α,β-Epoxy sulfones. The Darzens condensation with α-halosulfones

Vogt, Peter; Tavares, Donald F.

doi:10.1139/v69-477

Cited by 48 publications

(9 citation statements)

References 2 publications

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“…116 that was assigned by Bohlmann and Haffer. It has also given substance to the stereochemistry of a range of other a,P-epoxysulfones, such as 5 a and b, that have been prepared by Vogt and Tavares (24). We prepared 5c as an unstable, crystalline material, using A nuclear Overhauser experiment on the two protons directly attached to the epoxide ring showed that these are trans to each other, which again confirmed the previous literature assignments of stereochemistry in these epoxysulfones.…”

Section: Resultssupporting

confidence: 82%

“…Tavares synthesized a,P-epoxysulphones, 5, by a Darzens-type of condensation and found that only the trans stereoisomer was formed (24). Their assignment of stereochemistry was based on known vicinal proton-proton coupling constants in oxiranes, but the differences in these constants between the cis and trans isomers are in fact too small to permit unambiguous assignments (25), and caution is required.…”

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confidence: 99%

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Stereochemical studies on the formation of α,β-epoxysulfones using α-chloro-β-hydroxysulfones of known configuration

Grossert¹,

Sotheeswaran²,

Dharmaratne³

et al. 1988

Can. J. Chem.

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adjacent to sulfonyl groups are known to proceed with difficulty, and there is evidence to suggest that these may not necessarily proceed by an SN2 pathway. The mechanism of these reactions could be studied in principle by using the conversion of a-chloro-P-hydroxysulfones of known configuration into a,P-epoxysulfones of known configuration. This paper describes results in which this has been attempted. However, the stereochemical aspects of the epoxide formation could not be assigned unequivocally because of the intervention of a very facile "retro-aldol" process when the chlorohydrins are subjected to treatment with bases, although the experimental results do suggest that the reaction does proceed in a regular SN2-like manner, with inversion at carbon. The X-ray crystal structures of two highly substituted a,P-epoxysulfones are presented, thus putting the structures, including stereochemistry, of a range of these compounds on firm ground. I1 est connu que les riactions de substitution sur des carbones voisins de groupements sulfonyles ne se produisent qu'avec difficult6 et il existe des donnCes sugg6rant que ces r6actions ne precedent pas n6cessairernent par une voie SN2. En principe, on peut 6tudier le rntcanisme de ces reactions en utilisant la transformation d'a-chloro P-hydroxysulfones de configurations connues en a,P-Cpoxysulfones de configurations connues. Dans ce travail, on dCcrit les resultats de telles Ctudes. Toutefois, dfi au fait qu'un processus ccrttro-aldolique~ facile intervient lorsque les chlorohydrines sont soumises a un traitement par les bases, on n'a pas pu attribuer sans equivoque les aspects stCrCochimiques de la formation de I'6poxyde mCme si les rCsultats expkrimentaux suggkrent que la reaction se produit de fait par le biais d'une reaction regulihre SN2, avec inversion au niveau du carbone. On prCsente les structures cristallines dCterminCes par diffraction des rayons-X de deux a,P-Cpoxysulfones fortement substitukes; on Ctablit donc avec certitude les structures, y compris leur stCrCochimie, d'un large Cventail de ces composCs.[Traduit par la revue]

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Section: Resultssupporting

confidence: 82%

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confidence: 99%

Stereochemical studies on the formation of α,β-epoxysulfones using α-chloro-β-hydroxysulfones of known configuration

Grossert¹,

Sotheeswaran²,

Dharmaratne³

et al. 1988

Can. J. Chem.

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“…The first example of the sulfone-stabilized oxiranyl anion was reported by Tavares in his reaction of epoxy sulfone 251 with sodium methoxide in deuteriomethanol, giving deuterated 252 in high yield (Scheme 40). 60 Eisch also mentioned the sulfonestabilized oxiranyl anions as already described above. 54,55 Extensive studies of the formation of sulfonestabilized oxiranyl anion and trapping with electrophiles were reported by Jackson.…”

Section: Sulfone-stabilized Oxiranyl Anionsmentioning

confidence: 92%

Oxiranyl Anions and Aziridinyl Anions

Satoh

1996

Chem. Rev.

240

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“…Chloromethyl phenyl sulfone (17) was prepared by a procedure described by Vogt and Tavares. 29 2-Phenyl-3-(phenylsulfonyl)oxirane (18). Oxirane 18 was prepared by modifying the method described by Zwanenburg et al 30 30 was used to prepare aldehyde 19.…”

Section: Methodsmentioning

confidence: 99%

Matrix Isolation of Diphenylsulfene and Diphenyl-α-sultine

1997

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Diphenylsulfene (5) and diphenyl-α-sultine 6 were generated in cryogenic matrices by three independent routes: (i) the thermal reaction of diphenylcarbene (8) and SO2, (ii) the photochemically induced hetero Wolff rearrangement of sulfonylcarbene 11, and (iii) oxygen transfer from ozone to diphenylsulfine 16. Isotopic labeling with 13C and 18O allows for the assignment of several characteristic IR vibrations of 5. Irradiation with λ > 375 nm results in the rearrangement of 5 to 6, which is the first α-sultine that has been characterized spectroscopically. The final product on UV irradiation of 6 is benzophenone (9) and sulfur monoxide.

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α,β-Epoxy sulfones. The Darzens condensation with α-halosulfones

Cited by 48 publications

References 2 publications

Stereochemical studies on the formation of α,β-epoxysulfones using α-chloro-β-hydroxysulfones of known configuration

Stereochemical studies on the formation of α,β-epoxysulfones using α-chloro-β-hydroxysulfones of known configuration

Oxiranyl Anions and Aziridinyl Anions

Matrix Isolation of Diphenylsulfene and Diphenyl-α-sultine

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