Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation

Christian A. M. R. van Slagmaat; Jurrie Noordijk; Luciano G. Monsegue; Siri Mogensen; Darya Hadavi; Peiliang Han; Peter J. L. M. Quaedflieg; Gerard K. M. Verzijl; Paul L. Alsters; Stefaan M. A. De Wildeman

doi:10.1039/d1gc02372a

Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation

Christian A. M. R. van Slagmaat^*
, Jurrie Noordijk
, Luciano G. Monsegue
, Siri Mogensen
, Darya Hadavi
, Peiliang Han
, Peter J. L. M. Quaedflieg
, Gerard K. M. Verzijl
, Paul L. Alsters
, Stefaan M. A. De Wildeman^*

^*Corresponding author for this work

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

Abstract

A novel and green route for the synthesis of cyclopentane-1,3-diamine (CPDA) from hemicellulosic feed-stock is established in this work. Through many explorations and optimizations, the single successful multi-step synthesis was found to comprise: (1) the Piancatelli rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone (4-HCP), (2) a highly improved isomerization of 4-HCP into cyclopentane-1,3-dione (CPDO) using the Ru Shvo catalyst, (3) conversion of CPDO into cyclopentane-1,3-dioxime (CPDX), and (4) a mild oxime hydrogenation of CPDX over Rh/C to afford the desired CPDA. In addition, diastereomerically pure cis- and trans-isomers of CPDA were reacted with (A) bio-based lactones, and (B) 5-(hydroxymethyl)furfural (HMF) to synthesize novel bifunctional diol monomers with internal amide and imine groups, respectively. Monomer 5, derived using gamma-valerolactone (GVL), was successfully applied in the synthesis of polyurethanes.

Original language	English
Pages (from-to)	7100-7114
Number of pages	15
Journal	Green Chemistry
Volume	23
Issue number	18
Early online date	19 Aug 2021
DOIs	https://doi.org/10.1039/d1gc02372a
Publication status	Published - 21 Sept 2021

Keywords

GAMMA-VALEROLACTONE
ALLYLIC ALCOHOLS
ENANTIOSELECTIVE SYNTHESIS
ASYMMETRIC HYDROGENATION
KINETIC RESOLUTION
ISOMERIZATION
CONVERSION
BIOMASS
CYCLOPENTANONE
CHEMICALS

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van Slagmaat, C. A. M. R., Noordijk, J., Monsegue, L. G., Mogensen, S., Hadavi, D., Han, P., Quaedflieg, P. J. L. M., Verzijl, G. K. M., Alsters, P. L., & De Wildeman, S. M. A. (2021). Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation. Green Chemistry, 23(18), 7100-7114. https://doi.org/10.1039/d1gc02372a

@article{ea9deee2072b4a90b1dd0cd707b67c9e,

title = "Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation",

abstract = "A novel and green route for the synthesis of cyclopentane-1,3-diamine (CPDA) from hemicellulosic feed-stock is established in this work. Through many explorations and optimizations, the single successful multi-step synthesis was found to comprise: (1) the Piancatelli rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone (4-HCP), (2) a highly improved isomerization of 4-HCP into cyclopentane-1,3-dione (CPDO) using the Ru Shvo catalyst, (3) conversion of CPDO into cyclopentane-1,3-dioxime (CPDX), and (4) a mild oxime hydrogenation of CPDX over Rh/C to afford the desired CPDA. In addition, diastereomerically pure cis- and trans-isomers of CPDA were reacted with (A) bio-based lactones, and (B) 5-(hydroxymethyl)furfural (HMF) to synthesize novel bifunctional diol monomers with internal amide and imine groups, respectively. Monomer 5, derived using gamma-valerolactone (GVL), was successfully applied in the synthesis of polyurethanes.",

