Biocatalytic Enantioselective Oxidation of Sec-Allylic Alcohols with Flavin-Dependent Oxidases

Somayyeh Gandomkar, Etta Jost, Doris Loidolt, Alexander Swoboda, Mathias Pickl, Wael Elaily, Bastian Daniel, Marco W. Fraaije, Peter Macheroux, Wolfgang Kroutil

Publikation: Beitrag in einer FachzeitschriftArtikelForschungBegutachtung

Abstract

The oxidation of allylic alcohols is challenging to perform in a chemo- as well as stereo-selective fashion at the expense of molecular oxygen using conventional chemical protocols. Here, we report the identification of a library of flavin-dependent oxidases including variants of the berberine bridge enzyme (BBE) analogue from Arabidopsis thaliana (AtBBE15) and the 5-(hydroxymethyl)furfural oxidase (HMFO) and its variants (V465T, V465S, V465T/W466H and V367R/W466F) for the enantioselective oxidation of sec-allylic alcohols. While primary and benzylic alcohols as well as certain sugars are well known to be transformed by flavin-dependent oxidases, sec-allylic alcohols have not been studied yet except in a single report. The model substrates investigated were oxidized enantioselectively in a kinetic resolution with an E-value of up to >200. For instance HMFO V465S/T oxidized the (S)-enantiomer of (E)-oct-3-en-2-ol (1 a) and (E)-4-phenylbut-3-en-2-ol with E>200 giving the remaining (R)-alcohol with ee>99% at 50% conversion. The enantioselectivity could be decreased if required by medium engineering by the addition of cosolvents (e. g. dimethyl sulfoxide).
Originalspracheenglisch
Seiten (von - bis)5264-5271
Seitenumfang8
FachzeitschriftAdvanced Synthesis and Catalysis
Jahrgang361
Ausgabenummer22
DOIs
PublikationsstatusVeröffentlicht - 19 Nov 2019

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Oxidoreductases
Alcohols
Furfural
Oxidation
Furaldehyde
Dimethyl sulfoxide
Enantiomers
Molecular oxygen
Enantioselectivity
Dimethyl Sulfoxide
Arabidopsis
Enzymes
Oxygen
Kinetics
allyl alcohol
4,6-dinitro-o-cresol
Substrates

Schlagwörter

    ASJC Scopus subject areas

    • Organische Chemie
    • !!Biochemistry

    Dies zitieren

    Biocatalytic Enantioselective Oxidation of Sec-Allylic Alcohols with Flavin-Dependent Oxidases. / Gandomkar, Somayyeh; Jost, Etta; Loidolt, Doris; Swoboda, Alexander; Pickl, Mathias; Elaily, Wael; Daniel, Bastian; Fraaije, Marco W.; Macheroux, Peter; Kroutil, Wolfgang.

    in: Advanced Synthesis and Catalysis, Jahrgang 361, Nr. 22, 19.11.2019, S. 5264-5271.

    Publikation: Beitrag in einer FachzeitschriftArtikelForschungBegutachtung

    Gandomkar, Somayyeh ; Jost, Etta ; Loidolt, Doris ; Swoboda, Alexander ; Pickl, Mathias ; Elaily, Wael ; Daniel, Bastian ; Fraaije, Marco W. ; Macheroux, Peter ; Kroutil, Wolfgang. / Biocatalytic Enantioselective Oxidation of Sec-Allylic Alcohols with Flavin-Dependent Oxidases. in: Advanced Synthesis and Catalysis. 2019 ; Jahrgang 361, Nr. 22. S. 5264-5271.
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