First synthesis and characterization of vinylselenols and vinyltellurols

Guillemin, Jean‐Claude; Bouayad, Asmae; Vijaykumar, Dange

doi:10.1039/b002886j

Cited by 40 publications

(56 citation statements)

References 17 publications

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“…This observation parallels that of Riague and Guillemin, who had earlier prepared several of the same allylic selenocyanates and reported their purification by vacuum distillation, 73 but it stands in contrast to the reported chemistry of simple allylic thiocyanates which are reported to undergo [2,3]-sigmatropic rearrangement to the corresponding allylic isothiocyanates in a matter of hours at room temperature. 74,75 Based on the work of Sharpless with 2-methyl-3-selenocyanato-1-heptene, secondary and presumably tertiary selenocyanates can be expected to undergo a [1,3]-sigmatropic rearrangement to their primary regioisomers.…”

Section: Allylic Selenosulfide Rearrangementcontrasting

confidence: 50%

Dechalcogenative Allylic Selenosulfide and Disulfide Rearrangements: Complementary Methods for the Formation of Allylic Sulfides in the Absence of Electrophiles. Scope, Limitations, and Application to the Functionalization of Unprotected Peptides in Aqueous Media.

et al. 2007

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Primary allylic selenosulfates (seleno Bunte salts) and selenocyanates transfer the allylic selenide moiety to thiols giving primary allylic selenosulfides, which undergo rearrangement in the presence of PPh 3 with the loss of selenium to give allylically rearranged allyl alkyl sulfides. This rearrangement may be conducted with prenyl-type selenosulfides to give isoprenyl alkyl sulfides. Alkyl secondary and tertiary allylic disulfides, formed by sulfide transfer from allylic heteroaryl disulfides to thiols, undergo desulfurative allylic rearrangement on treatment with PPh 3 in methanolic acetonitrile at room temperature. With nerolidyl alkyl disulfides this rearrangement provides an electrophile-free method for the introduction of the farnesyl chain onto thiols. Both rearrangements are compatible with the full range of functionality found in the proteinogenic amino acids and it is demonstrated that the desulfurative rearrangement functions in aqueous media, enabling the derivatization of unprotected peptides. It is also demonstrated that the allylic disulfide rearrangement can be inducted in the absence of phosphine at room temperature by treatment with piperidine, or simply by refluxing in methanol. Under these latter conditions the reaction is also applicable to allyl aryl disulfides, providing allylically rearranged allyl aryl sulfides in good yields.

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Section: Allylic Selenosulfide Rearrangementcontrasting

confidence: 50%

Dechalcogenative Allylic Selenosulfide and Disulfide Rearrangements: Complementary Methods for the Formation of Allylic Sulfides in the Absence of Electrophiles. Scope, Limitations, and Application to the Functionalization of Unprotected Peptides in Aqueous Media.

et al. 2007

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“…General procedure for the preparation of low-boiling thiol, [32] selenols, [13,33] and tellurols [13,33] [Eqs. (4)-(6)]:…”

Section: Methodsmentioning

confidence: 99%

“…Ethenethiol, selenols, and tellurols were prepared starting from the corresponding disulfide, diselenide, or ditelluride by the approach reported for etheneselenol [13,29] and using the apparatus described in reference [29]. A two-necked 50 mL flask containing the precursor (2 mmol in 10 mL of tetraglyme) was fitted on a vacuum line equipped with two traps, and the solution was degassed.…”

Section: Methodsmentioning

confidence: 99%

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Acidity Trends in α,β‐Unsaturated Sulfur, Selenium, and Tellurium Derivatives: Comparison with C‐, Si‐, Ge‐, Sn‐, N‐, P‐, As‐, and Sb‐Containing Analogues

