The reaction mechanism of claisen rearrangement obtained by transition state spectroscopy and single direct-dynamics trajectory

Izumi Iwakura*, Yu Kaneko, Shigehiko Hayashi, Atsushi Yabushita, Takayoshi Kobayashi

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

Chemical bond breaking and formation during chemical reactions can be observed using "transition state spectroscopy". Comparing the measurement result of the transition state spectroscopy with the simulation result of single direct-dynamics trajectory, we have elucidated the reaction dynamics of Claisen rearrangement of allyl vinyl ether. Observed the reaction of the neat sample liquid, we have estimated the time constants of transformation from straight-chain structure to aromatic-like six-membered ring structure forming the C1-C6 bond. The result clarifies that the reaction proceeds via three steps taking longer time than expected from the gas phase calculation. This finding provides new hypothesis and discussions, helping the development of the field of reaction mechanism analysis.

Original languageEnglish
Pages (from-to)1995-2004
Number of pages10
JournalMolecules
Volume18
Issue number2
DOIs
StatePublished - Feb 2013

Keywords

  • 5-fs pulse laser
  • Claisen rearrangement
  • Reaction mechanism

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