Aryl-bis(thioaryl)sulfonium salts and their use for the preparation of S-aryl-episulfonium salts

Gybin, A. S.; Smit, W. A.; Bogdanov, V. S.; Krimer, M. Z.; KALYAN, J. B.

doi:10.1016/s0040-4039(01)85480-0

Cited by 52 publications

(15 citation statements)

References 5 publications

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“…[9] X-ray crystallographic data have recently been collected for the thiiranium ions 1 and 2, which bear tert-butyl substituents in a cis and trans arrangement, respectively. Both methods will be encountered throughout the ensuing discussion.…”

Section: Generation and Structure Of Thiiranium Ionsmentioning

confidence: 99%

“…Both methods will be encountered throughout the ensuing discussion. [9,10] As reactive intermediates, thiiranium ions normally decompose in one of two ways: [ * ] 1) loss of a b proton to form allylic sulfides, or 2) nucleophilic capture (Scheme 4). However, in certain cases thiiranium ions have been isolated with non-nucleophilic counterions, especially SbCl 6 À and BF 4 À , as fine crystalline powders with sharp melting points (although they decompose on melting).…”

Section: Generation and Structure Of Thiiranium Ionsmentioning

confidence: 99%

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Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Fox

House

Warren

2002

Angew. Chem. Int. Ed.

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Thiiranium (episulfonium) ions had been acknowledged as reaction intermediates for many years, but it was not until 1977 that Nicolaou demonstrated systematically that these reactive heterocyclic cations could be trapped by carboxylic acids to give lactones. In the years that followed this report, extensive research greatly extended the scope of this reaction, particularly with regard to the methods for generating thiiranium ions, the types of nucleophiles that are compatible with this reaction, and the selectivity involved in the cyclization reactions. For many years we have been using thiiranium ions for the synthesis of saturated heterocycles. Whereas Nicolaou's method relied on electrophilic sulfenylation of alkenes, we have generated thiiranium ions by displacement of a leaving group with neighboring-group participation by a sulfanyl group. Many of the examples we have reported are of cyclizations that are reversible and so where two (and in some cases more) products can result, the outcome of the reactions provides fundamental information about the relative stability of different heterocyclic ring systems. This Review will begin with a brief introduction to sulfanyl participation as a method for generating thiiranium (and thiolanium) ions, and will go on to explore the idea of using sulfanyl migrations in synthesis. Initially, emphasis will be placed on mechanisms of [1,2] sulfanyl migrations: we will look specifically at [1,2] sulfanyl migrations (usually PhS) with elimination, substitution, and cyclization. Emphasis will then shift to the factors that affect the outcome of cyclization reactions. In particular, we will cover cyclizations with hydroxy nucleophiles and examine situations in which there are more than one hydroxy nucleophile present. We will also examine cyclizations with other nucleophiles, namely amines and sulfides. After our discussion of [1,2] sulfanyl migrations, we will look very briefly at the scope of [1,4] sulfanyl participation, before finally drawing up some guidelines that (we hope) will help other organic chemists take advantage of the rearrangement reactions that the sulfanyl group has to offer.

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Section: Generation and Structure Of Thiiranium Ionsmentioning

confidence: 99%

Section: Generation and Structure Of Thiiranium Ionsmentioning

confidence: 99%

Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Fox

House

Warren

2002

Angew. Chem. Int. Ed.

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“…Such cationic intermediates are known as mediators from the cationic pool method. [37,38] Cationic 1,2-diaryldisulfides intermediates undergo usually CÀS-bond formations leading to thianthrene architectures. [39] In conclusion, the oxidative treatment of 1,2-diaryldisulfides using MoCl 5 or mixtures thereof with TiCl 4 gives a quick access to thianthrenes in moderate to excellent yields.…”

mentioning

confidence: 99%

Oxidative Coupling of Diaryldisulfides by MoCl₅ to Thianthrenes

Spurg

Schnakenburg

Waldvogel

2009

Chemistry A European J

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“…Such cationic intermediates are known as mediators from the cationic pool method 37. 38 Cationic 1,2‐diaryldisulfides intermediates undergo usually CS‐bond formations leading to thianthrene architectures 39…”

Section: Methodsmentioning

confidence: 99%

Volume strain changes of plasticized poly(vinylidene fluoride) during tensile and creep tests

Cangémi

Elkoun

G’Sell

et al. 2003

J of Applied Polymer Sci

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ABSTRACT:The volume strain changes of plasticized poly(vinylidene fluoride) during tensile and creep tests were characterized. A negative volume strain was observed. This phenomenon was ascribed to compaction taking place during mechanical testing, which further delayed the onset of plastic instability and, therefore, the cavitation process. It was suggested that this compaction was caused by the orientation of amorphous chain segments leading to material densification.

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Aryl-bis(thioaryl)sulfonium salts and their use for the preparation of S-aryl-episulfonium salts

Cited by 52 publications

References 5 publications

Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Oxidative Coupling of Diaryldisulfides by MoCl₅ to Thianthrenes

Volume strain changes of plasticized poly(vinylidene fluoride) during tensile and creep tests

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Aryl-bis(thioaryl)sulfonium salts and their use for the preparation of S-aryl-episulfonium salts

Cited by 52 publications

References 5 publications

Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Oxidative Coupling of Diaryldisulfides by MoCl5 to Thianthrenes

Volume strain changes of plasticized poly(vinylidene fluoride) during tensile and creep tests

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Product

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Oxidative Coupling of Diaryldisulfides by MoCl₅ to Thianthrenes