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

doi:10.1002/cssc.201700617

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 journal › Article › Academic › peer-review

17 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 language	English
Pages (from-to)	3202-3211
Journal	ChemSusChem
Volume	10
Issue number	16
DOIs	https://doi.org/10.1002/cssc.201700617
Publication status	Published - 2017

Keywords

Biomass
Crystal structures
Epimers
Isohexides
Oxygen heterocycles

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/cssc.201700617

CCDC 890378: Experimental Crystal Structure Determination
Wu, J. (Creator), Thiyagarajan, S. (Creator), Guerra, C. F. (Creator), Eduard, P. (Creator), Lutz, M. (Creator), Noordover, B. A. J. (Creator), Koning, C. E. (Creator) & van Es, D. S. (Creator), Wageningen University & Research, 2017
DOI: 10.5517/ccdc.csd.ccywhw5
Dataset
CCDC 890377: Experimental Crystal Structure Determination
Wu, J. (Creator), Thiyagarajan, S. (Creator), Guerra, C. F. (Creator), Eduard, P. (Creator), Lutz, M. (Creator), Noordover, B. A. J. (Creator) & van Es, D. S. (Creator), Wageningen University & Research, 2017
DOI: 10.5517/ccdc.csd.ccywhv4
Dataset

Cite this

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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 = "VCH",

number = "16",

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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

AN - SCOPUS:85023199725

SN - 1864-5631

VL - 10

SP - 3202

EP - 3211

JO - ChemSusChem

JF - ChemSusChem

IS - 16

ER -

Isohexide Dinitriles: A Versatile Family of Renewable Platform Chemicals

Abstract

Keywords

UN SDGs

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Datasets

CCDC 890378: Experimental Crystal Structure Determination

CCDC 890377: Experimental Crystal Structure Determination

Cite this