Isohexide dinitriles: a versatile family of renewable platform chemicals

J. Wu; S. Thiyagarajan; C. Fonseca Guerra; P. Eduard; M. Lutz; B.A.J. Noordover; C.E. Koning; D.S. van Es

doi:10.1002/cssc.201700617

Isohexide dinitriles: a versatile family of renewable platform chemicals

J. Wu, S. Thiyagarajan, C. Fonseca Guerra, P. Eduard, M. Lutz, B.A.J. Noordover, C.E. Koning, D.S. van Es

Physical Chemistry

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

13 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
Number of pages	10
Journal	ChemSusChem
Volume	10
Issue number	16
DOIs	https://doi.org/10.1002/cssc.201700617
Publication status	Published - 24 Aug 2017

Keywords

Biomass
Crystal structures
Epimers
Isohexides
Oxygen heterocycles
Green Chemistry Technology
Nitriles/chemistry
Stereoisomerism
Molecular Conformation
Models, Molecular
Quantum Theory
Catalysis
Kinetics
Bridged Bicyclo Compounds, Heterocyclic/chemistry

UN SDGs

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

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10.1002/cssc.201700617

Cite this

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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.",

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author = "J. Wu and S. Thiyagarajan and {Fonseca Guerra}, C. and P. Eduard and M. Lutz and B.A.J. Noordover and C.E. Koning and {van Es}, D.S.",

year = "2017",

month = aug,

day = "24",

doi = "10.1002/cssc.201700617",

language = "English",

volume = "10",

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T1 - Isohexide dinitriles

T2 - a versatile family of renewable platform chemicals

AU - Wu, J.

AU - Thiyagarajan, S.

AU - Fonseca Guerra, C.

AU - Eduard, P.

AU - Lutz, M.

AU - Noordover, B.A.J.

AU - Koning, C.E.

AU - van Es, D.S.

PY - 2017/8/24

Y1 - 2017/8/24

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

KW - Green Chemistry Technology

KW - Nitriles/chemistry

KW - Stereoisomerism

KW - Molecular Conformation

KW - Models, Molecular

KW - Quantum Theory

KW - Catalysis

KW - Kinetics

KW - Bridged Bicyclo Compounds, Heterocyclic/chemistry

UR - http://www.scopus.com/inward/record.url?scp=85023199725&partnerID=8YFLogxK

U2 - 10.1002/cssc.201700617

DO - 10.1002/cssc.201700617

M3 - Article

C2 - 28590079

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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