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[R2S-CH2-OTf]+ OTf– as a Reagent with an Optionally Mono-or Biselectrophilic Csp3 Center

  • Robert Weiss EMAIL logo , Matthias Handke and Frank Hampel
Published/Copyright: June 2, 2014
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 53 Issue 8

Abstract

Sulfonium salts [R2S-CH2-OTf]+ OTf- 1a,b are synthetically versatile 1,1-biselectrophiles featuring the sulfonio- and triflato-substituents as leaving groups of differential nucleofugic power. Reactions with a number of neutral nucleophiles |Nu yield a series of novel sulfoniom ethylated onium salts [R2S-CH2-Nu]2+ 2OTf- 2 - 8 under very mild conditions. Structures of salts 2a, 5a and 6b were confirm ed by X -ray analysis. With certain N -hetarenes exchange of both nucleofuges in la was achieved, yielding the symmetrical 1,1-bisonium salts 9 and 10. With pyridine(derivatives) selective substitution of the sulfoniofunction in 1,1-bisonium systems 2a and 5a was also realized. These reactions represent typical examples of nucleophilic substitutions at geminally bisonio substituted Csp3 centers, which we recently have introduced as a novel variant of Sɴ2 reactivity.

Keywords: Geminal Bisonium Salts; SN-Reaction; Synthesis; Regioselectivity; X -Ray Data
Received: 1998-3-11
Published Online: 2014-6-2
Published in Print: 1998-8-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

Articles in the same Issue

  1. Variations in the Chain Structure of Cationic (Phosphine)gold(I) Dialkyldithiophosphate Complexes
  2. The Solution and Solid State Structure of L-Carnitine L-Tartrate
  3. Wechselwirkungen in Molekülkristallen, 143. ortho-Benzol-Derivate mit ineinander verzahnten Chlormethyl-und Methylamino-Substituenten: Strukturen und Rotationsenthalpie-Hyperflächen/ Interactions in M olecular Crystals, 143. ortho-Benzene Derivatives with M eshed Cogwheel Chlorom ethyl and Methylamino Substituents: Structures and Rotation Enthalpy Hypersurfaces
  4. