An enzyme cascade synthesis of ε-caprolactone and its oligomers

Sandy Schmidt, Christian Scherkus, Jan Muschiol, Ulf Menyes, Till Winkler, Werner Hummel, Harald Gröger, Andreas Liese, Hans Georg Herz, Uwe T. Bornscheuer

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Poly-ε-caprolactone (PCL) is chemically produced on an industrial scale in spite of the need for hazardous peracetic acid as an oxidation reagent. Although Baeyer-Villiger monooxygenases (BVMO) in principle enable the enzymatic synthesis of ε-caprolactone (ε-CL) directly from cyclohexanone with molecular oxygen, current systems suffer from low productivity and are subject to substrate and product inhibition. The major limitations for such a biocatalytic route to produce this bulk chemical were overcome by combining an alcohol dehydrogenase with a BVMO to enable the efficient oxidation of cyclohexanol to ε-CL. Key to success was a subsequent direct ring-opening oligomerization of in situ formed ε-CL in the aqueous phase by using lipase A from Candida antarctica, thus efficiently solving the product inhibition problem and leading to the formation of oligo-ε-CL at more than 20 g L-1 when starting from 200 mM cyclohexanol. This oligomer is easily chemically polymerized to PCL.

Original languageEnglish
Pages (from-to)2784-2787
Number of pages4
JournalAngewandte Chemie / International Edition
Volume54
Issue number9
DOIs
Publication statusPublished - 23 Feb 2015

Fingerprint

Cyclohexanols
Mixed Function Oxygenases
Oligomers
Enzymes
Peracetic Acid
Oxidation
Oligomerization
Molecular oxygen
Candida
Alcohol Dehydrogenase
Lipases
Lipase
Alcohols
Productivity
Acids
Substrates
polycaprolactone
caprolactone

Keywords

  • Baeyer-Villiger monooxygenases
  • Cascade reactions
  • Enzyme catalysis
  • Polymer synthesis
  • ε-caprolactone

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Schmidt, S., Scherkus, C., Muschiol, J., Menyes, U., Winkler, T., Hummel, W., ... Bornscheuer, U. T. (2015). An enzyme cascade synthesis of ε-caprolactone and its oligomers. Angewandte Chemie / International Edition , 54(9), 2784-2787. https://doi.org/10.1002/anie.201410633

An enzyme cascade synthesis of ε-caprolactone and its oligomers. / Schmidt, Sandy; Scherkus, Christian; Muschiol, Jan; Menyes, Ulf; Winkler, Till; Hummel, Werner; Gröger, Harald; Liese, Andreas; Herz, Hans Georg; Bornscheuer, Uwe T.

In: Angewandte Chemie / International Edition , Vol. 54, No. 9, 23.02.2015, p. 2784-2787.

Research output: Contribution to journalArticleResearchpeer-review

Schmidt, S, Scherkus, C, Muschiol, J, Menyes, U, Winkler, T, Hummel, W, Gröger, H, Liese, A, Herz, HG & Bornscheuer, UT 2015, 'An enzyme cascade synthesis of ε-caprolactone and its oligomers' Angewandte Chemie / International Edition , vol. 54, no. 9, pp. 2784-2787. https://doi.org/10.1002/anie.201410633
Schmidt, Sandy ; Scherkus, Christian ; Muschiol, Jan ; Menyes, Ulf ; Winkler, Till ; Hummel, Werner ; Gröger, Harald ; Liese, Andreas ; Herz, Hans Georg ; Bornscheuer, Uwe T. / An enzyme cascade synthesis of ε-caprolactone and its oligomers. In: Angewandte Chemie / International Edition . 2015 ; Vol. 54, No. 9. pp. 2784-2787.
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