Non-thermal reaction triggered by a stimulated Raman process using 5-fs laser pulses in the electronic ground state: Claisen rearrangement of allyl phenyl ether

Abstract

The vibrational populations of allyl phenyl ether were excited by a broadband visible 5-fs laser pulse by the stimulated Raman process to promote a 'non-thermal' Claisen rearrangement reaction in the electronic ground state. Analyses of the time-resolved vibrational spectra observed in the subpicosecond region has shown that the Claisen rearrangement proceeds in the following three-step pathway: (1) weakening of the C(3)O bond to generate a bis-allyl intermediate, (2) formation of the weak C(1)C(5) bond results in the generation of a six-membered structure, and (3) simultaneous processes of C(3)O breaking and C(1)C(5) formation leading to the generation of a keto-intermediate. (C) 2010 Elsevier B.V. All rights reserved.