143788-51-6Relevant articles and documents
Dioxygenase-catalysed sulfoxidation of bicyclic alkylaryl sulfides and chemoenzymatic synthesis of acyclic disulfoxides
Boyd, Derek R.,Sharma, Narain D.,Haughey, Simon A.,Kennedy, Martina A.,Malone, John F.,Shepherd, Steven D.,Allen, Christopher C. R.,Dalton, Howard
, p. 549 - 559 (2004)
Toluene- and naphthalene-dioxygenase-catalysed oxidation of six bicyclic disulfide substrates, using whole cells of Pseudomonas putida, gave the corresponding monosulfoxides with high ee values and enantiocomplementarity, in most cases. Two alcohol-sulfox
Sulfoxides of High Enantiopurity from Bacterial Dioxygenase-catalysed Oxidation
Allen, Christopher C. R.,Boyd, Derek R.,Dalton, Howard,Sharma, Narain D.,Haughey, Simon A.,et al.
, p. 119 - 120 (2007/10/02)
Selected strains of the bacterium Pseudomonas putida (previously shown to effect dioxygenase-catalysed asymmetric cis-dihydroxylation of alkenes) have been found to yield chiral sulfoxides from the corresponding sulfides with a strong preference for the (R)- or (S)-configurations but without evidence of sulfone formation; similar results obtained using an Escherichia coli clone (pKST11, containing the Tod C1 C2 B and A genes encoding toluene dioxygenase from P. putida NCIMB 11767) are again consistent with a stereoselective dioxygenase-catalysed sulfoxidation.
Stereoselectivity of enzymatic and chemical oxygenation of sulfur atoms in 2-methyl-1,3-benzodithiole
Cashman, John R.,Olsen, Leslie D.,Boyd, Derek R.,McMordie, R. Austin S.,Dunlop, Robert,Dalton, Howard
, p. 8772 - 8777 (2007/10/02)
S-Monooxygenation of 2-methyl-1,3-benzodithiole, to yield cis- and trans-2-methyl-1,3-benzodithiole 1-oxide, has been studied as a new stereochemical probe using achiral and chiral chemical oxidants and enzymes from microbial and animal sources. Chemical oxidants showed a preference for trans S-oxide formation, and this preference was enhanced in the presence of a chiral matrix. The ability of pure enzymes to stereodifferentiate between geminal lone pairs on a prochiral sulfur atom, or geminal sulfur atoms on a prochiral carbon atom, has been observed. Thus, intact fungal and bacterial oxidations showed a marked selectivity (87-96%) for formation of the cis S-oxide isomers. In addition, highly purified hog liver and rabbit lung flavin-containing monooxygenases showed a marked preference for formation of the cis S-oxide and the pro-R sulfur atom. Other monooxygenase-catalyzed sulfoxidations of 2-methyl-1,3-benzodithiole, including cytochrome P-450 2B1 (P450PB-B), showed a markedly lower stereoselectivity.
Synthesis, Separation and Absolute Configuration Assignment to Enantiomers of 1,3-Benzodithiole 1-Oxide and 2-Alkyl-1,3-Benzodithiole 1-Oxides
Boyd, Derek R.,Sharma, Narain D.,Dorman, James H.,Dunlop, Robert,Malone, John F.,et al.
, p. 1105 - 1110 (2007/10/02)
1,3-Benzodithiole 1-oxide, 5, has been resolved into enantiomers using chiral stationary phase high performance liquid chromatography.Alkylation of an excess (25percent) of the late eluting (+)-(1R) enantiomer of the sulfoxide 5 under basic conditions yielded both cis and trans isomers of 2-methyl (6cis-1R,2S,6trans-1R,2R), 2-ethyl (7cis-1R,2S, 7trans-1R,2R) and 2-isopropyl (8cis-1R,2S, 8trans-1R,2R)-benzodithiole 1-oxide (25percent e.e.) and allowed a stereochemically correlation of absolute configuration between the suloxides 5 - 8. Treatment of racemic 1,3-benzodithiole 1-oxide (51S/51R) with potassium bis(trimethylsilyl)amide and (S)-(+)-1-iodo-2-methylbutane yielded four diastereoisomers of 2-(2'-methylbutyl)-1,3-benzodithiole 1-oxide (9cis-1R,2S,2'S, 9cis-1S,2R,2'S, 9trans-1S,2S,2'S, 9trans-1R,2R,2'S) which were separated by chiral stationary phase HPLC (CSP-HPLC).The most strongly retained diastereoisomer was analysed by X-ray crystallography and was assigned the (1S:1S:2'S) absolute configuration.Further alkylation of 9trans-1S,2S,2'S under similar conditions yielded 2-(2'S-methylbutyl)-2-(2"S-methylbutyl)-1,3-benzodithiole 1-oxide 10 of (1S,2'S,2"S) configuration exclusively.The same stereoisomer of the sulfoxide 10 was also obtained by dialkylation of the early eluting (-)-enantiomer of 1,3-benzodithiole 1-oxide (51S) using (+)-1-iodo-2-metrhylbutane, thus enabling the unequivocal establishment of the absolute configurations of the enantiomers of 1,3-benzodithiole 1-oxides listed in Table 1.A comparison of circular dichroism (CD) spectra for sulfoxides 5 - 9 indicates that this method may also be used to correlate absolute configurations of 2-alkyl substituted 1,3-benzodithiole 1-oxides.
