title: Elucidation of the regio- and chemoselectivity of enzymatic allylic oxidations with Pleurotus sapidus - conversion of selected spirocyclic terpenoids and computational analysis.
abstract: Allylic oxidations of olefins to enones allow the efficient synthesis of value-added products from simple olefinic precursors like terpenes or terpenoids. Biocatalytic variants have a large potential for industrial applications, particularly in the pharmaceutical and food industry. Herein we report efficient biocatalytic allylic oxidations of spirocyclic terpenoids by a lyophilisate of the edible fungus Pleurotus sapidus. This ''mushroom catalysis'' is operationally simple and allows the conversion of various unsaturated spirocyclic terpenoids. A number of new spirocyclic enones have thus been obtained with good regio- and chemoselectivity and chiral separation protocols for enantiomeric mixtures have been developed. The oxidations follow a radical mechanism and the regioselectivity of the reaction is mainly determined by bond-dissociation energies of the available allylic CH-bonds and steric accessibility of the oxidation site.
authors.affiliation: Department of Chemistry, University of Hamburg, Bundesstr. 45, 20146 Hamburg, Germany.
authors.forename: Verena
authors.initials: V
authors.lastname: Weidmann
authors.forename: Mathias
authors.initials: M
authors.lastname: Schaffrath
authors.forename: Holger
authors.initials: H
authors.lastname: Zorn
authors.forename: Julia
authors.initials: J
authors.lastname: Rehbein
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Maison
keywords: CH-activation; allylic oxidation; chiral separation; enones; flavors; natural products; terpenes