Biokatalytische einstufige Alkenspaltung von Arylalkenen: ein enzymatisches Äquivalent zur reduktiven Ozonisierung

Mang, Harald; Gross, Johannes; Lara, Miguel; Goessler, Christian; Guebitz, Georg M.; Kroutil, Wolfgang

doi:10.1002/ange.200601574

Cited by 7 publications

(4 citation statements)

References 56 publications

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“…The enzyme TM1459 showed high chemoselectivity towards alkene cleavage versus epoxidation (which was not observed or negligible for most substrates) as opposed to most known peroxidase systems and manganese‐protein based systems, with the exception of the manganese‐dependent enzyme discovered in Trametes hirsuta 1f,3b. In the heme‐containing Coprinus cinereus peroxidase, benzaldehyde derivatives were observed as major products from (substituted) styrenes in reactions with hydrogen peroxide, however with significant amounts of epoxide as side‐product (ratio epoxide to benzaldehyde between 1:1.2 and 1:10.76b).…”

Section: Resultsmentioning

confidence: 97%

Oxidative Alkene Cleavage Catalysed by Manganese‐Dependent Cupin TM1459 from Thermotoga maritima

et al. 2015

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An ovel biocatalytic oxidative alkene cleavagea ctivity was identifiedi np rotein TM1459 from Thermotoga maritima,aso far uncharacterised metalloprotein with ac upinf old, which preferentially binds manganese (over iron and zinc). Va rious styrene derivatives were converted with high chemoselectivity to the corresponding carbonylc ompounds by the manganese-containing protein,u sing organic hydroperoxide and molecular oxygen as oxidant. 4-Chloroacetophenone could be obtainedi n4 0% conversion from 4-chloro-a-methylstyrene (50 mM) in ab iphasic systemu sing ethyl acetate as organic cosolvent (5% v/v), while 76% conversion was obtained at al ower substrate concentration (10 mM). This novel biocatalyst can be easily over-expressed in Escherichia coli in exceptionally high yield andp urified, andt hus mayo ffer av aluablea nd safer alternative in oxidative C=Cb ond cleavage reactions for synthetic applications.

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Section: Resultsmentioning

confidence: 97%

Oxidative Alkene Cleavage Catalysed by Manganese‐Dependent Cupin TM1459 from Thermotoga maritima

et al. 2015

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“…This methodology would offer metal-free, cost-effective access to synthetically useful transformations with an environmentally friendly character in comparison with traditional processes. [5][6][7] Current applications include the selective formylation of primary and secondary aliphatic alcohols, oxidation of benzylic alcohols, benzylic C=C cleavage reactions, and benzylic sp 3 CÀH oxidation. Further applications of the present protocol to other reactions are in progress.…”

Section: Discussionmentioning

confidence: 99%

“…[5][6][7] As shown in Table 3, a series of primary and secondary aliphatic alcohols were selectively converted to the corresponding formates 1 c-g in moderate to high yields (entries 1-6) whereas the tertiary aliphatic alcohol remained unchanged (entry 7), probably because of steric hindrance.…”

Section: Substrate Scopementioning

confidence: 99%

The Free‐Radical Chemistry of Polyethylene Glycol: Organic Reactions in Compressed Carbon Dioxide

Wang

Miao

et al. 2009

ChemSusChem

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The thermal oxidative degradation of polyethylene glycol (PEG) is known to occur in an oxygen atmosphere at elevated temperatures. In this study, PEG radicals assumed to result from thermal oxidative degradation are successfully applied, in combination with compressed CO(2), to initiate a range of free-radical reactions, such as selective formylation of primary and secondary aliphatic alcohols, oxidation of benzylic alcohols, benzylic C==C bond cleavage, and benzylic sp(3) C--H oxidation, demonstrating enormous synthetic potential in a cost-efficient, practically useful, and environmentally friendly manner; not requiring any catalyst or additional free-radical initiator. We find that both PEG and molecular oxygen are prerequisites in order to perform these reactions smoothly. Given that dense CO(2) is immune to free-radical chemistry; it is an ideal solvent for such reactions. As a result, compressed CO(2) allows reactions initiated by PEG radicals to be tuned by subtly adjusting reaction parameters such as the CO(2) pressure, thereby enhancing the product selectivity. By attaining a high selectivity towards the desired products this methodology is practical for organic syntheses.

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“…[71] Quercetinase is an induced extracellular dioxygenase produced by Aspergillus flavus when grown on rutin, a flavonoid glycoside, and is Cu(II)-dependent. [42] It is noteworthy that other C=C double bonds are not transformed, thus, the enzyme distinguishes between double bonds adjacent to a phenyl group and others. Cleavage of acireductone to 2-keto-4-thiomethylbutyrate and formic acid is an unusual transformation step in the l-methionine salvage pathway (Scheme 18D).…”

Section: Non-iron Metal-dependent Alkene Cleaving Enzymesmentioning

confidence: 99%

Oxidative Alkene Cleavage by Chemical and Enzymatic Methods

2013

Self Cite

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The cleavage of alkenes to the corresponding carbonyl products is a widely employed method in organic synthesis, especially to introduce oxygen functionalities into molecules, remove protecting groups and tailor large molecules. Chemical methods available for alkene cleavage include, for instance, ozonolysis, several metal-based variants (KMnO 4 , OsO 4 , RuO 4 , etc.), electrochemical alternatives, singlet oxygen, hypervalent iodine and organic molecules in combination with oxygen. Furthermore, several enzymatic methods for alkene cleavage have been described to establish safe, mild and selective oxidation methods. Various heme and non-heme iron-dependent enzymes catalyse the alkene cleavage at ambient temperature and atmospheric pressure in an aqueous buffer, showing good chemo-and regioselectivities in selected cases. Quite recently some Cu-, Mn-and Ni-dependent enzymes have been identified for this reaction. This review gives an overview of the different chemical and enzymatic methods available for the cleavage of alkenes.

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Biokatalytische einstufige Alkenspaltung von Arylalkenen: ein enzymatisches Äquivalent zur reduktiven Ozonisierung

Cited by 7 publications

References 56 publications

Oxidative Alkene Cleavage Catalysed by Manganese‐Dependent Cupin TM1459 from Thermotoga maritima

Oxidative Alkene Cleavage Catalysed by Manganese‐Dependent Cupin TM1459 from Thermotoga maritima

The Free‐Radical Chemistry of Polyethylene Glycol: Organic Reactions in Compressed Carbon Dioxide

Oxidative Alkene Cleavage by Chemical and Enzymatic Methods

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