Enantioselective Bio-Hydrolysis of Geranyl-Derived rac-Epoxides: A Chemoenzymatic Route to trans-Furanoid Linalool Oxide

Matthijs J. van Lint, Aysegül Gümüs, Eelco Ruijter, Kurt Faber, Romano V.A. Orru, Mélanie Hall

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim In contrast to many chemical dihydroxylation methods, enzymatic epoxide hydrolysis provides an environmentally benign route to vicinal diols, which are important intermediates in the synthesis of fine chemicals and pharmaceuticals. Using epoxide hydrolases, enantiopure diols are accessible under mild conditions. In order to assess the selectivity of epoxide hydrolases on geraniol-derived oxiranes, a range of derivatives were screened against a large variety of enzyme preparations. For nearly all substrates, a matching hydrolase with excellent enantioselectivity (≥95% ee) could be found. In addition, a chemoenzymatic approach for the stereoselective synthesis of furanoid linalool oxide was developed. Combination of enzymatic enantioselective hydrolysis with stereoselective Tsuji-Trost reaction granted diastereoselective access to trans-(2R,5R)-configured linalool oxide with high diastereomeric and enantiomeric excess (97% de and 97% ee). (Figure presented.).
Original languageEnglish
Pages (from-to)813-825
JournalAdvanced Synthesis and Catalysis
Volume361
Issue number4
DOIs
Publication statusAccepted/In press - 1 Jan 2019

Fingerprint

Epoxide Hydrolases
Hydrolases
Enzymatic hydrolysis
Epoxy Compounds
Hydrolysis
Oxides
Enantioselectivity
Derivatives
Drug products
Substrates
Enzymes
Pharmaceutical Preparations
linalool oxide
geraniol

Keywords

  • Biocatalysis
  • Epoxide hydrolases
  • Furanoid linalool oxide
  • Geraniol epoxide
  • Tsuji-Trost reaction

Cite this

@article{bcd45b5f68814ecf96a543f9f6478917,
title = "Enantioselective Bio-Hydrolysis of Geranyl-Derived rac-Epoxides: A Chemoenzymatic Route to trans-Furanoid Linalool Oxide",
abstract = "{\circledC} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim In contrast to many chemical dihydroxylation methods, enzymatic epoxide hydrolysis provides an environmentally benign route to vicinal diols, which are important intermediates in the synthesis of fine chemicals and pharmaceuticals. Using epoxide hydrolases, enantiopure diols are accessible under mild conditions. In order to assess the selectivity of epoxide hydrolases on geraniol-derived oxiranes, a range of derivatives were screened against a large variety of enzyme preparations. For nearly all substrates, a matching hydrolase with excellent enantioselectivity (≥95{\%} ee) could be found. In addition, a chemoenzymatic approach for the stereoselective synthesis of furanoid linalool oxide was developed. Combination of enzymatic enantioselective hydrolysis with stereoselective Tsuji-Trost reaction granted diastereoselective access to trans-(2R,5R)-configured linalool oxide with high diastereomeric and enantiomeric excess (97{\%} de and 97{\%} ee). (Figure presented.).",
keywords = "Biocatalysis, Epoxide hydrolases, Furanoid linalool oxide, Geraniol epoxide, Tsuji-Trost reaction",
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Enantioselective Bio-Hydrolysis of Geranyl-Derived rac-Epoxides: A Chemoenzymatic Route to trans-Furanoid Linalool Oxide. / van Lint, Matthijs J.; Gümüs, Aysegül; Ruijter, Eelco; Faber, Kurt; Orru, Romano V.A.; Hall, Mélanie.

In: Advanced Synthesis and Catalysis, Vol. 361, No. 4, 01.01.2019, p. 813-825.

Research output: Contribution to JournalArticleAcademicpeer-review

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AU - van Lint, Matthijs J.

AU - Gümüs, Aysegül

AU - Ruijter, Eelco

AU - Faber, Kurt

AU - Orru, Romano V.A.

AU - Hall, Mélanie

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N2 - © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim In contrast to many chemical dihydroxylation methods, enzymatic epoxide hydrolysis provides an environmentally benign route to vicinal diols, which are important intermediates in the synthesis of fine chemicals and pharmaceuticals. Using epoxide hydrolases, enantiopure diols are accessible under mild conditions. In order to assess the selectivity of epoxide hydrolases on geraniol-derived oxiranes, a range of derivatives were screened against a large variety of enzyme preparations. For nearly all substrates, a matching hydrolase with excellent enantioselectivity (≥95% ee) could be found. In addition, a chemoenzymatic approach for the stereoselective synthesis of furanoid linalool oxide was developed. Combination of enzymatic enantioselective hydrolysis with stereoselective Tsuji-Trost reaction granted diastereoselective access to trans-(2R,5R)-configured linalool oxide with high diastereomeric and enantiomeric excess (97% de and 97% ee). (Figure presented.).

AB - © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim In contrast to many chemical dihydroxylation methods, enzymatic epoxide hydrolysis provides an environmentally benign route to vicinal diols, which are important intermediates in the synthesis of fine chemicals and pharmaceuticals. Using epoxide hydrolases, enantiopure diols are accessible under mild conditions. In order to assess the selectivity of epoxide hydrolases on geraniol-derived oxiranes, a range of derivatives were screened against a large variety of enzyme preparations. For nearly all substrates, a matching hydrolase with excellent enantioselectivity (≥95% ee) could be found. In addition, a chemoenzymatic approach for the stereoselective synthesis of furanoid linalool oxide was developed. Combination of enzymatic enantioselective hydrolysis with stereoselective Tsuji-Trost reaction granted diastereoselective access to trans-(2R,5R)-configured linalool oxide with high diastereomeric and enantiomeric excess (97% de and 97% ee). (Figure presented.).

KW - Biocatalysis

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