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 journalArticleAcademicpeer-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 languageEnglish
Pages (from-to)7100-7114
Number of pages15
JournalGreen Chemistry
Volume23
Issue number18
Early online date19 Aug 2021
DOIs
Publication statusPublished - 21 Sep 2021

Keywords

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

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