Enzymatic and chemoenzymatic synthesis and stereochemical assignment of cis-dihydrodiol derivatives of monosubstituted benzenes

Boyd, Derek R.; Sharma, Narain D.; Byrne, Breige E.; Hand, Mark V.; Malone, John F.; Sheldrake, Gary N.; Blacker, John; Dalton, Howard

doi:10.1039/a800809d

Cited by 68 publications

(69 citation statements)

References 8 publications

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“…Samples of all the corresponding cis-dihydrodiols, with the exception of the compound B (R = t-Bu), were readily available from previous work in these laboratories using the enzyme TDO (present in whole cells of the UV4 constituent mutant strain of the bacterium Pseudomonas putida). [12,13] In the case of the ketone substrate A (R = COCF 3 ) it was found that P. putida UV4 cells contained a dehydrogenase enzyme as well as TDO resulting in a one-pot stereoselective ketone reduction/arene cis-dihydroxylation and thus the enantiopure cis-dihydrodiol product B had an exocyclic chiral (S)-substituent [R = CH(OH)CF 3 ]. [15] Dehydrogenation and Hydrogen Transfer Hydrogenation of cis-Dihydrodiols B to Yield Catechols C and cis-Tetrahydrodiols D, Respectively, Using Pd/C Among the parameters examined during the current study of the dehydrogenation of cis-dihydrodiols B with Pd/C to yield the corresponding catechols C, were the effects of cis-dihydrodiol substituent type, Scheme 1. solvent, temperature, catalyst state and gas atmosphere.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, the UV4 mutant strain of Pseudomonas putida containing toluene dioxygenase (TDO) can accumulate the cis-dihydrodiol derivatives B from a wide range of substituted benzene substrates since the corresponding toluene cis-diol dehydrogenase enzyme activity has been blocked. [12,13] The combination of a preformed cis-dihydrodiol metabolite using one bacte-rial strain, e.g., P. putida UV4, as substrate for a cisdiol dehydrogenase enzyme, present in a different wild-type [14] or recombinant strain, [15] has been used to produce 3-substituted catechols C (Scheme 1). Thus, 3-fluorocatechol C (R = F) was produced using UV4 and ML2 strains of P. putida.…”

Section: Introductionmentioning

confidence: 99%

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A Comparative Study of the Synthesis of 3‐Substituted Catechols using an Enzymatic and a Chemoenzymatic Method

Berberian¹,

Allen

Sharma³

et al. 2007

Adv Synth Catal

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A series of cis-dihydrodiol metabolites, available from the bacterial dioxygenase-catalysed oxidation of monosubstituted benzene substrates using Pseudomonas putida UV4 , have been converted to the corresponding catechols using both a heterogeneous catalyst (Pd/C) and a naphthalene cis-diol dehydrogenase enzyme present in whole cells of the recombinant strain Escherichia coli DH5a(pUC129: nar B). A comparative study of the merits of both routes to 3-substituted catechols has been carried out and the two methods have been found to be complementary. A similarity in mechanism for catechol formation under both enzymatic and chemoenzymatic conditions, involving regioselective oxidation of the hydroxyl group at C-1, has been found using deuterium labelled toluene cis-dihydrodiols. The potential, of combining a biocatalytic step (dioxygenase-catalysed cis-dihydroxylation) with a chemocatalytic step (Pd/C-catalysed dehydrogenation), into a one-pot route to catechols, from the parent substituted benzene substrates, has been realised.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Comparative Study of the Synthesis of 3‐Substituted Catechols using an Enzymatic and a Chemoenzymatic Method

Berberian¹,

Allen

Sharma³

et al. 2007

Adv Synth Catal

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“…These results show that the P. putida F1 chemotactic response to toluene results from direct detection of the aromatic hydrocarbon itself and not a metabolite, and they also show that the membrane protein TodX is not required for the chemotactic response. TFT is a structural analog of toluene that can be converted to a cis-dihydrodiol by toluene dioxygenase (2). TFT itself elicited a chemotactic response, but neither toluene cisdihydrodiol nor TFT cis-dihydrodiol was an attractant for P. putida F1 (Table 1).…”

Section: Resultsmentioning

confidence: 99%

Toluene-Degrading Bacteria Are Chemotactic towards the Environmental Pollutants Benzene, Toluene, and Trichloroethylene

