Optically active 1,3-dithiane 1-oxide: optical resolution and absolute configuration

Bryan, R. F.; Carey, Francis A.; Dailey, Oliver D.; Maher, Robert J.; Miller, Richard W.

doi:10.1021/jo00395a022

Cited by 25 publications

(2 citation statements)

References 11 publications

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“…Methods that exploit the ability of chiral sulfoxides to control the stereochemical outcome of reactions at nearby centers have become important additions to the repertoire of organic synthesis.1h7 All of these strategies depend on access to homochiral sulfoxides and a variety of methods for their synthesis have been described.8 Several useful sulfoxides are accessible in high optical purities by chemical oxidations followed by diastereomeric separation. 9 The direct asymmetric oxidations of prochiral thioethers provide a more direct route, but these reactions often display a variable degree of enantiomeric enrichment that is highly dependent on the nature of the substrate.10h16 These limitations, coupled with a desire to develop ecologically more benign processes, have inspired a search for bioorganic oxidation methods. A large number of microorganisms17h19 including bakerÏs yeast20 catalyze oxidations at sulfur.…”

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confidence: 99%

Asymmetric oxidations at sulfur catalyzed by engineered strains that overexpress cyclohexanone monooxygenase

Chen¹,

Kayser²,

Mihovilovic³

et al. 1999

New J. Chem.

106

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Recombinant strains of bakerÏs yeast (Saccharomyces cerevisiae) and Escherichia coli expressing cyclohexanone monooxygenase from Acinetobacter sp. NCIB 9871 have been used as whole-cell biocatalysts for oxidations of several sulÐdes, dithianes and dithiolanes to the corresponding sulfoxides. The enantio-and diastereoselectivities of these reactions compare favorably with oxidations catalyzed by the puriÐed monooxygenase or the parent microorganism (a class II pathogen). The facility of handling yeast reactions makes these biotransformations an attractive alternative route to optically pure sulfoxides.

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confidence: 99%

Asymmetric oxidations at sulfur catalyzed by engineered strains that overexpress cyclohexanone monooxygenase

Chen¹,

Kayser²,

Mihovilovic³

et al. 1999

New J. Chem.

106

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“…While this microbial oxidation process is very common, the reverse (deoxygenation) step has rarely been observed.1° Three fungi which had previously been used to produce figurations of the isolated sulphoxide (2) were determined by comparison with the results recently obtained from the chemical resolution of (2). While the preferred conformation of (2) (chair form with the oxygen atom equatorial) is indicated in the formula it is established that this conformer is in a rapid state of equilibration with the alternative form having an axial oxygen atom Microbial metabolism of 1,3-dithian (1) using a shake culture method with each of the three fungi gave the thioacetal monosulphoxide (2) in moderate yield (12sayo) (Table 1). The optical yields and absolute con-excess (e.e.)…”

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confidence: 99%

Stereoselective enzyme-catalysed oxidation–reduction reactions of thioacetals–thioacetal sulphoxides by fungi

Auret¹,

Boyd²,

Breen³

et al. 1981

J. Chem. Soc., Perkin Trans. 1

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Enzymes present in the fungus Mortierella isabellina catalyse the transfer of an oxygen atom to the cyclic thioaceta 1,3-dithian and from 1.3-dithian 1 -oxide, 1,3,5-trithian 1 -oxide, and cis-l,3-dithian 1,3-dioxide. The oxidation of 1,3-dithian and the acyclic thioacetal bis-(p-tolylthi0)methane to form the corresponding monosulphoxides occurred in the presence of growing cultures of Aspergillus foefidus and a Helminthosporium species. The degree and preferred direction of stereoselectivity occurring during the asymmetric oxidation and reduction steps was deduced from the enantiomeric excess (e.e.) and absolute stereochemistry of the isolated lf3-dithian 1 -oxide and p-tolylthio-(p-tolylsulphinyl) methane.THIOACETAL derivatives of carbonyl compounds serve as protecting groups and also as a method of rendering the carbonyl group susceptible to both electrophilic and nucleophilic attack (umpolung l), Current interest in the potential of optically active thioacetal monosulplioxide groups as chiral acyl anion equivalent^,^-^ allied to a paucity of information concerning the stability or fate of thioacetal groups during metabolism has prompted the present report. This study also forms part of a programme from these laboratories concerned with the mechanism and stereochemistry of enzyme-catalysed oxygen atom-transfer processes in xenobiotic metabolism (in animal: b a~t e r i a l ,~ and fungal systems). Thioether substrates have previously been transformed into sulphoxide 6-8 and sulphone products 63779 by fungi. While this microbial oxidation process is very common, the reverse (deoxygenation) step has rarely been observed.1°Three fungi which had previously been used to produce figurations of the isolated sulphoxide (2) were determined by comparison with the results recently obtained from the chemical resolution of (2). While the preferred conformation of (2) (chair form with the oxygen atom equatorial) is indicated in the formula it is established that this conformer is in a rapid state of equilibration with the alternative form having an axial oxygen atom (84% equatorial : 16?(, axial at equilibrium).ll The optical purities of the isolated metabolite (2) were relatively low ( <25y0) in comparison with alkyl-aryl thioether oxidations by these fungi6+' Thus a preference for the (+)-(R)-enantiomer [17-2270 enantiomeric TABLE 1Peracid a and enzyme-catalysed asyninietric oxidation of (1) and (3) Yield of Yield of t hioace tal monosulphoxide [a1 689 ( ") Optical Absolute yield ( Y o ) configuration recovered (yo) (%) (EtOH) Substrate Oxidant (1) 0,-iM. isabellina 29.34 16, 38 0, 0 0, 0 R F ( 3 ) 0 , -A . foetidus b 2 O c 0 R g (1) O,-Helminthospoviiim 8, 5 12,27 -35, -29 15,13 (1) 0 , -A . foetidus 32, 19, 42 40, 23, 52 +45, +51, +39 20, 22, 17 R (1) (+)-PCA h > 90 4-0.9 0.4 R (3) O,-HeZminthosporium b 3 -1 5 c 20 S (3) (+)-PCA b > 90 + 2 3 (3) 0 , -M . isabellina b b * (+)-Peroxycamphoric acid (PCA) in CHC1, solution a t -5 "C. No product could be detected. c In acetone solvent.optically pure sulphoxides from the corres...

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1S‐(−)‐1,3‐Dithiane 1‐Oxide

et al. 2003

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1S‐(−)‐1,3‐dithiane 1‐oxide intermediate: 2‐(2,2‐dimethylpropanoyl)‐1,3‐dithiane intermediate: anti‐ and syn‐1S‐(2,2‐dimethylpropanoyl)‐1,3‐dithiane 1‐oxide product: 1S‐(−)‐1,3‐dithiane 1‐oxide reactant: (+)‐[(8,8‐dimethoxycamphoryl)sulfonyl]oxaziridine

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Optically active 1,3-dithiane 1-oxide: optical resolution and absolute configuration

Cited by 25 publications

References 11 publications

Asymmetric oxidations at sulfur catalyzed by engineered strains that overexpress cyclohexanone monooxygenase

Asymmetric oxidations at sulfur catalyzed by engineered strains that overexpress cyclohexanone monooxygenase

Stereoselective enzyme-catalysed oxidation–reduction reactions of thioacetals–thioacetal sulphoxides by fungi

1S‐(−)‐1,3‐Dithiane 1‐Oxide

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