Asymmetric synthesis with cinchona-decorated cyclodextrin in a continuous-flow membrane reactor

Peter Kisszekelyi, Abdulaziz Alammar, Jozsef Kupai, P. Huszthy, Julia Barabas, Tibor Holtzl, Lajos Szente, Carlo Bawn, Ralph Adams, Gyorgy Szekely

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

This work presents a cyclodextrin-enhanced organocatalytic method from molecular to process design. Cinchona-thiourea and -squaramide catalysts were covalently anchored to inherently large, stable and well-defined permethyl-β-cyclodextrins. The asymmetric catalysis was successfully demonstrated on the Michael reaction of 1,3-diketones and trans-β-nitrostyrene. Both emerging green and conventional solvents were screened for the asymmetric addition (up to 99% ee), and the Kamlet–Taft solvent parameters were correlated to the enantioselectivity. Quantum chemical modelling revealed that the catalyst anchoring resulted in favorable structural changes, and stronger intermolecular interactions between the catalyst and the reagents. Continuous organocatalysis was performed in coiled tube flow reactor coupled with a membrane separation unit, which allowed complete recovery of the catalyst and 50% solvent (2-MeTHF) recycling. The 100% conversion, 98% purity, 99% ee, 100% in-line catalyst recovery, and 80 g L −1 h −1 productivity makes it an attractive catalytic platform.

Original languageEnglish
Pages (from-to)255-261
Number of pages7
JournalJournal of Catalysis
DOIs
Publication statusPublished - Mar 1 2019

Fingerprint

Cinchona
Cyclodextrins
reactors
membranes
Membranes
catalysts
Catalysts
synthesis
recovery
Michael reaction
Recovery
Thiourea
Thioureas
Enantioselectivity
thioureas
Pipe flow
recycling
productivity
Catalysis
catalysis

Keywords

  • Catalyst recovery
  • CNXCXSMYMLPAMS-UHFFFAOYSA-N
  • Continuous processes
  • FHPSEPBVFKHFNY-UHFFFAOYSA-N
  • Flow chemistry
  • GANRWJWDBLKUJA-UHFFFAOYSA-N
  • HBOZSVVDCDBTLC-UHFFFAOYSA-N
  • HGVZOZLENNRYCV-FEBSWUBLSA-N
  • In-line recycling
  • NRTGMGHTTXZAHK-FEQNNBRFSA-N
  • Organic solvent nanofiltration
  • Organocatalysis
  • PKIQKQBPSHXGJH-PBFVBANWSA-N
  • URYLJCBFCXEADB-UHFFFAOYSA-N
  • USUKGXSBXPEYAE-UHFFFAOYSA-N
  • VXCPMTROKJXPOD-AVOXONOSSA-N

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Asymmetric synthesis with cinchona-decorated cyclodextrin in a continuous-flow membrane reactor. / Kisszekelyi, Peter; Alammar, Abdulaziz; Kupai, Jozsef; Huszthy, P.; Barabas, Julia; Holtzl, Tibor; Szente, Lajos; Bawn, Carlo; Adams, Ralph; Szekely, Gyorgy.

In: Journal of Catalysis, 01.03.2019, p. 255-261.

Research output: Contribution to journalArticle

Kisszekelyi, P, Alammar, A, Kupai, J, Huszthy, P, Barabas, J, Holtzl, T, Szente, L, Bawn, C, Adams, R & Szekely, G 2019, 'Asymmetric synthesis with cinchona-decorated cyclodextrin in a continuous-flow membrane reactor' Journal of Catalysis, pp. 255-261. https://doi.org/10.1016/j.jcat.2019.01.041
Kisszekelyi, Peter ; Alammar, Abdulaziz ; Kupai, Jozsef ; Huszthy, P. ; Barabas, Julia ; Holtzl, Tibor ; Szente, Lajos ; Bawn, Carlo ; Adams, Ralph ; Szekely, Gyorgy. / Asymmetric synthesis with cinchona-decorated cyclodextrin in a continuous-flow membrane reactor. In: Journal of Catalysis. 2019 ; pp. 255-261.
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AU - Barabas, Julia

AU - Holtzl, Tibor

AU - Szente, Lajos

AU - Bawn, Carlo

AU - Adams, Ralph

AU - Szekely, Gyorgy

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N2 - This work presents a cyclodextrin-enhanced organocatalytic method from molecular to process design. Cinchona-thiourea and -squaramide catalysts were covalently anchored to inherently large, stable and well-defined permethyl-β-cyclodextrins. The asymmetric catalysis was successfully demonstrated on the Michael reaction of 1,3-diketones and trans-β-nitrostyrene. Both emerging green and conventional solvents were screened for the asymmetric addition (up to 99% ee), and the Kamlet–Taft solvent parameters were correlated to the enantioselectivity. Quantum chemical modelling revealed that the catalyst anchoring resulted in favorable structural changes, and stronger intermolecular interactions between the catalyst and the reagents. Continuous organocatalysis was performed in coiled tube flow reactor coupled with a membrane separation unit, which allowed complete recovery of the catalyst and 50% solvent (2-MeTHF) recycling. The 100% conversion, 98% purity, 99% ee, 100% in-line catalyst recovery, and 80 g L −1 h −1 productivity makes it an attractive catalytic platform.

AB - This work presents a cyclodextrin-enhanced organocatalytic method from molecular to process design. Cinchona-thiourea and -squaramide catalysts were covalently anchored to inherently large, stable and well-defined permethyl-β-cyclodextrins. The asymmetric catalysis was successfully demonstrated on the Michael reaction of 1,3-diketones and trans-β-nitrostyrene. Both emerging green and conventional solvents were screened for the asymmetric addition (up to 99% ee), and the Kamlet–Taft solvent parameters were correlated to the enantioselectivity. Quantum chemical modelling revealed that the catalyst anchoring resulted in favorable structural changes, and stronger intermolecular interactions between the catalyst and the reagents. Continuous organocatalysis was performed in coiled tube flow reactor coupled with a membrane separation unit, which allowed complete recovery of the catalyst and 50% solvent (2-MeTHF) recycling. The 100% conversion, 98% purity, 99% ee, 100% in-line catalyst recovery, and 80 g L −1 h −1 productivity makes it an attractive catalytic platform.

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