Parales

Ditty

Harwood

2000

Appl Environ Microbiol

217

157

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The bioremediation of polluted groundwater and toxic waste sites requires that bacteria come into close physical contact with pollutants. This can be accomplished by chemotaxis. Five motile strains of bacteria that use five different pathways to degrade toluene were tested for their ability to detect and swim towards this pollutant. Three of the five strains (Pseudomonas putida F1, Ralstonia pickettii PKO1, and Burkholderia cepacia G4) were attracted to toluene. In each case, the response was dependent on induction by growth with toluene. Pseudomonas mendocina KR1 and P. putida PaW15 did not show a convincing response. The chemotactic responses of P. putida F1 to a variety of toxic aromatic hydrocarbons and chlorinated aliphatic compounds were examined. Compounds that are growth substrates for P. putida F1, including benzene and ethylbenzene, were chemoattractants. P. putida F1 was also attracted to trichloroethylene (TCE), which is not a growth substrate but is dechlorinated and detoxified by P. putida F1. Mutant strains of P. putida F1 that do not oxidize toluene were attracted to toluene, indicating that toluene itself and not a metabolite was the compound detected. The two-component response regulator pair TodS and TodT, which control expression of the toluene degradation genes in P. putida F1, were required for the response. This demonstration that soil bacteria can sense and swim towards the toxic compounds toluene, benzene, TCE, and related chemicals suggests that the introduction of chemotactic bacteria into selected polluted sites may accelerate bioremediation processes.Bacterial chemotaxis has been studied in detail for Escherichia coli and Salmonella enterica serovar Typhimurium (35). Simple sugars, amino acids, and organic acids are chemoattractants for these enteric bacteria. Aromatic acids such as benzoate, 4-hydroxybenzoate, and salicylate are attractants for Pseudomonas putida PRS2000 (15). Recently, the soil bacterium P. putida G7 was reported to be attracted to the pollutant naphthalene (12,24,31). This expanded the range of organic compounds that are known to serve as bacterial chemoattractants to include aromatic hydrocarbons. However, nothing is known about chemotaxis towards other common aromatic hydrocarbons such as toluene and benzene. Five distinct pathways have been described for the aerobic degradation of toluene. All pathways are initiated with the oxidation of toluene, but five different oxidation products are formed (Fig. 1). P. putida F1 contains toluene 2,3-dioxygenase, an enzyme that oxidizes the aromatic ring of toluene, incorporating both atoms of molecular oxygen. After a dehydrogenation step, 3-methylcatechol is formed. This compound is further degraded via meta ring fission (8, 10, 11). P. putida PaW15 (a leucine auxotroph of strain mt-2) initiates degradation at the methyl group of toluene, eventually forming benzoate. Benzoate is converted to catechol, which is also degraded by a meta cleavage route (41). Strains that monooxygenate the aromatic ring of toluene have also be...

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“…In our original studies 7 we showed that the substrate 6 required for the crucial IMDA reaction could be obtained through Negishi cross-coupling of the iodide 7 with the easily generated organozinc species 8. Compound 7 is the readily accessible [12][13][14] acetonide derivative of cis-1,2-dihydrocatechol (4), 15 while the iodide precursor to compound 8 can be produced in just four steps from diallyl alcohol. 7 The opening stage of the present synthesis involved, as we have shown previously but repeat here for the sake of completeness, conversion (Scheme 2) of the known 8 and racemic iodide 9 into the organozinc species 8 by successive treatment of the former compound with t-butyllithium and then zinc iodide between -78 and 18 °C followed by crosscoupling of the latter with iodide 7 in the presence of Pd(Ph 3 P) 4 .…”

Section: Scheme 1 Retrosynthetic Analysis Of Platencin (2)mentioning

confidence: 99%

A Second-Generation Chemoenzymatic Total Synthesis of Platencin

Muhammad

Draffan

Banwell

et al. 2015

Synlett

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A total synthesis of the potent antibacterial agent platencin is described. The reaction sequence used involves, as starting material, an enantiomerically pure cis-1,2-dihydrocatechol derived from the whole-cell biotransformation of iodobenzene. Simple chemical manipulations of this metabolite provide a triene that engages in a thermally promoted intramolecular Diels-Alder reaction to establish the octahydro-2H-2,4a-ethanonaphthalene core of platencin.

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Enzymatic and chemoenzymatic synthesis and stereochemical assignment of cis-dihydrodiol derivatives of monosubstituted benzenes

Cited by 68 publications

References 8 publications

A Comparative Study of the Synthesis of 3‐Substituted Catechols using an Enzymatic and a Chemoenzymatic Method

A Comparative Study of the Synthesis of 3‐Substituted Catechols using an Enzymatic and a Chemoenzymatic Method

Toluene-Degrading Bacteria Are Chemotactic towards the Environmental Pollutants Benzene, Toluene, and Trichloroethylene

A Second-Generation Chemoenzymatic Total Synthesis of Platencin

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