Gold-catalyzed [4C+3C] intramolecular cycloaddition of allenedienes: Synthetic potential and mechanistic implications

Beatriz Trillo, Fernando López, Sergi Montserrat, Gregor Ujaque, Luis Castedo, Agustí Lledós, Jose L. Mascareñas

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Abstract

An experiment was conducted to discover that Au complex generated in situ from [(IPr)AuCl] and AgSbF6 catalyzes the [4C+3C] intramolecular cycloaddition of a variety of allenedienes at room temperature. Allenediene was treated with 10 mol% of AuCl3 or AuCl, the desired [4C+3C] cycloadduct was obtained in good yield. Screening of other Au catalysts revealed that the cycloaddition was particularly rapid and efficient with the Au complex, which features a N-heterocyclic carbene (IPr) ligand. NMR monitoring of the cycloaddition of allenediene using 10 mol% of several catalysts revealed that while exhibiting a significantly lower energy barrier for the 1,2-H shift step. The reaction of cyclopentylallene derivative in the presence of catalyst, in addition to providing the expected tricycle that results from a 1,2 alkyl shift in the intermediate carbene species, led to a minor cycloadduct identified as the bicycle.
Original languageEnglish
Pages (from-to)3336-3339
JournalChemistry - A European Journal
Volume15
Issue number14
DOIs
Publication statusPublished - 23 Mar 2009

Keywords

  • Allenes
  • Carbocycles
  • Cycloaddition
  • Density functional calculations
  • Gold
  • Homogeneous catalysis

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    Trillo, B., López, F., Montserrat, S., Ujaque, G., Castedo, L., Lledós, A., & Mascareñas, J. L. (2009). Gold-catalyzed [4C+3C] intramolecular cycloaddition of allenedienes: Synthetic potential and mechanistic implications. Chemistry - A European Journal, 15(14), 3336-3339. https://doi.org/10.1002/chem.200900164