Universität zu Köln

Weidmann, Verena, Kliewer, Serge, Sicka, Marko, Bycinskij, Sergej, Kleczka, Margarethe, Rehbein, Julia, Griesbeck, Axel G. ORCID: 0000-0002-6546-3482, Zorn, Holger ORCID: 0000-0002-8383-8196 and Maison, Wolfgang (2015). Studies towards the synthetic applicability of biocatalytic allylic oxidations with the lyophilisate of Pleurotus sapidus. J. Mol. Catal. B-Enzym., 121. S. 15 - 22. AMSTERDAM: ELSEVIER SCIENCE BV. ISSN 1873-3158

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Abstract

The edible fungus Pleurotus sapidus (PSA) is a particularly interesting biocatalytic system for allylic oxidation and has a remarkably broad substrate range from terpenoids to fatty acids. The oxidations are most likely catalyzed by a lipoxygenase and involve the formation of peroxides via radical intermediates in the first rate-limiting step. We provide herein a rationalization of the observed regioselectivity of these conversions by means of computational determination of bond dissociation enthalpies of a set of tailor-made spirocyclic terpenoids. It was found that only strongly activated allylic positions (BDH298 of <80 kcal/mol) with neighboring heteroatoms or with activating alkyl groups are oxidized to the corresponding unsaturated lactones or enones, respectively. With the synthesis and purification of allylic hydroperoxide intermediates, we have been able to characterize the putative direct precursors of enones in PSA oxidations. Our results suggest a two-step oxidation mechanism involving hydroperoxide intermediates which are rapidly converted to the observed enones by an enzymatic reaction. (C) 2015 Elsevier B.V. All rights reserved.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Weidmann, Verena UNSPECIFIED UNSPECIFIED UNSPECIFIED Kliewer, Serge UNSPECIFIED UNSPECIFIED UNSPECIFIED Sicka, Marko UNSPECIFIED UNSPECIFIED UNSPECIFIED Bycinskij, Sergej UNSPECIFIED UNSPECIFIED UNSPECIFIED Kleczka, Margarethe UNSPECIFIED UNSPECIFIED UNSPECIFIED Rehbein, Julia UNSPECIFIED UNSPECIFIED UNSPECIFIED Griesbeck, Axel G. UNSPECIFIED orcid.org/0000-0002-6546-3482 UNSPECIFIED Zorn, Holger UNSPECIFIED orcid.org/0000-0002-8383-8196 UNSPECIFIED Maison, Wolfgang UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-388030
DOI:	10.1016/j.molcatb.2015.07.008
Journal or Publication Title:	J. Mol. Catal. B-Enzym.
Volume:	121
Page Range:	S. 15 - 22
Date:	2015
Publisher:	ELSEVIER SCIENCE BV
Place of Publication:	AMSTERDAM
ISSN:	1873-3158
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language MONOUNSATURATED FATTY-ACIDS; C-H BONDS; STEROID CHEMISTRY; OLEFINS; HYDROPEROXIDES; (+)-VALENCENE; LIPOXYGENASE; DIOXYGENASE; SPIROETHERS; OXYGENATION Multiple languages Biochemistry & Molecular Biology; Chemistry, Physical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/38803