REACTS WITH THE ALKYNE. STERIC HINDRANCE AT THE PROPARGYLIC PO! SITION S EEMS TO INFLUENCE STRONGLY THE YIELD OF THE METATHESIS: CYCLIZATION IS MUCH EFFICIENT WHEN IT DECREASED. A DESMETHYL PRECURSOR OF THE TARGET BICYCLE WAS THEN OBTAINED IN SEVEN PERCENTS OVER EIGHT STEPS. ASYMMETRIC SYNTHESIS OF THE BICYCLE AS WELL AS FORMATION OF ALPHA-METHYLENE-GAMMA-BUTYROLACTONES WERE THEN STUDIED.PARALLEL TO THIS WORK, A NEW METHODOLOGY WAS DEVELOPED FOR THE METATHESIS OF ALLYLIC AMINO COMPOUNDS, WHICH ARE GENERALLY POOR METATHESIS-PARTNERS. THE USE OF BORON-BASED LEWIS ACIDS, ALLOWED TO CLEANLY OBTAIN COUPLING PRODUCTS. THIS NEW METHOD GAVE ACCESS TO A WIDE RANGE OF FUNCTIONALIZED OLEFINS, IN GOOD YIELDS, WHEN REACTIONS WERE LED IN REFLUXING TOLUENE FOR TWELVE HOURS, USING FIVE PERCENTS OF HOVEYDA-BLECHERT CATALYST AND ONLY ONE EQUIVALENT OF METATHESIS-PARTNER.
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https://pastel.archives-ouvertes.fr/pastel-00001926
Contributor : Ecole Polytechnique <>
Submitted on : Thursday, April 26, 2007 - 8:00:00 AM
Last modification on : Wednesday, July 3, 2019 - 10:48:04 AM
Long-term archiving on: : Thursday, September 30, 2010 - 7:26:19 PM

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Emeline Vedrenne. Vers la synthèse totale de la paulitine. Etude de nouvelles réactions de métathèse.. Chimie. Ecole Polytechnique X, 2006. Français. ⟨pastel-00001926⟩

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