Biocatalytic preparation and absolute configuration of enantiomerically pure fungistatic anti-2-benzylindane derivatives. Study of the detoxification mechanism by Botrytis cinerea

Enantiomerically pure 2-benzylindane derivatives were prepared using biocatalytic methods and their absolute configuration determined. (1R,2S)-2-Benzylindan-1-ol ((1R,2S)-2) and (S)-2-benzylindan-1-one ((S)-3) were produced by fermenting baker’s yeast. Lipase-mediated esterifications and hydrolysis of the corresponding racemic substrates gave rise to the enantiopure compounds (1S,2R)-2-benzylindan-1-ol ((1S,2R)-2) and (1R,2S)-2-benzylindan-1-ol ((1R,2S)-2), respectively. The antifungal activity of these products against two strains of the plant pathogen Botrytis cinerea was tested. The metabolism of anti-(±)-2-benzylindan-1-ol (anti-(±)-2) by B. cinerea as part of the fungal detoxification mechanism is also described and revealed interesting differences in the genome of both strains

Stereoselective Synthesis of Functionalized 1,3 Diols through a New Tandem Isomerization-Aldolisation Reaction Mediated by Nickel Catalysts.

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La réaction d'isomération-aldolisation en synthèse asymétrique et en version intramoléculaire

Ce travail de thèse s inscrit dans la continuité des études sur la réaction tandem isomérisation aldolisation amorcées au laboratoire quelques années plus tôt. Le chapitre 1 concerne l approfondissement du mécanisme réactionnel, où différentes expérimentations ont été réalisées afin de vérifier l hypothèse suivant laquelle l intermédiaire clé de cette réaction serait un énol libre. Le chapitre 2 concerne le développement d une version asymétrique de la réaction tandem à partir d un alcool allylique chiral porteur d un motif imidazolidine. Au cours du chapitre 3, nous avons pu réaliser pour la première fois la réaction tandem isomérisation aldolisation en série intramoléculaire, et l appliquer à la préparation d indanones. Enfin, la version intramoléculaire a été utilisée comme nouvelle méthode catalytique pour la transposition des furanoses vinyliques en cyclopentènones, cette partie faisant l objet du dernier chapitre de ce mémoire.This thesis work is an extension of the studies regarding the isomerization aldolisation reaction, which have been carried out in our group for last few years. Chapter 1 deals with reaction mechanism, in which various experiments have been performed in order to check the hypothesis which suggests that key intermediate may be a free enol towards the aldol reaction. Chapter 2 deals with the development of an asymetric version, starting with an allylic alcohol bearing an imidazolidine group. In chapter 3, we demonstrated for the first time the intramolecular isomerization aldolisation reaction, and it is employed for the preparation of indanones moieties. Finally, in chapter 4, a new catalytic method with intramolecular version for the transformation of a vinylfuranosides into cyclopentenones has been developed.RENNES1-BU Sciences Philo (352382102) / SudocSudocFranceF

Application of the intramolecular isomerisation-aldolisation from allylic alcohols and allylic silylethers to the synthesis of indanones and indenones.

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Direct Access to Fluorinated Thiadiazolo[3,2-a]pyrimidin-7-one Systems

International audienceA mild, simple method for the regioselective synthesis of thiadiazolo[3,2-a]pyrimidin-7-ones bearing a perfluoroalkyl group is reported. In order to study the core reactivity, various nucleophile substitutions were performed involving the reactive carbon-bromide bond via a one-pot strategy

Preparation of 3‐Alkylidenephthalides: Recent Advances

3-Alkylidenephtalides represent a large class of structurally diverse molecules containing natural products or pharmaceutically designed compounds, and they exhibit a wide variety of biological activities. The goal of this review is to focus on the recent advances for the preparation of 3-alkylidenephtalides