First C-C bond formation in the Pauson-Khand reaction: Influence of carbon-carbon triple bond polarization on regiochemistry. A density functional theory study

Theodorus J.M. de Bruin, Carine Michel, Karoly Vekey, Andrew E. Greene, Yves Gimbert, Anne Milet

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The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented.

Original languageEnglish
Pages (from-to)4281-4288
Number of pages8
JournalJournal of Organometallic Chemistry
Issue number20
Publication statusPublished - Oct 1 2006



  • DFT studies
  • Olefin insertion
  • Pauson-Khand reaction
  • Triple-bond polarization

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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