An Alternative Mechanism for Diels-Alder Reactions of Evans Auxiliary Derivatives

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Abstract

The mechanism proposed by Evans for the dialkylaluminum chloride promoted Diels-Alder reaction of cyclopentadiene with alpha,beta-unsaturated N-acyloxazolidinones has been widely used as a basis for the rationalization of the experimental selectivities observed in many different types of reactions in which oxazolidinones or imidazolidinones are used as chiral auxiliaries. In this manuscript we introduce a new and more general model based on molecular modeling and NMR spectroscopy data that avoids several ambiguous concepts raised by the Evans model and fully explains all available experimental data. While the Evans proposal relies on the formation of high-energetic ionic chelates that promote the rotation of the amide bond in the N-acyloxazoliclinone molecule, outmodel is based on the catalysis by means of low-energetic mono- or bicomplexes at the chain and the ring carbonyl groups that are easily observed by NMR spectroscopy measurements. The observed selectivities are explained by a chirality-transfer concept, in which an achiral Lewis acid works as a bridge for the transfer of chirality between a chiral auxiliary and a prochiral reactive center. Different to the Evans proposal, this mechanism fully explains the experimental selectivities for low Lewis acid concentrations, based on the catalysis by means of concurrent monocomplexes at the chain or the ring carbonyl groups, as well as the increased reaction rates and selectivities experimentally observed for high Lewis acid concentrations. The model can be extrapolated to nonchelating and other chelating Lewis acids, thereby allowing for the rationalization of much experimental data that were never explained by the Evans proposal.
Original languageEnglish
Pages (from-to)7665-7677
JournalChemistry-A European Journal
Volume15
Issue number31
DOIs
Publication statusPublished - 1 Jan 2009

Keywords

  • Density functional calculations
  • Transition states
  • NMR spectroscopy
  • Evans auxiliary
  • Diels-alder reactions

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