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Article Dans Une Revue Journal of Molecular Modeling Année : 2017

Racemization and transesterification of alkyl hydrogeno-phenylphosphinates

Résumé

In this article, we explore, both theoretically and experimentally, the general reactivity of alkyl hydrogeno-phenylphosphinates with alcohols. We show that alcohol molecules act exclusively as nucleophilic species, and add to alkyl hydrogeno-phenylphosphinates, leading to pentacoordinated intermediates. These intermediates are shown to subsequently competitively undergo alcohol eliminations and/or Berry pseudorotations. This offers several possible routes for racemizations and/or alcohol exchange reactions. Transition standard Gibbs free energies predicted from DFT calculations for the overall alcohol exchange mechanism are shown to be compatible with those experimentally measured in case ethanol reacts with ethyl hydrogeno-phenylphosphinate (134.5∼136.0 kJ mol −1 at 78 °C).

Domaines

Chimie organique
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Dates et versions

hal-01683223 , version 1 (16-04-2018)

Identifiants

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Guilhem Javierre, Rémy Fortrie, Marion Jean, Delphine Moraleda, Jean-Valère Naubron, et al.. Racemization and transesterification of alkyl hydrogeno-phenylphosphinates. Journal of Molecular Modeling, 2017, 23 (5), pp.168. ⟨10.1007/s00894-017-3343-7⟩. ⟨hal-01683223⟩
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