keywords = "GAMMA-VALEROLACTONE, ALLYLIC ALCOHOLS, ENANTIOSELECTIVE SYNTHESIS, ASYMMETRIC HYDROGENATION, KINETIC RESOLUTION, ISOMERIZATION, CONVERSION, BIOMASS, CYCLOPENTANONE, CHEMICALS",

author = "\{van Slagmaat\}, \{Christian A. M. R.\} and Jurrie Noordijk and Monsegue, \{Luciano G.\} and Siri Mogensen and Darya Hadavi and Peiliang Han and Quaedflieg, \{Peter J. L. M.\} and Verzijl, \{Gerard K. M.\} and Alsters, \{Paul L.\} and \{De Wildeman\}, \{Stefaan M. A.\}",

year = "2021",

month = sep,

day = "21",

doi = "10.1039/d1gc02372a",

language = "English",

volume = "23",

pages = "7100--7114",

journal = "Green Chemistry",

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publisher = "Royal Society of Chemistry",

number = "18",

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T1 - Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation

AU - van Slagmaat, Christian A. M. R.

AU - Noordijk, Jurrie

AU - Monsegue, Luciano G.

AU - Mogensen, Siri

AU - Hadavi, Darya

AU - Han, Peiliang

AU - Quaedflieg, Peter J. L. M.

AU - Verzijl, Gerard K. M.

AU - Alsters, Paul L.

AU - De Wildeman, Stefaan M. A.

PY - 2021/9/21

Y1 - 2021/9/21

N2 - A novel and green route for the synthesis of cyclopentane-1,3-diamine (CPDA) from hemicellulosic feed-stock is established in this work. Through many explorations and optimizations, the single successful multi-step synthesis was found to comprise: (1) the Piancatelli rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone (4-HCP), (2) a highly improved isomerization of 4-HCP into cyclopentane-1,3-dione (CPDO) using the Ru Shvo catalyst, (3) conversion of CPDO into cyclopentane-1,3-dioxime (CPDX), and (4) a mild oxime hydrogenation of CPDX over Rh/C to afford the desired CPDA. In addition, diastereomerically pure cis- and trans-isomers of CPDA were reacted with (A) bio-based lactones, and (B) 5-(hydroxymethyl)furfural (HMF) to synthesize novel bifunctional diol monomers with internal amide and imine groups, respectively. Monomer 5, derived using gamma-valerolactone (GVL), was successfully applied in the synthesis of polyurethanes.

AB - A novel and green route for the synthesis of cyclopentane-1,3-diamine (CPDA) from hemicellulosic feed-stock is established in this work. Through many explorations and optimizations, the single successful multi-step synthesis was found to comprise: (1) the Piancatelli rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone (4-HCP), (2) a highly improved isomerization of 4-HCP into cyclopentane-1,3-dione (CPDO) using the Ru Shvo catalyst, (3) conversion of CPDO into cyclopentane-1,3-dioxime (CPDX), and (4) a mild oxime hydrogenation of CPDX over Rh/C to afford the desired CPDA. In addition, diastereomerically pure cis- and trans-isomers of CPDA were reacted with (A) bio-based lactones, and (B) 5-(hydroxymethyl)furfural (HMF) to synthesize novel bifunctional diol monomers with internal amide and imine groups, respectively. Monomer 5, derived using gamma-valerolactone (GVL), was successfully applied in the synthesis of polyurethanes.

KW - GAMMA-VALEROLACTONE

KW - ALLYLIC ALCOHOLS

KW - ENANTIOSELECTIVE SYNTHESIS

KW - ASYMMETRIC HYDROGENATION

KW - KINETIC RESOLUTION

KW - ISOMERIZATION

KW - CONVERSION

KW - BIOMASS

KW - CYCLOPENTANONE

KW - CHEMICALS

U2 - 10.1039/d1gc02372a

DO - 10.1039/d1gc02372a

M3 - Article

SN - 1463-9262

VL - 23

SP - 7100

EP - 7114

JO - Green Chemistry

JF - Green Chemistry

IS - 18

ER -

Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation

Abstract

Keywords

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