The Reaction of Elemental Sulfur with Organic Compounds. IV. The Reactions of <i>N</i>-Arenesulfonylsulfilimine and Sulfoximine with Sulfur and Diaryl Disulfide

Ōae, Shigeru; Tsuchida, Yoshiyuki; Tsujihara, Kenji; Furukawa, Naomichi

doi:10.1246/bcsj.45.2856

Cited by 23 publications

(5 citation statements)

References 11 publications

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“…22 There are many examples of S-S bond cleavage as a result of nucleophilic attack by nitrogen nucleophiles. 19,23 The relatively small value for the Brönsted β nuc = 0.26 for catalysis by substituted pyridines is also compatible with a facile process for the second step k 2 and the change in rate-limiting step 24 with increasing picoline concentration (Fig. 6) occurs when k 2 [ pic] ≫ k −1 .…”

Section: Sulfurisation By 'Aged' Padsmentioning

confidence: 73%

Phosphorothioate anti-sense oligonucleotides: the kinetics and mechanism of the sulfurisation of phosphites by phenylacetyl disulfide (PADS)

et al. 2016

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In the pharmaceutical industry the sulfurisation of nucleotide-phosphites to produce more biologically stable thiophosphates is often achieved using 'aged' solutions of phenylacetyl disulfide (PADS) which consist of a mixture of polysulfides that are more efficient sulfur transfer reagents. However, both 'fresh' and 'aged' solutions of PADS are capable of the sulfurisation of phosphites. The rates of both processes in acetonitrile are first order in sulfurising agent, phosphite and a pyridine base, although with 'aged' PADS the rate becomes independent of base at high concentrations. The Brönsted β values for sulfurisation using 'fresh' and 'aged' PADS with substituted pyridines are 0.43 and 0.26, respectively. With 'fresh' PADS the Brönsted β = 0.51 for substituted trialkyl phosphites is consistent with a mechanism involving nucleophilic attack of the phosphite on the PADS disulfide bond to reversibly generate a phosphonium intermediate, the rate-limiting breakdown of which occurs by a base catalysed elimination process, confirmed by replacing the ionisable hydrogens in PADS with methyl groups. The comparable polysulfide phosphonium ion intermediate seen with 'aged' PADS presents a more facile pathway for product formation involving S-S bond fission as opposed to C-S bond fission.

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Section: Sulfurisation By 'Aged' Padsmentioning

confidence: 73%

Phosphorothioate anti-sense oligonucleotides: the kinetics and mechanism of the sulfurisation of phosphites by phenylacetyl disulfide (PADS)

et al. 2016

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“…Sulfinimidoyl thiophenyl 8 which is formed on the first stage of the reaction transforms to sulfonamide 9. It is known that the compounds with the similar structure are unstable and easily undergo the homolytic break on N S bond with subsequent symmetrization of radicals [24,25].…”

Section: Resultsmentioning

confidence: 99%

2‐Benzothiazolyl‐N‐(arenesulfonyl)‐sulfinimidoyl fluorides

Pashinnik

Guzyr

Borovikov

et al. 2005

Heteroatom Chemistry

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“…For example, heating diphenyl NH‐sulfoximine together with elemental sulfur to 160 °C for 15 minutes produced diphenyl sulfoxide in an almost stoichiometric yield (Scheme 66, eqn. b, method A) [119] . Alternatively, diphenyl sulfoxide could be obtained by refluxing a mixture of diphenyl sulfoximine and diphenyl disulfide in 1,2‐dichlorobenzene for 5 hours (Scheme 66, eqn.…”

Section: Sulfoximine Conversion Pathwaysmentioning

confidence: 99%

Syntheses and Transformations of Sulfoximines

Zheng

Chen

Feng

et al. 2020

The Chemical Record

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Sulfoximines are widely used as medicines, agricultural chemicals, chiral precursors, and chiral ligands in asymmetric synthesis, as well as pivotal intermediates for the construction of heterocyclic compounds. NH‐sulfoximines may be synthesized from thioethers, sulfoxides, sulfilimines, and sulfinamides. NH‐sulfoximines can undergo various transformations, such as arylations, alkylations, vinylations, and alkynylations. Here, we review the methods that have been applied to the syntheses and transformations of NH‐sulfoximines.

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The Reaction of Elemental Sulfur with Organic Compounds. IV. The Reactions of N-Arenesulfonylsulfilimine and Sulfoximine with Sulfur and Diaryl Disulfide

Cited by 23 publications

References 11 publications

Phosphorothioate anti-sense oligonucleotides: the kinetics and mechanism of the sulfurisation of phosphites by phenylacetyl disulfide (PADS)

Phosphorothioate anti-sense oligonucleotides: the kinetics and mechanism of the sulfurisation of phosphites by phenylacetyl disulfide (PADS)

2‐Benzothiazolyl‐N‐(arenesulfonyl)‐sulfinimidoyl fluorides

Syntheses and Transformations of Sulfoximines

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