Dimethyl Sulfoxide Oxidations

Epstein, William W.; Sweat, Faye

doi:10.1021/cr60247a001

Cited by 310 publications

(94 citation statements)

References 48 publications

(95 reference statements)

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“…The kinetic data could also be consistent with a rate determining hydrogen reduction to rhodium(1) through reactions [3] and [6], followed by a rapid oxidation ofthe rhodium(1) by DMSO. However, DMSO complexes of low valent transition metals such as manganese(I1) (17), ruthenium(I1) (29), and iridium(1) (3) are known and also our final reaction solutions appear to contain rhodium(I), so such a mechanism seems unlikely and we strongly favor reaction through a rhodium(II1) hydride.…”

Section: The Fall-ofill Catalytic Activitysupporting

confidence: 67%

“…These workers state that hydrides are the most effective catalysts. Rhodium(1) complexes are known to activate molecular oxygen through an oxidative addition reaction (32) and these could well be produced from the rhodium(II1) hydrides according to reaction [6]. Hence, from these considerations, it seemed possible that the increase in rate of gas uptake in our experiment using the hydrogen/ oxygen mixture might be due to an induced catalytic oxidation through the rhodium(II1) hydride intermediates or the slowly produced rhodium(1) species.…”

Section: The Fall-ofill Catalytic Activitymentioning

confidence: 95%

“…Reaction [6] is a fast reaction (I) and hence the production of rhodium(1) will depend on the comparative rates of the decomposition of the hydride according to reaction [6] and its reaction with DMSO according to a reaction such as [5]. Production of rhodium (1) could be more favorable at higher concentrations of dimethylsulfide since this ligand is expected to stabilize the lower valent state (more class b character).…”

Section: The Fall-ofill Catalytic Activitymentioning

confidence: 99%

“…This has been shown to be a catalytic reduction of the solvent and these studies are described in this paper. DMSO has come to be widely used as an advantageous medium for inorganic chemical reactions because of its ability to dissolve fairly high concentrations of many inorganic solutes (4,5), and has been used extensively as an oxidizing agent in organic synthesis (5,6). A few Group 111-V main group halides have been shown to reduce DMSO (6); most transition metal halides form coordination compounds (7), although niobium and tantalum pentahalides d o abstract the oxygen atom of the sulfoxide t o form the corresponding oxyhalide and halogen substituted sulfides (8).…”

Section: Introductionmentioning

confidence: 99%

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Catalytic reduction of dimethylsulfoxide by molecular hydrogen using rhodium(III) complexes

James¹,

Ng²,

Rempel³

1969

Can. J. Chem.

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Dimethylsulfoxide is reduced by lnolecular hydrogen under mild conditions to din~ethylsulfide and water in the presence of rhodium(II1) complexes as catalysts. The kinetics of the systems using RhC13.3HZ0 and ~i s -R h C l~( E t , S )~ havc been investigated, and a mechanisn-r involving reduction of coordinated dimethylsulfoxide in a rhodium(II1) hydride complex is postulated. The catalytic efficiency of the systems decreases slowly due to the production of inactive rhodium(1) species.

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Section: The Fall-ofill Catalytic Activitysupporting

confidence: 67%

Section: The Fall-ofill Catalytic Activitymentioning

confidence: 95%

Section: The Fall-ofill Catalytic Activitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Catalytic reduction of dimethylsulfoxide by molecular hydrogen using rhodium(III) complexes

James¹,

Ng²,

Rempel³

1969

Can. J. Chem.

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“…In order to investigate the mode of formation of 13, 9-acetyl-3"-methylthiomethylmidecamycin (7) was brought into reaction with DMSO and acetic anhydride in the presence of carbon tetrachloride, yielding 13, identical with that directly prepared from the 9,2'-diacetate (2). Use of acetic anhydride-d,; or propioiic anhydride in the reaction of 7 gave the trideuterioacetoxymethyl derivative (13-d3 to play some role in the fission of C-S bond.…”

Section: Preparation Of 3"-acyloxymethyl Derivatives Of Midecamycinmentioning

confidence: 99%

Modifications of a macrolide antibiotic midecamycin. II. Reaction of midecamycin and 9-acetylmidecamycin with dimethylsulfoxide and acetic anhydride.

Inouye¹,

Omoto²,

Iwamatsu³

et al. 1980

J. Antibiot.

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Treatment of 9,2'-diacetylmidecamycin (2) with DMSO and acetic anhydride afforded 3"-methylthiomethyl derivative (3) preferably in the presence of pyridine. Reaction of midecamycin (1) with DMSO and acetic anhydride gave 2'-acetyl-9-dehydro-3"-methylthiomethyl derivative (9) indicating that the three hydroxyl groups reacted in a different way to the reagent. When compound 2 was reacted with DMSO and acetic anhydride in the presence of CCl4, 3"-acetoxymethyl derivative (13) was a major product, which was formed via 3 through the PUMMERER rearrangement.The structures of 3, 9 and 13 were confirmed by examining NMR and mass spectra of these compounds and their deuterio analogues. They showed antimicrobial spectra similar to 1 but superior in vivo activity.

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