title: The reaction mechanism of Claisen rearrangement obtained by transition state spectroscopy and single direct-dynamics trajectory.
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.
authors: Innovative Use of Light and Materials/Life, PREST, JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan. iwakura@ils.uec.ac.jp
authors: Izumi
authors: I
authors: Iwakura
authors: Yu
authors: Y
authors: Kaneko
authors: Shigehiko
authors: S
authors: Hayashi
authors: Atsushi
authors: A
authors: Yabushita
authors: Takayoshi
authors: T
authors: Kobayashi
mesh_terms: D008956:Models, Chemical; D008968:Molecular Conformation; D017550:Spectroscopy, Fourier Transform Infrared; D013057:Spectrum Analysis / Q000379:methods*; D013059:Spectrum Analysis, Raman; D013997:Time Factors; D014753:Vinyl Compounds / Q000737:chemistry
chemical_list: D014753:Vinyl Compounds; C100195:vinyl ether
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