The Reaction Mechanism of Claisen RearrangementObtained by Transition State Spectroscopy and SingleDirect-Dynamics Trajectory

Molecules

Izumi Iwakura¹  Yu Kaneko¹  Shigehiko Hayashi¹  Atsushi Yabushita¹ 

[1] ¹Innovative Use of Light and Materials/Life, PREST, JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan

关键词: Claisen rearrangement;    5-fs pulse laser;    reaction mechanism;   

DOI  :  10.3390/molecules18021995

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.