Isohexide Dinitriles

A Versatile Family of Renewable Platform Chemicals

Jing Wu*, Shanmugam Thiyagarajan, Célia Fonseca Guerra, Pieter Eduard, Martin Lutz, Bart A.J. Noordover, Cor E. Koning, Daan S. van Es

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

3 Citations (Scopus)

Abstract

Building blocks of isohexides extended by one carbon atom at the 2- or 5-positions are now synthetically accessible by a convenient, selective, base-catalyzed epimerization of the corresponding dinitriles. Kinetic experiments using the strong organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) show that all three possible isohexide dinitrile isomers exist within a dynamic equilibrium. An epimerization mechanism based on density functional theory (DFT) calculations is proposed. Structural identification of all three possible isomers is based on NMR analysis and single crystal x-ray crystallography. DFT calculations confirm that the observed crystal structures are indeed the lowest energy conformers of these isohexide derivatives.
Original languageEnglish
Pages (from-to)3202-3211
JournalChemSusChem
Volume10
Issue number16
DOIs
Publication statusPublished - 2017

Fingerprint

Isomers
Density functional theory
crystallography
Crystallography
crystal structure
nuclear magnetic resonance
Carbon
Crystal structure
Nuclear magnetic resonance
Single crystals
crystal
Derivatives
X rays
kinetics
Atoms
Kinetics
carbon
energy
experiment
Experiments

Keywords

  • Biomass
  • Crystal structures
  • Epimers
  • Isohexides
  • Oxygen heterocycles

Cite this

Wu, Jing ; Thiyagarajan, Shanmugam ; Guerra, Célia Fonseca ; Eduard, Pieter ; Lutz, Martin ; Noordover, Bart A.J. ; Koning, Cor E. ; van Es, Daan S. / Isohexide Dinitriles : A Versatile Family of Renewable Platform Chemicals. In: ChemSusChem. 2017 ; Vol. 10, No. 16. pp. 3202-3211.
@article{98bd58d304be4ac68318a9310636cc23,
title = "Isohexide Dinitriles: A Versatile Family of Renewable Platform Chemicals",
abstract = "Building blocks of isohexides extended by one carbon atom at the 2- or 5-positions are now synthetically accessible by a convenient, selective, base-catalyzed epimerization of the corresponding dinitriles. Kinetic experiments using the strong organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) show that all three possible isohexide dinitrile isomers exist within a dynamic equilibrium. An epimerization mechanism based on density functional theory (DFT) calculations is proposed. Structural identification of all three possible isomers is based on NMR analysis and single crystal x-ray crystallography. DFT calculations confirm that the observed crystal structures are indeed the lowest energy conformers of these isohexide derivatives.",
keywords = "Biomass, Crystal structures, Epimers, Isohexides, Oxygen heterocycles",
author = "Jing Wu and Shanmugam Thiyagarajan and Guerra, {C{\'e}lia Fonseca} and Pieter Eduard and Martin Lutz and Noordover, {Bart A.J.} and Koning, {Cor E.} and {van Es}, {Daan S.}",
year = "2017",
doi = "10.1002/cssc.201700617",
language = "English",
volume = "10",
pages = "3202--3211",
journal = "ChemSusChem",
issn = "1864-5631",
publisher = "Wiley-VCH Verlag",
number = "16",

}

Wu, J, Thiyagarajan, S, Guerra, CF, Eduard, P, Lutz, M, Noordover, BAJ, Koning, CE & van Es, DS 2017, 'Isohexide Dinitriles: A Versatile Family of Renewable Platform Chemicals', ChemSusChem, vol. 10, no. 16, pp. 3202-3211. https://doi.org/10.1002/cssc.201700617

Isohexide Dinitriles : A Versatile Family of Renewable Platform Chemicals. / Wu, Jing; Thiyagarajan, Shanmugam; Guerra, Célia Fonseca; Eduard, Pieter; Lutz, Martin; Noordover, Bart A.J.; Koning, Cor E.; van Es, Daan S.

In: ChemSusChem, Vol. 10, No. 16, 2017, p. 3202-3211.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Isohexide Dinitriles

T2 - A Versatile Family of Renewable Platform Chemicals

AU - Wu, Jing

AU - Thiyagarajan, Shanmugam

AU - Guerra, Célia Fonseca

AU - Eduard, Pieter

AU - Lutz, Martin

AU - Noordover, Bart A.J.

AU - Koning, Cor E.

AU - van Es, Daan S.

PY - 2017

Y1 - 2017

N2 - Building blocks of isohexides extended by one carbon atom at the 2- or 5-positions are now synthetically accessible by a convenient, selective, base-catalyzed epimerization of the corresponding dinitriles. Kinetic experiments using the strong organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) show that all three possible isohexide dinitrile isomers exist within a dynamic equilibrium. An epimerization mechanism based on density functional theory (DFT) calculations is proposed. Structural identification of all three possible isomers is based on NMR analysis and single crystal x-ray crystallography. DFT calculations confirm that the observed crystal structures are indeed the lowest energy conformers of these isohexide derivatives.

AB - Building blocks of isohexides extended by one carbon atom at the 2- or 5-positions are now synthetically accessible by a convenient, selective, base-catalyzed epimerization of the corresponding dinitriles. Kinetic experiments using the strong organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) show that all three possible isohexide dinitrile isomers exist within a dynamic equilibrium. An epimerization mechanism based on density functional theory (DFT) calculations is proposed. Structural identification of all three possible isomers is based on NMR analysis and single crystal x-ray crystallography. DFT calculations confirm that the observed crystal structures are indeed the lowest energy conformers of these isohexide derivatives.

KW - Biomass

KW - Crystal structures

KW - Epimers

KW - Isohexides

KW - Oxygen heterocycles

U2 - 10.1002/cssc.201700617

DO - 10.1002/cssc.201700617

M3 - Article

VL - 10

SP - 3202

EP - 3211

JO - ChemSusChem

JF - ChemSusChem

SN - 1864-5631

IS - 16

ER -