Direct biocatalytic synthesis of functionalized catechols: a green alternative to traditional methods with high effective mass yield

Bui, Vu; Hansen, Trond Vidar; Stenstrøm, Yngve; Hudlický, Tomáš

doi:10.1039/b006988o

Cited by 28 publications

(17 citation statements)

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“…Substituted catechols, especially 3-substituted catechols, are useful precursors for making pharmaceuticals (14); one of these compounds, 3-methoxycatechol, is an important intermediate for the antivascular agents combretastatin A-1 and combretastatin B-1 (5). Methoxyhydroquinone is used in the synthesis of triptycene quinones that have been shown to have anti-leukemia cell activity (16), and methylhydroquinone has been recently reported to be used in the synthesis of (Ϯ)-helibisabonol A and puraquinonic acid, which are precursors of agrochemical herbicides and antileukemia drugs, respectively (15,20).…”

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“…Canada et al (6) used DNA shuffling to evolve toluene ortho-monooxygenase (TOM) from Burkholderia cepacia G4 for 1-naphthol synthesis, and one mutant (TomA3 V106A) with sixfold-increased activity was found. Furthermore, substituted catechols (e.g., 3-bromocatechol, 3-methoxycatechol, 3-iodocatechol, and 3-methylcatechol) were synthesized from substituted benzenes in two steps by using recombinant Escherichia coli expressing both toluene dioxygenase and dihydrocatechol dehydrogenase (5).…”

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Altering Toluene 4-Monooxygenase by Active-Site Engineering for the Synthesis of 3-Methoxycatechol, Methoxyhydroquinone, and Methylhydroquinone

et al. 2004

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Wild-type toluene 4-monooxygenase (T4MO) of Pseudomonas mendocina KR1 oxidizes toluene to p-cresol (96%) and oxidizes benzene sequentially to phenol, to catechol, and to 1,2,3-trihydroxybenzene. In this study T4MO was found to oxidize o-cresol to 3-methylcatechol (91%) and methylhydroquinone (9%), to oxidize m-cresol and p-cresol to 4-methylcatechol (100%), and to oxidize o-methoxyphenol to 4-methoxyresorcinol (87%), 3-methoxycatechol (11%), and methoxyhydroquinone (2%). Apparent V max values of 6.6 ؎ 0.9 to 10.7 ؎ 0.1 nmol/min/ mg of protein were obtained for o-, m-, and p-cresol oxidation by wild-type T4MO, which are comparable to the toluene oxidation rate (15.1 ؎ 0.8 nmol/min/mg of protein). After these new reactions were discovered, saturation mutagenesis was performed near the diiron catalytic center at positions I100, G103, and A107 of the alpha subunit of the hydroxylase ( . Variant I100L produced 3-methoxycatechol from o-methoxyphenol four times faster than wild-type T4MO, and G103S/A107T produced methylhydroquinone (92%) from o-cresol fourfold faster than wild-type T4MO and there was 10 times more in terms of the percentage of the product. Variant G103S produced 40-fold more methoxyhydroquinone from o-methoxyphenol than the wild-type enzyme produced (80 versus 2%) and produced methylhydroquinone (80%) from o-cresol. Hence, the regiospecific oxidation of o-methoxyphenol and o-cresol was changed for significant synthesis of 3-methoxycatechol, methoxyhydroquinone, 3-methylcatechol, and methylhydroquinone. The enzyme variants also demonstrated altered monohydroxylation regiospecificity for toluene; for example, G103S/ A107G formed 82% o-cresol, so saturation mutagenesis converted T4MO into an ortho-hydroxylating enzyme. Furthermore, G103S/A107T formed 100% p-cresol from toluene; hence, a better para-hydroxylating enzyme than wild-type T4MO was formed. Structure homology modeling suggested that hydrogen bonding interactions of the hydroxyl groups of altered residues S103, S107, and T107 influence the regiospecificity of the oxygenase reaction.

