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.
|Journal||Chemistry - A European Journal|
|Publication status||Published - 23 Mar 2009|
- Density functional calculations
- Homogeneous catalysis
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