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Approche théorique de la réactivité des isonitriles en chimie organique

Abstract : Isocyanides are known for a long time, but have been studied only recently. A theoretical approach allowed us to investigate in details the Nef and the Ugi reactions. We first focused on the former. After elucidating its mechanism, we studied solvent effects and proposed new experimental conditions. We then studied the acyl moiety and isocyanide influences, such as the leaving group one. All the variations were rationalized by linking the activation energy to the leaving group pKa. Simultaneously, we studied the Ugi reaction. The mechanism proposed by Ugi for this complex reaction was still unverified 50 years after its discovery. A thorough and quasi-complete study of all the possible mechanisms were lead, using a mixed theoretical and experimental approach. The mechanism of this reaction was demonstrated, in both methanol and toluene. Rate determining steps and driving forces were highlighted and differ from those proposed by Ugi. A variation of the Ugi reaction is the Ugi-Smiles coupling, for which numerous experimental results are still unexplained. We thus studied the Smiles rearrangement. We showed the key-role of an intramolecular hydrogen bond on the reaction feasibility, and extended this observation to intermolecular reactions. We also studied the four substituent influence on the barrier, aiming to build a predictive model.
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Submitted on : Tuesday, January 24, 2012 - 3:27:26 PM
Last modification on : Monday, December 14, 2020 - 2:40:02 PM
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  • HAL Id : tel-00662613, version 1


Nicolas Chéron. Approche théorique de la réactivité des isonitriles en chimie organique. Autre. Ecole normale supérieure de lyon - ENS LYON, 2011. Français. ⟨NNT : 2011ENSL0688⟩. ⟨tel-00662613⟩



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