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Fonctionnalisations sélectives de composés aromatiques et hétéromatiques.

Abstract : In the first part of this thesis, we investigated the rearrangement of Silyl ketene acetals of (hetero) of arylacétates methylthiomethyl (phenyl) 2. This rearrangement, discovered in the laboratory, allows selective functionalization of the ortho-acid (hetero) Arylacetic (Figure 1). We have synthesized esters 1a-g in September and we have observed the formation of silyl ketene acetals by NMR except in the case of the derivative of thiophene substituted di 1d. Transposition of silyl ketene acetals 2a-c, eg takes place in refluxing THF. The indole derivatives appears to be deteriorating rapidly. In order to extend the scope of this rearrangement, we tried to synthesize the phenylacetate méthylphosphinodiphényle 4 (Figure 2). However, the problems encountered during the synthesis and purification does not permit us to test the rearrangement. This project was abandoned. In the second part of this thesis, we studied the activation of carbonyl compounds by Lewis acids like R3SiNTf2. These Lewis acids were synthesized in situ. They were first used for the NMR study of the complexation of trans-methyl crotonate. The study was then extended to other carbonyl derivatives α, β-unsaturated and other methyl esters. It was revealed that the complexes are 1:1 stoichiometry, that silicon is tetravalent and NTF2 anionic group. The balance of complexation is more or less shifted towards the complexed species as a function of substrate and the Lewis acid. Comparative Study showed that Lewis acids are powerful. This acidity has been used in the reaction of β-arylated derivatives of acrylic Oxazolidin-2-one (Figure 3). This allows the reaction of aromatic compounds carboxyethyl Off 5 via an N, O-silyl ketene acetal 8.A wide variety of (hetero) aromatic rings can be used and the yield depends on the nucleophilicity of the latter and the presence or absence of a substituent on the double bond of oxazolidinone derivatives. The N, O-silyl ketene acetals 8a were eventually used in situ in a Mukaiyama-aldol reaction with benzaldehyde allowing a β-sequence tandem arylation / Mukaiyama aldol of.
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Céline Franc. Fonctionnalisations sélectives de composés aromatiques et hétéromatiques.. Chimie. Ecole Polytechnique X, 2004. Français. ⟨pastel-00002299⟩



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