138769-97-8

Upstream product

• 67451-62-1 cis-(1S,2S)-1,2-dihydroxy-3-bromocyclohexa-3,5-diene 
• 5188-07-8 sodium thiomethoxide 
• 138769-92-3 cis-(1S,2S)-1,2-dihydroxy-3-iodocyclohexa-3,5-diene 
• 100-68-5 methyl-phenyl-thioether 
• 17314-32-8 tributyl(methylthio)stannane 
• 1193-82-4 racemic methyl phenyl sulfoxide 
• 104-95-0 (4-bromophenyl)thioanisole 
• 108-86-1 bromobenzene 
• 591-50-4 iodobenzene 
• 777094-95-8 (1S,2R)-3-bromo-6-(methylsulfanyl)cyclohexa-3,5-diene-1,2-diol 
• 499201-99-9 (1S,2S)-1,2-dihydroxy-3-(R)-methylsulfinylcyclohexa-3,5-diene 

Downstream Products

• 793697-46-8 (1S,2S)-3-(methylsulfanyl)cyclohex-5-ene-1,2-diol 
• 928122-18-3 (1S,6S)-6-[Dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-2-methylsulfanyl-cyclohex-2-enol 
• 898235-75-1 (1R,2S)-2-[Dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-cyclohexanol 

Relevant academic research and scientific papers

Toluene dioxygenase-mediated oxidation of bromo(methylsulfanyl)benzenes. Absolute configuration of metabolites and evaluation of chemo- and regioselectivity trends

A series of 2-, 3-, and 4-bromo-1-(methylsulfanyl)benzenes was subjected to whole-cell fermentation with Escherichia coli JM 109 (pDTG601), a recombinant strain that expresses toluene dioxygenase. New metabolites were isolated and their structure and abso

Stereoselective reductase-catalysed deoxygenation of sulfoxides in aerobic and anaerobic bacteria.

Direct and indirect evidence, of unexpected stereoselective reductase-catalysed deoxygenations of sulfoxides, was found. The deoxygenations proceeded simultaneously, with the expected dioxygenase-catalysed asymmetric sulfoxidation of sulfides, during some biotransformations with the aerobic bacterium Pseudomonas putida UV4. Stereoselective reductase-catalysed asymmetric deoxygenation of racemic alkylaryl, dialkyl and phenolic sulfoxides was observed, without evidence of the reverse sulfoxidation reaction, using anaerobic bacterial strains. A purified dimethyl sulfoxide reductase, obtained from the intact cells of the anaerobic bacterium Citrobacter braakii DMSO 11, yielded, from the corresponding racemates, enantiopure alkylaryl sulfoxide and thiosulfinate samples.

Enzymatic oxidation of thioanisoles: Isolation and absolute configuration of metabolites

Oxidation of p-bromothioanisole with toluene dioxygenase provides the corresponding diene diol 2 in good yield. Electrochemical reduction of 2 gives access to diene diol 3, which is not accessible by direct bio-oxidation of thioanisole. Absolute configura

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

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.

Toluene and naphthalene dioxygenase-catalysed sulfoxidation of alkyl aryl sulfides

A series of alkyl aryl sulfides were metabolised, using selected strains of the soil bacterium Pseudomonas putida containing either toluene dioxygenase (TDO) or naphthalene dioxygenase (NDO), to give chiral sulfoxides. Alkyl aryl sulfoxides 2a-2k, 4a-4j and 4l, having enantiomeric excess (ee) values of >90%, were obtained by use of the appropriate strain of P. putida (UV4 or NCIMB 8859). Enantiocomplementarity was observed for the formation of sulfoxides 2a, 2b, 2d, 2j, 4a, 4b and 4d, with TDO-catalysed (UV4) oxidation favouring the (R) enantiomer and NDO-catalysed oxidation (NCIMB 8859) the (S) enantiomer. Evidence of involvement of the TDO enzyme was obtained using a recombinant strain of Escherichia coli (pKST 11). The marked degree of stereoselectivity appears to be mainly due to enzyme-catalysed asymmetric sulfoxidation, however the possibility of a minor contribution from kinetic resolution, in some cases, cannot be excluded.

Enzymatic and Chemical Syntheses of cis-Dihydrodiol Derivatives of Monocyclic Arenes

Metabolism of bromobenzene and iodobenzene by growing cultures of Pseudomonas putida UV4 gave the corresponding cis-dihydrodiol products 1 and 2 in high yields; subsequent direct chemical substitution of the halogen atoms in these metabolites provided a new range of enantiomerically pure cis-dihydrodiols of known absolute configuration.