- Enzyme-catalysed synthesis and absolute configuration assignments of cis-dihydrodiol metabolites from 1,4-disubstituted benzenes
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A series of ten cis-dihydrodiol metabolites has been obtained by bacterial biotransformation of the corresponding 1,4-disubstituted benzene substrates using Pseudomonas putida UV4, a source of toluene dioxygenase (TDO). Their enantiomeric excess (ee) values have been established using chiral stationary phase HPLC and 1H NMR spectroscopy. Absolute con_figurations of the majority of cis-dihydrodiols have been established using stereochemical correlation and X-ray crystallography and the remainder have been tentatively assigned using NMR spectroscopic methods but finally confirmed by circular dichroism (CD) spectroscopy. These configurational assignments support and extend the validity of an empirical model, previously used to predict the preferred stereochemistry of TDO-catalysed cis-dihydroxylation of ten 1,4-disubstituted benzene substrates, to more than twenty-five examples.
- Boyd, Derek R.,Sharma, Narain D.,Coen, Gerard P.,Gray, Peter J.,Malone, John F.,Gawronski, Jacek
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p. 5804 - 5811
(2008/02/13)
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- Enzymatic and chemoenzymatic synthesis and stereochemical assignment of cis-dihydrodiol derivatives of monosubstituted benzenes
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Toluene dioxygenase-catalysed oxidation of mono-substituted benzene substrates (R = F, Cl, Br, I, Me, Et, CH2OAc, CH=CH2, C=CH, CF3, CN, OMe, OEt, SMe) in growing cultures of Pseudomonas putida UV4 yielded the corresponding cis-dihydrodiol metabolites. Palladium-catalysed cross-coupling of cis-(1S,2S)-1,2-dihydroxy-3-iodocyclohexa-3,5-diene with a range of tributyltin compounds provided a chemoenzymatic route to a further series of cis-dihydrodiol derivatives of monosubstituted benzenes (R = D, CH2CH=CH2, Bun, SEt, SPr1, SBu1, SPh, SC6H4Me-4). The enantiopurities and absolute configurations of the cis-dihydrodiols, obtained by both enzymatic and chemoenzymatic routes, were determined by several new methods including 1H NMR spectroscopic analysis of the bis-MTPA esters of the 4-phenyl-1,2,4-triazoline-3,5-dione cycloadducts, X-ray crystallography, circular dichroism spectroscopy and stereochemical correlation.
- Boyd, Derek R.,Sharma, Narain D.,Byrne, Breige,Hand, Mark V.,Malone, John F.,Sheldrake, Gary N.,Blacker, John,Dalton, Howard
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p. 1935 - 1943
(2007/10/03)
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- Biochemical process to produce catechol or 1,2-dihydroxycyclohexa-3,5-diene compound(s)
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A process for the preparation of a catechol and/or a compound comprising a 1,2-dihydroxycyclohexa-3,5-diene ring, which comprises growing a microorganism in the presence of a carbon source, the microorganism being capable of converting the corresponding aromatic compound into the catechol and/or the compound comprising a 1,2-dihydroxycyclohexa-3,5-diene ring; and supplying the corresponding aromatic compound to the microorganism; characterized in that the carbon source is molasses.
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