Guillemin

Riague

Gal

et al. 2005

Chemistry A European J

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The gas-phase acidity of CH3-CH2XH (X=S, Se, Te), CH2=CHXH (X=S, Se, Te) and PhXH (X=S, Se) compounds was measured by means of Fourier transform ion cyclotron resonance mass spectrometry. To analyze the role that unsaturation plays on the intrinsic acidity of these systems, a parallel theoretical study, in the framework of the G2 and the G2(MP2) theories, was carried out for all ethyl, ethenyl (vinyl), ethynyl, and phenyl O-, S-, Se-, and Te-containing derivatives. Unsaturated compounds are stronger acids than their saturated analogues, because of the strong pi-electron donor ability of the heteroatoms that contributes to a large stabilization of the unsaturated anions. Ethynyl derivatives are stronger acids than vinyl compounds, while phenyl derivatives have an intrinsic acidity intermediate between that of the corresponding vinyl and ethynyl analogues. The CH2=CHXH vinyl compounds (enol-like) behave systematically as slightly stronger acids than their CH3-C(H)X (keto-like) tautomers. Vinyl derivatives are stronger acids than ethyl compounds, because the anion stabilization attributable to unsaturation is greater than that undergone in the neutral compounds. Conversely, the enhanced acidity of the ethynyl derivatives with respect to the vinyl compounds is due to two concomitant effects, the stabilization of the anion and the destabilization of the neutral compound. The acidities of ethyl, vinyl, and ethynyl derivatives containing heteroatoms of Groups 14, 15, and 16 of the periodic table are closely related, and reflect the differences in electronegativity of the CH3CH2-, CH2=CH-, and CH[triple chemical bond]C- groups.

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“… For the selenocyanates another question is the possible conjugation of the two unsaturated fragments. The recent synthesis of compounds 1 – 3 12, 13 allows us to investigate these questions in experimental and theoretical approaches. To the best of our knowledge, we here report the first study by photoelectron spectroscopy devoted to aliphatic selenols.…”

Section: Introductionmentioning

confidence: 99%

Alkenyl Selenols and Selenocyanates: Synthesis, Spectroscopic Characterization by Photoelectron Spectroscopy, and Quantum Chemical Study

Bajor¹,

Veszprémi²,

Riague³

et al. 2004

Chemistry A European J

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Vinyl, allyl, and homoallyl selenols were easily prepared by a chemoselective reduction of the corresponding selenocyanates with aluminum hydrides. Two stable vinyl and five stable allyl conformers of both series were predicted on the potential-energy surface. The interaction of SeH or SeCN groups with the vinyl group has been investigated with UV photoelectron spectroscopy and quantum chemical calculations, using the MP2/cc-pVTZ and B3LYP/cc-pVTZ levels. In the vinyl derivatives, a surprisingly strong direct conjugation of the selenium lone electron pair and the C=C double bond was observed. On the other hand, in allyl position the selenium lone pair is independent on the C=C double bond, and the hyperconjugation between the Se-C bond and the double bond is the ruling effect. Thus is clarified the type and extent of the interaction between the SeH or SeCN group and the unsaturated moiety.

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First synthesis and characterization of vinylselenols and vinyltellurols

Cited by 40 publications

References 17 publications

Dechalcogenative Allylic Selenosulfide and Disulfide Rearrangements: Complementary Methods for the Formation of Allylic Sulfides in the Absence of Electrophiles. Scope, Limitations, and Application to the Functionalization of Unprotected Peptides in Aqueous Media.

Dechalcogenative Allylic Selenosulfide and Disulfide Rearrangements: Complementary Methods for the Formation of Allylic Sulfides in the Absence of Electrophiles. Scope, Limitations, and Application to the Functionalization of Unprotected Peptides in Aqueous Media.

Acidity Trends in α,β‐Unsaturated Sulfur, Selenium, and Tellurium Derivatives: Comparison with C‐, Si‐, Ge‐, Sn‐, N‐, P‐, As‐, and Sb‐Containing Analogues

Alkenyl Selenols and Selenocyanates: Synthesis, Spectroscopic Characterization by Photoelectron Spectroscopy, and Quantum Chemical Study

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