Derivatives of Sulfenic Acids. II. Characterization of Olefins with 2,4-Dinitrobenzenesulfenyl Chloride

Kharasch, Norman; Buess, Charles M.

doi:10.1021/ja01176a036

Cited by 81 publications

(16 citation statements)

References 2 publications

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“…While we do not completely understand the reasons for this anomalous behaviour it seems likely that the lower configurational-selectivity observed must reflect in part the planar configuration of these aryl groups compared to, for example, 2,4,6-trimethyl-or 2,4,6-triisopropylbenzenesulphenyl chloride, where the alkyl groups in the ortho positions occupy a larger volume in space close to the reaction center and thus present a bulkier local environment during the product determining step. In summary, the data presented here and in earlier segments of this series allow us to define the reaction hypersurface for the interaction of sulphenyl chlorides with allenes as one which follows an AdE2 mechanism (13) similar to that first proposed by Kharasch and Buess for simple alkenes (14). The first step appears to be rate determining formation of an alkylidenethiiranium ion by S,2 attack on sulphur.…”

Section: E Favoredsupporting

confidence: 57%

Electrophilic additions to allenes. VI. The role of steric versus electronic effects in the reactions of arenesulphenyl halides with allenes

Garrattz¹,

Beaulieu²

1980

Can. J. Chem.

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. Can. J. Chem. 58, 2737Chem. 58, (1980. The role of steric and electronic effects during the rate and product determining steps for the addition of arenesulphenyl chlorides to 1,3-disubstituted allenes has been briefly examined. Both effects appear to be generally of minimal importance during the rate determining step. The available rate data indicate the presence of little, if any, build up of positive charge on sulphur. These results are interpreted in terms of an &2 attack on bivalent sulphur leading to an alkylidenethiiranium ion intermediate. Steric effects are of greater importance in the product determining step, particularly when the sulphenyl chlorides possess two bulky ortho substituents, as in the case of 2,4,6-triisopropylbenzenesulphenyl chloride. Chem. 58,2737Chem. 58, (1980. On a examine brievement le rBle des effets sterique et klectronique dans les &tapes determinant la vitesse de la reaction et la valeur des produits d'addition des chlorures d'arene-sulphenyle sur les alltnes disubstitues en positions 1,3. Les deux effets semblent n'avoir qu'une faible importance sur I'ttape determinant la vitesse de la reaction. Les donnees cinetiques disponibles indiquent la presence d'une faible charge positive sur le soufre. On interprete ces resultats en termes d'une attaque SN2 sur le soufre bivalent conduisant a un ion alkylidenethiiranium intermediaire. Les effets steriques jouent un rBle important dans l'etape determinant la nature des produits formis en particulier quand le chlorure de sulphdnyle possede deux substituants encombrants en position ortho comme dans le cas du chlorure de triisopropyl-2,4,6 benzenesulphCnyle.[Traduit par le journal]In previous papers of this series we have reported the reactions of benzenesulphenyl chloride and some derivatives thereof with a series of 1,3-disubstituted allenes (1-3). In all cases studied the arylthio moiety was observed to attack regiospecifically on the central allenic carbon, with the E isomer formed preferentially or exclusively under conditions of kinetic control. The ratio of products was interpreted as corresponding to the percentage of attack on each face of the respective n systems, and therefore reflecting the direction of approach of the electrophile towards the allenic system. The preponderance of the E isomer led us to propose that one observes steric approach control, wherein the steric interactions in the product determining

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Section: E Favoredsupporting

confidence: 57%

Electrophilic additions to allenes. VI. The role of steric versus electronic effects in the reactions of arenesulphenyl halides with allenes

Garrattz¹,

Beaulieu²

1980

Can. J. Chem.

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“…In 1949 the first mechanistic insights from Kharasch and Buess proposed the intermediacy of a 3‐membered, cyclic sulfonium (thiiranium or episulfonium) ion (Scheme 1 B). [10b] In molecular orbital terms, the approach of the alkene to the sulfenium ion source results in a π→σ* interaction that promotes the ionization of the leaving group (X) on sulfur with simultaneous formation of a three‐membered ring intermediate.…”

Section: Historical Background and Development Of Mechanistic Understmentioning

confidence: 99%

Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances

2020

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The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization of alkenes initiated by electrophilic sulfenyl group transfer. The addition of sulfenium ions to alkenes results in the generation of chiral, non‐racemic thiiranium ions. These highly reactive intermediates are susceptible to attack by a myriad of nucleophiles in a stereospecific ring‐opening event to afford anti 1,2‐sulfenofunctionalized products. The practical application of sulfenium ion transfer has been enabled by advances in the field of Lewis base catalysis. This Review will chronicle the initial discovery and characterization of thiiranium ion intermediates followed by the determination of their configurational stability and the challenges of developing enantioselective variants. Once the framework for the reactivity and stability of thiiranium ions has been established, a critical analysis of pioneering studies will be presented. Finally, a comprehensive discussion of modern synthetic applications will be categorized around the type of nucleophile employed for sulfenofunctionalization.

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“…The involvement of sulfenyl bromides in BIIR sulfuration is difficult to determine. The electrophilic addition of sulfenyl halides to carbon–carbon double bonds is well documented,16, 30, 31 and such a reaction could conceivably produce allylic and alkyl sulfide structures similar to those observed in unaccelerated cures of conventional olefins (Scheme ). However, we found no evidence of the addition or substitution products that would be derived from the electrophilic attack of sulfenyl bromides on olefin.…”

Section: Discussionmentioning

confidence: 95%

Sulfuration and reversion reactions of brominated poly(isobutylene‐co‐isoprene)

Parent

White

Thom

et al. 2003

J. Polym. Sci. A Polym. Chem.

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The sulfuration and reversion products of brominated poly(isobutylene-coisoprene) (BIIR) were characterized through the use of a model compound, brominated 2,2,4,8,8-pentamethyl-4-nonene (BPMN). The reaction of BPMN with S 8 produced bisallylic polysulfides of various ranks, yielding sulfur bromide intermediates that likely contributed to the rapid oxidation of allylic sulfides into thiophenes. Reductive cure reversion to pentamethylnonene was also observed in the latter stages of vulcanization. The reaction of 2,2Ј-dithiobisbenzothiazole with BIIR and BPMN produced a stable adduct that reduced the concentration of allylic bromide available for vulcanization.

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Derivatives of Sulfenic Acids. II. Characterization of Olefins with 2,4-Dinitrobenzenesulfenyl Chloride

Cited by 81 publications

References 2 publications

Electrophilic additions to allenes. VI. The role of steric versus electronic effects in the reactions of arenesulphenyl halides with allenes

Electrophilic additions to allenes. VI. The role of steric versus electronic effects in the reactions of arenesulphenyl halides with allenes

Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances

Sulfuration and reversion reactions of brominated poly(isobutylene‐co‐isoprene)

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