Arene <i>cis</i>‐Diol Dehydrogenase‐Catalysed Regio‐ and Stereoselective Oxidation of Arene‐, Cycloalkane‐ and Cycloalkene‐<i>cis</i>‐diols to Yield Catechols and Chiral α‐Ketols

Boyd, Derek R.; Sharma, Narain D.; Berberian, M. Victoria; Cleij, Marcel; Hardacre, Christopher; Ljubez, Vera; McConville, Gareth; Stevenson, Paul J.; Kulakov, Leonid; Allen, Christopher C. R.

doi:10.1002/adsc.201500189

Cited by 9 publications

(10 citation statements)

References 68 publications

(80 reference statements)

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“…64 Nanocluster Pd/Au- 17 provides excellent enantioselectivities (91 – 99% ee) in the oxidation of diols, and results of the enantioselectivity from the oxidation of trans -diols are comparable to those reported using enzymes. 65,66…”

Section: Resultsmentioning

confidence: 99%

Chiral-Substituted Poly-N-vinylpyrrolidinones and Bimetallic Nanoclusters in Catalytic Asymmetric Oxidation Reactions

et al. 2016

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A new class of poly-N-vinylpyrrolidinones containing an asymmetric center at C5 of the pyrrolidinone ring were synthesized from l-amino acids. The polymers, particularly 17, were used to stabilize nanoclusters such as Pd/Au for the catalytic asymmetric oxidations of 1,3- and 1,2-cycloalkanediols and alkenes, and Cu/Au was used for C-H oxidation of cycloalkanes. It was found that the bulkier the C5 substituent in the pyrrolidinone ring, the greater the optical yields produced. Both oxidative kinetic resolution of (±)-1,3- and 1,2-trans-cycloalkanediols and desymmetrization of meso cis-diols took place with 0.15 mol % Pd/Au (3:1)-17 under oxygen atmosphere in water to give excellent chemical and optical yields of (S)-hydroxy ketones. Various alkenes were oxidized with 0.5 mol % Pd/Au (3:1)-17 under 30 psi of oxygen in water to give the dihydroxylated products in >93% ee. Oxidation of (R)-limonene at 25 °C occurred at the C-1,2-cyclic alkene function yielding (1S,2R,4R)-dihydroxylimonene 49 in 92% yield. Importantly, cycloalkanes were oxidized with 1 mol % Cu/Au (3:1)-17 and 30% HO in acetonitrile to afford chiral ketones in very good to excellent chemical and optical yields. Alkene function was not oxidized under the reaction conditions. Mechanisms were proposed for the oxidation reactions, and observed stereo- and regio-chemistry were summarized.

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Section: Resultsmentioning

confidence: 99%

Chiral-Substituted Poly-N-vinylpyrrolidinones and Bimetallic Nanoclusters in Catalytic Asymmetric Oxidation Reactions

et al. 2016

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“… ADH‐catalysed oxidation of 1,2‐diols to the corresponding ( R )‐ or ( S )‐α‐hydroxy ketones depending on the ADH used. BdhA: butane diol DH from B. subtilis ; BCDD: cis ‐diol DH from P. putida …”

Section: Oxidation Of Alcoholsmentioning

confidence: 99%

Biocatalytic Oxidation Reactions: A Chemist's Perspective

et al. 2018

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Oxidation chemistry using enzymes is approaching maturity and practical applicability in organic synthesis. Oxidoreductases (enzymes catalysing redox reactions) enable chemists to perform highly selective and efficient transformations ranging from simple alcohol oxidations to stereoselective halogenations of non‐activated C−H bonds. For many of these reactions, no “classical” chemical counterpart is known. Hence oxidoreductases open up shorter synthesis routes based on a more direct access to the target products. The generally very mild reaction conditions may also reduce the environmental impact of biocatalytic reactions compared to classical counterparts. In this Review, we critically summarise the most important recent developments in the field of biocatalytic oxidation chemistry and identify the most pressing bottlenecks as well as promising solutions.

