Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase
Peroxygenases are heme-dependent enzymes that use peroxide-borne oxygen to catalyze a wide range of oxyfunctionalization reactions. Herein, we report the engineering of an unusual cofactor-independent peroxygenase based on a promiscuous tautomerase that accepts different hydroperoxides (t-BuOOH and...
Published in: | Angewandte Chemie International Edition |
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2020
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Online Access: | https://hdl.handle.net/11370/3f4521bb-acfc-41f7-ad68-ae9bff4d983b https://research.rug.nl/en/publications/3f4521bb-acfc-41f7-ad68-ae9bff4d983b https://doi.org/10.1002/anie.202001373 https://pure.rug.nl/ws/files/131633242/anie.202001373.pdf |
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ftunigroningenpu:oai:pure.rug.nl:publications/3f4521bb-acfc-41f7-ad68-ae9bff4d983b 2024-06-23T07:45:42+00:00 Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase Xu, Guangcai Crotti, Michele Thangavelu, Saravan Kataja, Kim Poelarends, Gerrit J. 2020-06-22 application/pdf https://hdl.handle.net/11370/3f4521bb-acfc-41f7-ad68-ae9bff4d983b https://research.rug.nl/en/publications/3f4521bb-acfc-41f7-ad68-ae9bff4d983b https://doi.org/10.1002/anie.202001373 https://pure.rug.nl/ws/files/131633242/anie.202001373.pdf eng eng https://research.rug.nl/en/publications/3f4521bb-acfc-41f7-ad68-ae9bff4d983b info:eu-repo/semantics/openAccess Xu , G , Crotti , M , Thangavelu , S , Kataja , K & Poelarends , G J 2020 , ' Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase ' , Angewandte Chemie International Edition , vol. 59 , no. 26 , pp. 10374-10378 . https://doi.org/10.1002/anie.202001373 MICHAEL-TYPE ADDITIONS PEROXIDE-DRIVEN HYDROXYLATION ANTARCTICA LIPASE B 4-OXALOCROTONATE TAUTOMERASE ASYMMETRIC EPOXIDATION CHLOROPEROXIDASE ACETALDEHYDE OXIDATIONS ALDEHYDES ENZYMES article 2020 ftunigroningenpu https://doi.org/10.1002/anie.202001373 2024-06-03T16:56:23Z Peroxygenases are heme-dependent enzymes that use peroxide-borne oxygen to catalyze a wide range of oxyfunctionalization reactions. Herein, we report the engineering of an unusual cofactor-independent peroxygenase based on a promiscuous tautomerase that accepts different hydroperoxides (t-BuOOH and H 2 O 2 ) to accomplish enantiocomplementary epoxidations of various α,β-unsaturated aldehydes (citral and substituted cinnamaldehydes), providing access to both enantiomers of the corresponding α,β-epoxy-aldehydes. High conversions (up to 98 %), high enantioselectivity (up to 98 % ee), and good product yields (50–80 %) were achieved. The reactions likely proceed via a reactive enzyme-bound iminium ion intermediate, allowing tweaking of the enzyme's activity and selectivity by protein engineering. Our results underscore the potential of catalytic promiscuity for the engineering of new cofactor-independent oxidative enzymes. Article in Journal/Newspaper Antarc* Antarctica University of Groningen research database Angewandte Chemie International Edition 59 26 10374 10378 |
institution |
Open Polar |
collection |
University of Groningen research database |
op_collection_id |
ftunigroningenpu |
language |
English |
topic |
MICHAEL-TYPE ADDITIONS PEROXIDE-DRIVEN HYDROXYLATION ANTARCTICA LIPASE B 4-OXALOCROTONATE TAUTOMERASE ASYMMETRIC EPOXIDATION CHLOROPEROXIDASE ACETALDEHYDE OXIDATIONS ALDEHYDES ENZYMES |
spellingShingle |
MICHAEL-TYPE ADDITIONS PEROXIDE-DRIVEN HYDROXYLATION ANTARCTICA LIPASE B 4-OXALOCROTONATE TAUTOMERASE ASYMMETRIC EPOXIDATION CHLOROPEROXIDASE ACETALDEHYDE OXIDATIONS ALDEHYDES ENZYMES Xu, Guangcai Crotti, Michele Thangavelu, Saravan Kataja, Kim Poelarends, Gerrit J. Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase |
topic_facet |
MICHAEL-TYPE ADDITIONS PEROXIDE-DRIVEN HYDROXYLATION ANTARCTICA LIPASE B 4-OXALOCROTONATE TAUTOMERASE ASYMMETRIC EPOXIDATION CHLOROPEROXIDASE ACETALDEHYDE OXIDATIONS ALDEHYDES ENZYMES |
description |
Peroxygenases are heme-dependent enzymes that use peroxide-borne oxygen to catalyze a wide range of oxyfunctionalization reactions. Herein, we report the engineering of an unusual cofactor-independent peroxygenase based on a promiscuous tautomerase that accepts different hydroperoxides (t-BuOOH and H 2 O 2 ) to accomplish enantiocomplementary epoxidations of various α,β-unsaturated aldehydes (citral and substituted cinnamaldehydes), providing access to both enantiomers of the corresponding α,β-epoxy-aldehydes. High conversions (up to 98 %), high enantioselectivity (up to 98 % ee), and good product yields (50–80 %) were achieved. The reactions likely proceed via a reactive enzyme-bound iminium ion intermediate, allowing tweaking of the enzyme's activity and selectivity by protein engineering. Our results underscore the potential of catalytic promiscuity for the engineering of new cofactor-independent oxidative enzymes. |
format |
Article in Journal/Newspaper |
author |
Xu, Guangcai Crotti, Michele Thangavelu, Saravan Kataja, Kim Poelarends, Gerrit J. |
author_facet |
Xu, Guangcai Crotti, Michele Thangavelu, Saravan Kataja, Kim Poelarends, Gerrit J. |
author_sort |
Xu, Guangcai |
title |
Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase |
title_short |
Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase |
title_full |
Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase |
title_fullStr |
Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase |
title_full_unstemmed |
Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase |
title_sort |
enantiocomplementary epoxidation reactions catalyzed by an engineered cofactor‐independent non‐natural peroxygenase |
publishDate |
2020 |
url |
https://hdl.handle.net/11370/3f4521bb-acfc-41f7-ad68-ae9bff4d983b https://research.rug.nl/en/publications/3f4521bb-acfc-41f7-ad68-ae9bff4d983b https://doi.org/10.1002/anie.202001373 https://pure.rug.nl/ws/files/131633242/anie.202001373.pdf |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
Xu , G , Crotti , M , Thangavelu , S , Kataja , K & Poelarends , G J 2020 , ' Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐Natural Peroxygenase ' , Angewandte Chemie International Edition , vol. 59 , no. 26 , pp. 10374-10378 . https://doi.org/10.1002/anie.202001373 |
op_relation |
https://research.rug.nl/en/publications/3f4521bb-acfc-41f7-ad68-ae9bff4d983b |
op_rights |
info:eu-repo/semantics/openAccess |
op_doi |
https://doi.org/10.1002/anie.202001373 |
container_title |
Angewandte Chemie International Edition |
container_volume |
59 |
container_issue |
26 |
container_start_page |
10374 |
op_container_end_page |
10378 |
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1802641967805366272 |