Asymmetric cation-olefin monocyclization by engineered squalene-hopene cyclases

Eichenberger, Michael; Hüppi, Sean; Patsch, David; Aeberli, Natalie; Berweger, Raphael; Dossenbach, Sandro; Eichhorn, Eric; Flachsmann, Felix; Hortencio, Lucas; Voirol, Francis; Vollenweider, Sabine; Bornscheuer, Uwe T.; Buller, Rebecca

doi:10.1002/anie.202108037

Please use this identifier to cite or link to this item: https://doi.org/10.21256/zhaw-23939

Publication type:	Article in scientific journal
Type of review:	Peer review (publication)
Title:	Asymmetric cation-olefin monocyclization by engineered squalene-hopene cyclases
Authors:	Eichenberger, Michael Hüppi, Sean Patsch, David Aeberli, Natalie Berweger, Raphael Dossenbach, Sandro Eichhorn, Eric Flachsmann, Felix Hortencio, Lucas Voirol, Francis Vollenweider, Sabine Bornscheuer, Uwe T. Buller, Rebecca
et. al:	No
DOI:	10.1002/anie.202108037 10.21256/zhaw-23939
Published in:	Angewandte Chemie: International Edition
Volume(Issue):	60
Issue:	50
Page(s):	26080
Pages to:	26086
Issue Date:	2021
Publisher / Ed. Institution:	Wiley
ISSN:	1433-7851 1521-3773
Language:	English
Subjects:	Chemoenzymatic synthesis; Cyclization; Protein engineering; Squalene-hopene cyclase; Substrate engineering
Subject (DDC):	660: Chemical engineering
Abstract:	Squalene-hopene cyclases (SHCs) have great potential for the industrial synthesis of enantiopure cyclic terpenoids. A limitation of SHC catalysis has been the enzymes' strict (S)-enantioselectivity at the stereocenter formed after the first cyclization step. To gain enantio-complementary access to valuable monocyclic terpenoids, an SHC-wild-type library including 18 novel homologs was set up. A previously not described SHC (AciSHC) was found to synthesize small amounts of monocyclic (R)-γ-dihydroionone from (E/Z)-geranylacetone. Using enzyme and process optimization, the conversion to the desired product was increased to 79 %. Notably, analyzed AciSHC variants could finely differentiate between the geometric geranylacetone isomers: While the (Z)-isomer yielded the desired monocyclic (R)-γ-dihydroionone (>99 % ee), the (E)-isomer was converted to the (S,S)-bicyclic ether (>95 % ee). Applying the knowledge gained from the observed stereodivergent and enantioselective transformations to an additional SHC-substrate pair, access to the complementary (S)-γ-dihydroionone (>99.9 % ee) could be obtained.
URI:	https://digitalcollection.zhaw.ch/handle/11475/23939
Fulltext version:	Published version
License (according to publishing contract):	CC BY 4.0: Attribution 4.0 International
Departement:	Life Sciences and Facility Management
Organisational Unit:	Institute of Chemistry and Biotechnology (ICBT)
Published as part of the ZHAW project:	Biocatalytic Production - Engineering of terpene cyclases for the production of R-alpha-Ionone
Appears in collections:	Publikationen Life Sciences und Facility Management

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Eichenberger, M., Hüppi, S., Patsch, D., Aeberli, N., Berweger, R., Dossenbach, S., Eichhorn, E., Flachsmann, F., Hortencio, L., Voirol, F., Vollenweider, S., Bornscheuer, U. T., & Buller, R. (2021). Asymmetric cation-olefin monocyclization by engineered squalene-hopene cyclases. Angewandte Chemie: International Edition, 60(50), 26080–26086. https://doi.org/10.1002/anie.202108037

Eichenberger, M. et al. (2021) ‘Asymmetric cation-olefin monocyclization by engineered squalene-hopene cyclases’, Angewandte Chemie: International Edition, 60(50), pp. 26080–26086. Available at: https://doi.org/10.1002/anie.202108037.

M. Eichenberger et al., “Asymmetric cation-olefin monocyclization by engineered squalene-hopene cyclases,” Angewandte Chemie: International Edition, vol. 60, no. 50, pp. 26080–26086, 2021, doi: 10.1002/anie.202108037.

EICHENBERGER, Michael, Sean HÜPPI, David PATSCH, Natalie AEBERLI, Raphael BERWEGER, Sandro DOSSENBACH, Eric EICHHORN, Felix FLACHSMANN, Lucas HORTENCIO, Francis VOIROL, Sabine VOLLENWEIDER, Uwe T. BORNSCHEUER und Rebecca BULLER, 2021. Asymmetric cation-olefin monocyclization by engineered squalene-hopene cyclases. Angewandte Chemie: International Edition. 2021. Bd. 60, Nr. 50, S. 26080–26086. DOI 10.1002/anie.202108037

Eichenberger, Michael, Sean Hüppi, David Patsch, Natalie Aeberli, Raphael Berweger, Sandro Dossenbach, Eric Eichhorn, et al. 2021. “Asymmetric Cation-Olefin Monocyclization by Engineered Squalene-Hopene Cyclases.” Angewandte Chemie: International Edition 60 (50): 26080–86. https://doi.org/10.1002/anie.202108037.

Eichenberger, Michael, et al. “Asymmetric Cation-Olefin Monocyclization by Engineered Squalene-Hopene Cyclases.” Angewandte Chemie: International Edition, vol. 60, no. 50, 2021, pp. 26080–86, https://doi.org/10.1002/anie.202108037.