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Altering Toluene 4-Monooxygenase by Active-Site Engineering for the Synthesis of 3-Methoxycatechol, Methoxyhydroquinone, and Methylhydroquinone

et al. 2004

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“…Diagnostic criteria of cyclic voltammetry, the consumption of two electrons per molecule of 1a, and the spectroscopic data (IR, 1 H-NMR, 13 C-NMR and MS) of the isolated product, indicated that the reaction mechanism of electrooxidation of 1a in the presence of phenyl-Meldrum's acid (3) is EC (electrochemical and chemical reactions) mechanism 15) (Chart 1).…”

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“…The precipitated solid was collected by filtration and washed several times with water. After washing, products were characterized by IR, 1 H-NMR, 13 C-NMR, and MS. The isolated yields after washing are reported.…”

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“…11) Also, it is demonstrated that, in comparison with simple catechols, the "highly oxygenated compounds with catechol ring" exhibit interesting biological activities. 12,13) Therefore, the development of a simple synthetic route for the synthesis of "highly oxygenated compounds with catechol ring" from readily available reagents is one of the major tasks. In this direction, we recently reported the synthesis of some "highly oxygenated compounds with catechol ring."…”

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Electrochemical Oxidation of Catechols in the Presence of Phenyl-Meldrum's Acid. Synthesis and Kinetic Evaluation

Nematollahi

Bamzadeh

Shayani‐Jam

2010

CHEMICAL & PHARMACEUTICAL BULLETIN

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23Catechol, by itself, and mono-substituted catechols are active in part against Pseudomonas, Bacillus, but not Penicillium species. Many flavonoids and catechol derivatives turned out to be as antimicrobial agents. 1) In this connection, in order to synthesis catechol derivatives, we studied the electrochemical oxidation of benzenediols in the presence of CH acid nucleophiles, 2-4) SH acid nucleophiles, 5-9) nitrite ion 10) and triphenylphosphine. 11) Also, it is demonstrated that, in comparison with simple catechols, the "highly oxygenated compounds with catechol ring" exhibit interesting biological activities.12,13) Therefore, the development of a simple synthetic route for the synthesis of "highly oxygenated compounds with catechol ring" from readily available reagents is one of the major tasks. In this direction, we recently reported the synthesis of some "highly oxygenated compounds with catechol ring." 14) This idea prompted us to investigate the electrochemical oxidation of catechols in the presence of phenyl-Meldrum's acid as a nucleophile and represents a facile and one-pot electrochemical method for the synthesis of some new "highly oxygenated compounds with catechol ring." Also, an additional purpose of this work is the kinetic and mechanistic study of the electrochemical oxidation of catechols in the presence of phenyl-Meldrum's acid and the estimation of the observed homogeneous rate constants (k obs ) of reaction of electrochemically generated o-benzoquinones with this nucleophile by digital simulation of cyclic voltammograms. Results and DiscussionElectrochemical Investigations The cyclic voltammogram of 1.0 mM catechol (1a) in aqueous solution containing 0.2 M acetate buffer (pHϭ5.0) shows one anodic peak (A 1 ) and the corresponding cathodic peak which correspond to the transformation of catechol (1a) to o-benzoquinone (2a) and vice-versa, within a quasi-reversible two electron process (Fig. 1, curve a).2-11) The electrooxidation of catechol (1a) in the presence of phenyl-Meldrum's acid (3) was studied in some detail. Fig. 1, curve b, shows the first cyclic voltammogram obtained for a 1.0 mM solution of 1a in the presence of 0.1 mM phenyl-Meldrum's acid (3). The voltammogram exhibits one anodic peak (A 1 ) and one cathodic peak (C 1 ) that shows decreasing in comparison to the cathodic peak of catechol (1a) in the absence of 3. In this figure, curve c is the voltammogram of 3 in the absence of 1a.The effect of potential sweep rate on shape of cyclic voltammograms of catechol (1a) in the presence of phenylMeldrum's acid (3) was studied, too. It is seen that, proportional to the augmentation of the potential sweep rate, the height of peak C 1 increases. A similar situation is observed when the 3 to 1a concentration ratio is decreased. A plot of the peak current ratio (I pC1 /I pA1 ) versus the scan rate for a mixture of catechol (1a) and phenyl-Meldrum's acid (3) confirms the reactivity of o-benzoquinone (2a) toward phenylMeldrum's acid (3), appearing as an increase in the peak cur- Electrochemic...

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Formation of Alcohols and Phenols by Oxidation

Larock

Worlikar

2018

Comprehensive Organic Transformations

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Direct biocatalytic synthesis of functionalized catechols: a green alternative to traditional methods with high effective mass yield

Cited by 28 publications

References 31 publications

Altering Toluene 4-Monooxygenase by Active-Site Engineering for the Synthesis of 3-Methoxycatechol, Methoxyhydroquinone, and Methylhydroquinone

Altering Toluene 4-Monooxygenase by Active-Site Engineering for the Synthesis of 3-Methoxycatechol, Methoxyhydroquinone, and Methylhydroquinone

Electrochemical Oxidation of Catechols in the Presence of Phenyl-Meldrum's Acid. Synthesis and Kinetic Evaluation

Formation of Alcohols and Phenols by Oxidation

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