Katalytische Phenolhydroxylierung mit Sauerstoff: Substratvielfalt jenseits der Proteinmatrix von Tyrosinase

Hoffmann, Alexander; Citek, Cooper; Binder, Stephan; Goos, Arne; Rübhausen, Michael; Troeppner, Oliver; Ivanović‐Burmazović, Ivana; Wasinger, Erik C.; Stack, T. Daniel P.; Herres‐Pawlis, Sonja

doi:10.1002/ange.201301249

Cited by 44 publications

(45 citation statements)

References 38 publications

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“…For the Fe(III)-superoxo case (with [48] porphyrin ligands), usually the unpaired electron of the d 5 -LS iron center antiferromagnetically couples with the unpaired electron of the superoxo radical to deliver a diamagnetic ground state. For the Cu(II)-superoxo case, a similar case can be imagined [56][57][58]. However, there are some Cu(II)-superoxo model complexes (Fig.…”

Section: Activation Of Dioxygenmentioning

confidence: 90%

Use of EPR Spectroscopy to Unravel Reaction Mechanisms in (Catalytic) Bond Activation Reactions: Some Selected Examples

Manck

Sarkar

2015

Top Catal

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Paramagnetic species are ubiquitous intermediates in many different reactions involving chemical bond activation and catalysis. Despite this fact, the use of electron paramagnetic resonance (EPR) spectroscopy for unraveling reaction mechanisms for homogeneous catalytic reactions has been rather limited. This overview article details several areas dealing with small molecule activation in the homogeneous medium where EPR spectroscopy is potentially useful and has sometimes been used. We will present various examples from the literature to show the usefulness of this method in studying the activation and possible fixation of small molecules such as H 2 , O 2 , and N 2 . Additionally, some examples related to nitridyl radicals and their relation with carbene radicals will also be discussed with a focus on their detection through EPR spectroscopy. We will present the usefulness and the limitations of this method by discussing selected examples from the literature. This is not meant to be a comprehensive review.

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Section: Activation Of Dioxygenmentioning

confidence: 90%

Use of EPR Spectroscopy to Unravel Reaction Mechanisms in (Catalytic) Bond Activation Reactions: Some Selected Examples

Manck

Sarkar

2015

Top Catal

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“…[16] Highly enlightening results from the groups of Karlin [4a,-b,e, 9d, 17] and Ito [18] on Cu-O 2 chemistry, along with support from crystallographic [19] and spectroscopic [20] evidence, strongly suggest an electrophilic reactivity of a side-on-type peroxo intermediate for aromatic o-hydroxylation of monophenols by tyrosinase. [21] The oxygenase transformation of the oxindole 12 into 13 seems to follow a similar reaction mechanism. Thus, insertion of molecular oxygen into the copper(I) complex 16 generates a side-on m-h 2 :h 2 -peroxo complex (17; Scheme 3).…”

Section: Methodsmentioning

confidence: 98%

A Bioinspired Catalytic Oxygenase Cascade to Generate Complex Oxindoles

et al. 2014

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Catalytic, selective, and controlled oxidative functionalization of C-H bonds using molecular oxygen as an oxidant remains highly desirable and equally challenging in the development of synthetic methodologies. Presented herein is a one-pot oxygenase cascade reaction wherein a copper(I)-catalyzed oxygenase reaction transforms the allylic methyl group in 3-methylidene oxindoles into an aldehyde, which then undergoes an aldol-oxa-Michael addition sequence with β-ketoesters to yield dihydrofuran-bearing oxindoles.

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“…Differently substituted ketoesters yielded adducts decorated with alkyl, aryl, and heterocyclic moieties with good stereoselectivities and appreciable yields, thus demonstrating the scope and generality of the catalytic oxygenase cascade reaction (Scheme 2). [21] The oxygenase transformation of the oxindole 12 into 13 seems to follow a similar reaction mechanism. In a separate reaction of the pure aldehyde (E)-13 a and the ketoester 15 a (R = Et, R 2 = Me), the adduct 14 a was obtained in similar yields and diastereoselectivities.…”

Section: Methodsmentioning

confidence: 99%

A Bioinspired Catalytic Oxygenase Cascade to Generate Complex Oxindoles

Wang¹,

Bauer²,

Strohmann³

et al. 2014

Angewandte Chemie

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Catalytic, selective, and controlled oxidative functionalization of CÀH bonds using molecular oxygen as an oxidant remains highly desirable and equally challenging in the development of synthetic methodologies. Presented herein is a one-pot oxygenase cascade reaction wherein a copper(I)catalyzed oxygenase reaction transforms the allylic methyl group in 3-methylidene oxindoles into an aldehyde, which then undergoes an aldol-oxa-Michael addition sequence with bketoesters to yield dihydrofuran-bearing oxindoles.

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Katalytische Phenolhydroxylierung mit Sauerstoff: Substratvielfalt jenseits der Proteinmatrix von Tyrosinase

Cited by 44 publications

References 38 publications

Use of EPR Spectroscopy to Unravel Reaction Mechanisms in (Catalytic) Bond Activation Reactions: Some Selected Examples

Use of EPR Spectroscopy to Unravel Reaction Mechanisms in (Catalytic) Bond Activation Reactions: Some Selected Examples

A Bioinspired Catalytic Oxygenase Cascade to Generate Complex Oxindoles

A Bioinspired Catalytic Oxygenase Cascade to Generate Complex Oxindoles

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