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Issue 24, 2014
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Quantum mechanistic insights on aryl propargyl ether Claisen rearrangement

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The mechanism of aryl propargyl ether Claisen rearrangement in gas and solvent phase was investigated using DFT methods. Solvent phase calculations are carried out using N,N-diethylaniline as a solvent in the PCM model. The most favorable pathways involve a [3,3]-sigmatropic reaction followed by proton transfer in the first two steps and then deprotonation or [1,5]-sigmatropic reaction. Finally, cyclization yields benzopyran or benzofuran derivatives. The [3,3]-sigmatropic reaction is the rate-determining step for benzopyran and benzofuran with ΔG value of 38.4 and 37.9 kcal mol−1 at M06/6-31+G**//B3LYP/6-31+G* level in gas and solvent phase, respectively. The computed results are in good agreement with the experimental results. Moreover, it is found that the derivatives of aryl propargyl ether proceeded Claisen rearrangement and the rate-determining step may be shifted from the [3,3]-sigmatropic reaction to the tautomerization step. The NBO analysis revealed that substitution of the methyl groups on the aliphatic segment has decreased the stabilization energy E(2) and favors the aryl propargyl ether Claisen rearrangement.

Graphical abstract: Quantum mechanistic insights on aryl propargyl ether Claisen rearrangement

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Publication details

The article was received on 19 Feb 2014, accepted on 25 Mar 2014 and first published on 25 Mar 2014

Article type: Paper
DOI: 10.1039/C4OB00388H
Citation: Org. Biomol. Chem., 2014,12, 4163-4171
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    Quantum mechanistic insights on aryl propargyl ether Claisen rearrangement

    V. Srinivasadesikan, J. Dai and S. Lee, Org. Biomol. Chem., 2014, 12, 4163
    DOI: 10.1039/C4OB00388H

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