Synthesis of Sulphoxides

Drabowicz, J.; and, Piotr Kiełbasinski; Mikołajczyk, M.

doi:10.1002/9780470666357.ch3

Cited by 6 publications

(9 citation statements)

References 581 publications

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“…α,β-Unsaturated sulfoxides are valuable intermediates in a variety of synthetic transformations and useful building blocks in the synthesis of biologically active compounds . Vinyl sulfoxides display three main types of reactivity.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Synthesis of Racemic and Optically ActiveE-Vinyl andE-Dienyl Sulfoxides via Wittig Reaction of α-Sulfinyl Phosphonium Ylides

et al. 1998

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A series of α-sulfinyl phosphonium ylides have been obtained in the reaction of phosphonium mono- and diylides with sulfinic acid esters. The use of (−)-(S)-menthyl p-toluenesulfinate in this reaction afforded the corresponding (S)-((p-tolylsulfinyl)methyl)triphenylphosphonium ylide. The Wittig reaction of these ylides with saturated and unsaturated aldehydes resulted in the formation of racemic and optically active (+)-(R)-vinyl and dienyl sulfoxides with the E-geometry. The synthesis of (+)-(R)-((p-tolylsulfinyl)methyl)triphenylphosphonium iodide as a precursor of the optically active ylide has also been described.

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Section: Introductionmentioning

confidence: 99%

Stereoselective Synthesis of Racemic and Optically ActiveE-Vinyl andE-Dienyl Sulfoxides via Wittig Reaction of α-Sulfinyl Phosphonium Ylides

et al. 1998

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“…The chemoselective oxidation of sulfides to the corresponding sulfoxides is a very important transformation in organic synthesis, since the obtained sulfoxides are important intermediates or building blocks in the construction of pharmaceuticals, agrochemicals, and other valuable fine chemicals [1,2,3,4,5,6,7]. To realize this extremely useful transformation, several oxidants can be employed, such as hydrogen peroxide [8,9,10,11,12,13], molecular oxygen [14,15,16,17,18,19], tert -butyl hydroperoxide [20,21,22,23], cumene hydroperoxide [24,25,26,27], iodobenzene diacetate [28,29,30], sodium hypochlorite [31,32,33], and oxone [34].…”

Section: Introductionmentioning

confidence: 99%

pH-Dependence of the Aqueous Phase Room Temperature Brønsted Acid-Catalyzed Chemoselective Oxidation of Sulfides with H2O2

Shen

Zhou

et al. 2015

Molecules

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A pH-dependence of the Brønsted acid-catalyzed oxidation of sulfides to the corresponding sulfoxides with H2O2 is reported for the first time based on our systematic investigation of the catalytic performance of a series of Brønsted acids. For all of the Brønsted acids investigated, the catalytic performances do not depend on the catalyst loading (mol ratio of Brønsted acid to substrate), but rather depend on the pH value of the aqueous reaction solution. All of them can give more than 98% conversion and selectivity in their aqueous solution at pH 1.30, no matter how much the catalyst loading is and what the Brønsted acid is. This pH-dependence principle is a very novel perspective to understand the Brønsted-acid catalysis system compared with our common understanding of the subject.

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“…Its thermal chemistry is an active area of research and has been recently reviewed. 2,3 In contrast, the photochemistry of the sulfoxide is underdeveloped. 4 Though evidence of a number of intriguing phototransformations is ample, mechanistic information is meager, and we have undertaken a systematic study.…”

Section: Introductionmentioning

confidence: 99%

“…Because of its utility in asymmetric synthesis, the sulfoxide is a functional group of increasing interest in the organic chemistry community. Its thermal chemistry is an active area of research and has been recently reviewed. , In contrast, the photochemistry of the sulfoxide is underdeveloped…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of Excited State Quenching by Aromatic Sulfoxides

1996

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Aromatic sulfoxides quench singlet excited states of sensitizers whose singlet energies render energy transfer unlikely as a mechanism. Well over 50 rate constants for singlet quenching of various sensitizers by a series sulfoxides have been obtained, as have estimates of the redox potentials for the series of sulfoxides. These data strongly suggest that the mechanism for quenching involves electron transfer and/or exciplex formation. Charge (electron) transfer is from the sensitizer to the sulfoxide. IntroductionBecause of its utility in asymmetric synthesis, the sulfoxide is a functional group of increasing interest in the organic chemistry community. Its thermal chemistry is an active area of research and has been recently reviewed. 2,3 In contrast, the photochemistry of the sulfoxide is underdeveloped. 4 Though evidence of a number of intriguing phototransformations is ample, mechanistic information is meager, and we have undertaken a systematic study.One poorly understood area of fundamental importance is the mechanism by which sulfoxides quench sensitizers that have been used to carry out various chemical reactions. [5][6][7] The triplet energies of simple aromatic sulfoxides are fairly high, in the range of 75-81 kcal/mol, with the higher values reserved for alkyl aryl sulfoxides. 8 These exceed the triplet energies of molecules which have been reported as sensitizers, such as benzophenone (E T ) 69 kcal/mol) and naphthalene (E T ) 61 kcal/mol), though chemical transformations occur nonetheless. For example, Shelton and Davis found that tert-butyl phenyl sulfoxide decomposed under sensitization with acetophenone (E T ) 74 kcal/mol), triphenylene (E T ) 66 kcal/mol), and anthraquinone (E T ) 63 kcal/mol). 9 Anomalous sensitization can also occur from singlet states. Mislow and Hammond found that aryl methyl sulfoxide photoracemization could be brought about by naphthalene (Np) singlets. [10][11][12][13] This remains the best documented case of sulfoxide sensitization. Rate constants of 3 × 10 7 to 2 × 10 8 M -1 s -1 were determined for the quenching of Np by several aryl methyl sulfoxides. Elegant experiments correlated the rate constants with sensitized racemization of the sulfoxide. Recognizing the apparently endothermic energy transfer, Cooke and Hammond suggested that Np-sensitized racemization of tolyl methyl sulfoxide might result from exciplex formation. 12,13 Yet, there was no direct evidence for the exciplex and "use of electron-donating and -withdrawing substituents on the benzene ring failed to show a clear trend or a large variation in the quenching rate constants which would support the hypothesis that charge-transfer interactions are dominant." 13 Given the usually dramatic effect of small energetic changes on rate constants in the reported range, such insensitivity is surprising. To more rigorously examine the mechanism(s) of sulfoxide quenching, a greater spread of related compounds was needed, and the rate constants so obtained needed to be correlated with other physical parameters.We have...

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Synthesis of Sulphoxides

Cited by 6 publications

References 581 publications

Stereoselective Synthesis of Racemic and Optically ActiveE-Vinyl andE-Dienyl Sulfoxides via Wittig Reaction of α-Sulfinyl Phosphonium Ylides

Stereoselective Synthesis of Racemic and Optically ActiveE-Vinyl andE-Dienyl Sulfoxides via Wittig Reaction of α-Sulfinyl Phosphonium Ylides

pH-Dependence of the Aqueous Phase Room Temperature Brønsted Acid-Catalyzed Chemoselective Oxidation of Sulfides with H2O2

Mechanisms of Excited State Quenching by Aromatic Sulfoxides

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