Diels-Alder Reactions of Furans with Itaconic Anhydride: Overcoming Unfavorable Thermodynamics

Ashok D. Pehere; Shu Xu; Severin K. Thompson; Marc A. Hillmyer; Thomas R. Hoye

doi:10.1021/acs.orglett.6b00929

Diels-Alder Reactions of Furans with Itaconic Anhydride: Overcoming Unfavorable Thermodynamics

Ashok D. Pehere, Shu Xu, Severin K. Thompson, Marc A. Hillmyer, Thomas R. Hoye

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

Unfavorable thermodynamics often render furans reluctant to engage in high-yielding Diels-Alder (DA) cycloaddition reactions. Here, we report the highly efficient conversion of the biosourced reactants itaconic anhydride (IA) and furfuryl alcohol (FA) to a single DA adduct. The free energy advantages provided by anhydride ring opening and crystal lattice energy of the product overcome the loss of aromaticity of the furanoid diene. Detailed ¹H NMR studies provided valuable insights about relevant kinetic and thermodynamic features.

Original language	English (US)
Pages (from-to)	2584-2587
Number of pages	4
Journal	Organic Letters
Volume	18
Issue number	11
DOIs	https://doi.org/10.1021/acs.orglett.6b00929
State	Published - Jun 3 2016

Bibliographical note

Funding Information:
Financial support for this research was provided by the Minnesota Corn Growers Association and the Center for Sustainable Polymers at the University of Minnesota, an NSFsupported Center for Chemical Innovation (CHE-1413862). NMR data were recorded on an instrument purchased with support of the NIH Shared Instrumentation Grant program (S10OD011952). Computations were performed with resources made available by the University of Minnesota Supercomputing Institute (MSI).

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© 2016 American Chemical Society.

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abstract = "Unfavorable thermodynamics often render furans reluctant to engage in high-yielding Diels-Alder (DA) cycloaddition reactions. Here, we report the highly efficient conversion of the biosourced reactants itaconic anhydride (IA) and furfuryl alcohol (FA) to a single DA adduct. The free energy advantages provided by anhydride ring opening and crystal lattice energy of the product overcome the loss of aromaticity of the furanoid diene. Detailed 1H NMR studies provided valuable insights about relevant kinetic and thermodynamic features.",

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AU - Xu, Shu

AU - Thompson, Severin K.

AU - Hillmyer, Marc A.

AU - Hoye, Thomas R.

N1 - Funding Information: Financial support for this research was provided by the Minnesota Corn Growers Association and the Center for Sustainable Polymers at the University of Minnesota, an NSFsupported Center for Chemical Innovation (CHE-1413862). NMR data were recorded on an instrument purchased with support of the NIH Shared Instrumentation Grant program (S10OD011952). Computations were performed with resources made available by the University of Minnesota Supercomputing Institute (MSI). Publisher Copyright: © 2016 American Chemical Society.

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AB - Unfavorable thermodynamics often render furans reluctant to engage in high-yielding Diels-Alder (DA) cycloaddition reactions. Here, we report the highly efficient conversion of the biosourced reactants itaconic anhydride (IA) and furfuryl alcohol (FA) to a single DA adduct. The free energy advantages provided by anhydride ring opening and crystal lattice energy of the product overcome the loss of aromaticity of the furanoid diene. Detailed 1H NMR studies provided valuable insights about relevant kinetic and thermodynamic features.

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Diels-Alder Reactions of Furans with Itaconic Anhydride: Overcoming Unfavorable Thermodynamics

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