Rearrangements involving sulfenic acids and their derivatives

Braverman, S.

doi:10.1002/9780470772287.ch8

Cited by 19 publications

(19 citation statements)

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“…Several highly substituted sulfenates have been shown to undergo heterolysis in solution. [14][15][16][17] By contrast, it was proposed that the solution-phase thermal decomposition of benzyl p-toluenesulfenate mainly to the sulfoxide went by a concerted mechanism. 18 To the best of our knowledge, no gas-phase data regarding thermolysis of sulfenic esters exist.…”

Section: Introductionmentioning

confidence: 99%

Thermochemistry of Sulfenic Esters (RSOR‘): Not Just Another Pretty Peroxide

Gregory

Jenks

1998

J. Org. Chem.

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A computational study on the thermochemistry of several simple sulfenic acids (RSOH) and esters (RSOR′) is reported. The enthalpies of R-S, S-O, and O-R′ homolytic cleavage are calculated at the G2 level of theory and compared to related peroxides and disulfides. Less expensive B3LYP calculations were unsatisfactory. When R and R′ are both alkyl, the O-C bond is expected to be the weakest in the molecule; for CH 3 SOCH 3 , C-S, S-O, and O-C bond dissociation enthalpies of 67, 64, and 49 kcal/mol are predicted by G2. Compared to peroxides, sulfenic esters are predicted to have weaker O-C bonds and S-O bonds that are stronger than the analogous O-O bonds. The C-S bonds of sulfenic esters are predicted to be somewhat stronger than those of disulfides. A rationalization is given for the observation that radical stabilization is greater for RSO• than ROO• , RSS• , or ROS • .

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Section: Introductionmentioning

confidence: 99%

Thermochemistry of Sulfenic Esters (RSOR‘): Not Just Another Pretty Peroxide

Gregory

Jenks

1998

J. Org. Chem.

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“…An accessible entry to allenic systems consists of the [2,3]sigmatropic rearrangement of propargylic sulfenates to allenic sulfoxides. This reaction, which takes place spontaneously at low temperature, has been applied extensively in organic synthesis [8,9]. In order to follow this reaction type, the first step was to prepare pseudo-geminal bis(propargylic) alcohols 2a-c (Scheme 1) by the reaction of the corresponding lithium acetylide with 4,15-diformyl [2.2]paracyclophane (1) [10].…”

Section: The Interaction Of Pseudo-geminal Bis(propargylic)[22]pc Almentioning

confidence: 99%

“…Further investigations involved the replacement of the trichloromethyl group with a nitrophenyl substituent [12]. This was accomplished by the reaction of bis(propargylic) alcohols 2a,d with o-nitrobenzenesulfenyl chloride via a double [2,3]sigmatropic rearrangement of the corresponding sulfenyl esters (Scheme 3) [8,9].…”

Section: Abmentioning

confidence: 99%

Chalchogenide induced intramolecular interactions in [2.2]paracyclophanes: a review

Sarbu¹,

Bahrin²,

Hopf³

et al. 2019

Studia UBB Chemia

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“…To address the question of whether a sulfenic acid can undergo intramolecular reaction with an alkene under mild conditions to generate an alkylating intermediate, we set out to characterize the reactivity of [ortho-(3-methylbut-2-enyl)phenyl]sulfenic acid (7). Typically, it is not possible to isolate sulfenic acids due to their instability (33,(51)(52)(53)(54); however, methods exist for the in situ generation of this functional group (12,22,32,48,(55)(56)(57)(58)(59)(60)(61). In the present study, we employed a β-phenylsulfinyl aldehyde 6a and a β-phenylsulfinyl ester derivative 6b as phenylsulfenic acid precursors.…”

Section: Design Of Sulfenic Acid Precursorsmentioning

confidence: 99%

Evidence for a Morin Type Intramolecular Cyclization of an Alkene with a Phenylsulfenic Acid Group in Neutral Aqueous Solution

Keerthi

Sivaramakrishnan

Gates

2008

Chem. Res. Toxicol.

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Sulfenic acids (RSOH) are among the most common sulfur-centered reactive intermediates generated in biological systems. Given the biological occurrence of sulfenic acids, it is important to explore the reactivity of these intermediates under physiological conditions. The Morin rearrangement is a synthetic process developed for the conversion of penicillin derivatives into cephalosporins that proceeds via nucleophilic attack of an alkene on a sulfenic acid intermediate. In its classic form, the Morin reaction involves initial elimination of a sulfenic acid from a cyclic sulfoxide, followed by intramolecular cyclization of the resulting alkene and sulfenic acid groups to generate an episulfonium ion intermediate that undergoes further reaction to yield ring-expanded products. On the basis of the existing literature, it is difficult to assess whether the reaction between an alkene and a sulfenic group can occur under mild conditions because the conditions required to generate the sulfenic acid from the sulfoxide precursor in the Morin reaction typically involve high temperatures and strong acid. In the work described here, beta-sulfinylketone precursors were used to generate a "Morin type" sulfenic acid intermediate under mild conditions. This approach made it possible to demonstrate that the intramolecular cyclization of an alkene with a phenylsulfenic acid to generate an episulfonium ion intermediate can occur in neutral aqueous solution at room temperature.

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Rearrangements involving sulfenic acids and their derivatives

Cited by 19 publications

References 295 publications

Thermochemistry of Sulfenic Esters (RSOR‘): Not Just Another Pretty Peroxide

Thermochemistry of Sulfenic Esters (RSOR‘): Not Just Another Pretty Peroxide

Chalchogenide induced intramolecular interactions in [2.2]paracyclophanes: a review

Evidence for a Morin Type Intramolecular Cyclization of an Alkene with a Phenylsulfenic Acid Group in Neutral Aqueous Solution

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