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“…The TDO‐catalyzed cis ‐dihydroxylation of substituted benzyl alcohol enantiomers yielded triol diastereomers ( 80a–e and 81a–e , Diagram 5). These triols, in turn, proved to be good substrates for a naphthalene diol dehydrogenase enzyme, which catalyzed their biotransformations, to yield individual (+)‐ and (−)‐catechol enantiomers ( 82a–e ) . As separations (Δ δ OMe ) of diagnostic 1 H–NMR signals of the boronates, formed using MEPBA 4a S with (+) and (−)‐catechols ( 82a–e ), were relatively small ( δ OMe 3.15–3.28), it was considered appropriate to test the new boronic acid (+)‐MPPBA 4c R (Table ) .…”

Section: Resultsmentioning

confidence: 99%

“… These triols, in turn, proved to be good substrates for a naphthalene diol dehydrogenase enzyme, which catalyzed their biotransformations, to yield individual (+)‐ and (−)‐catechol enantiomers ( 82a–e ) . As separations (Δ δ OMe ) of diagnostic 1 H–NMR signals of the boronates, formed using MEPBA 4a S with (+) and (−)‐catechols ( 82a–e ), were relatively small ( δ OMe 3.15–3.28), it was considered appropriate to test the new boronic acid (+)‐MPPBA 4c R (Table ) . The magnitude of the observed values (Δ δ OMe 20–120), for boronates from enantiomers of catechols ( 82a–e ) with (+)‐MPPBA 4c R , confirmed that the reagent can be successfully applied, to determine the ee values of chiral catechol metabolites derived from benzylic alcohols, and possibly also to catechols derived from alkylaryl sulfoxides …”

Section: Resultsmentioning

confidence: 99%

Enantiopurity and absolute configuration determination of arene cis‐dihydrodiol metabolites and derivatives using chiral boronic acids

et al. 2017

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The relative merits of the methods employed to determine enantiomeric excess (ee) values and absolute configurations of chiral arene and alkene cis-1,2-diol metabolites, including boronate formation, using racemic or enantiopure (+) and (−)-2-(1-methoxyethyl)phenylboronic acid (MEPBA), are discussed. group was on the structural/stereochemical identification of new cis-dihydrodiol metabolites, from monoand di-substituted benzene and polycyclic aromatic hydrocarbon substrates, using different dioxygenase enzymes. [1][2][3][4][5][6][7][8][9][10] The instability of arene cis-dihydrodiol metabolites, and their unavailability in sufficient quantities, were early barriers to their utilization in synthetic chemistry. [1][2][3][4][5][6][7][8] In 1983, the development of a proprietary constituent mutant strain of P. putida (UV4) by ICI, expressing toluene dioxygenase (TDO), led to the commercial production of arene cis-dihydrodiols, e.g., B (X = Y = H and X = Me, Y = H), and the first applications of this strain in synthesis. 11-13The availability of other mutant (Pseudomonas and Sphingomonas) and recombinant (Escherichia coli) strains, expressing TDO, naphthalene dioxygenase (NDO), biphenyl dioxygenase (BPDO), and benzoate dioxygenase for biotransformation resulted in a marked increase in worldwide interest in this type of bacterial metabolite. To date,

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Arene cis‐Diol Dehydrogenase‐Catalysed Regio‐ and Stereoselective Oxidation of Arene‐, Cycloalkane‐ and Cycloalkene‐cis‐diols to Yield Catechols and Chiral α‐Ketols

Cited by 9 publications

References 68 publications

Chiral-Substituted Poly-N-vinylpyrrolidinones and Bimetallic Nanoclusters in Catalytic Asymmetric Oxidation Reactions

Chiral-Substituted Poly-N-vinylpyrrolidinones and Bimetallic Nanoclusters in Catalytic Asymmetric Oxidation Reactions

Biocatalytic Oxidation Reactions: A Chemist's Perspective

Enantiopurity and absolute configuration determination of arene cis‐dihydrodiol metabolites and derivatives using chiral boronic acids

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