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• Iwakura, I
• Kaneko, Y
• Hayashi, S
• Yabushita, A
• Kobayashi, T
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• Iwakura, I
• Kaneko, Y
• Hayashi, S
• Yabushita, A
• Kobayashi, T
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• Iwakura, I
• Kaneko, Y
• Hayashi, S
• Yabushita, A
• Kobayashi, T

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Molecules 2013, 18(2), 1995-2004; doi:10.3390/molecules18021995

Article

The Reaction Mechanism of Claisen Rearrangement Obtained by Transition State Spectroscopy and Single Direct-Dynamics Trajectory

Izumi Iwakura ^1,2,* , Yu Kaneko ³ , Shigehiko Hayashi ³ , Atsushi Yabushita ⁴  and Takayoshi Kobayashi ^2,4

¹ Innovative Use of Light and Materials/Life, PREST, JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan ² University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585, Japan ³ Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa, Sakyo, Kyoto 606-8502, Japan ⁴ Department of Electrophysics, National Chiao-Tung University, Hsinchu 300, Taiwan

* Author to whom correspondence should be addressed.

Received: 9 January 2013; in revised form: 14 January 2013 / Accepted: 28 January 2013 / Published: 4 February 2013

Download PDF Full-Text [558 KB, uploaded 4 February 2013 08:30 CET]

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.

Keywords: Claisen rearrangement; 5-fs pulse laser; reaction mechanism

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