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Issue 31, 2013
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Aromatics from pyrones: esters of terephthalic acid and isophthalic acid from methyl coumalate

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Abstract

The Diels–Alder reaction of methyl coumalate with alkenes bearing electron-withdrawing groups provides terephthalates or isophthalates in good yields, with the regioselectivity depending on the electron-withdrawing group. The reaction of methyl coumalate with the salt of acrylic acid gave only the monoester of isophthalic acid. Density functional theory (B3LYP/6-31 + G(d,p)) computations of the energies of the competing transition states of the para-selective Diels–Alder reactions are in good agreement with experiment. The surprising regioselectivity of methyl coumalate with activated alkenes is attributed to a secondary orbital interaction between the pyrone oxygen and the dienophile LUMO, which switches the regiochemistry expected from simple frontier molecular orbital theory arguments.

Graphical abstract: Aromatics from pyrones: esters of terephthalic acid and isophthalic acid from methyl coumalate

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Supplementary files

Article information


Submitted
09 May 2013
Accepted
23 May 2013
First published
24 May 2013

RSC Adv., 2013,3, 12721-12725
Article type
Paper

Aromatics from pyrones: esters of terephthalic acid and isophthalic acid from methyl coumalate

G. A. Kraus, G. R. Pollock III, C. L. Beck, K. Palmer and A. H. Winter, RSC Adv., 2013, 3, 12721 DOI: 10.1039/C3RA42287A

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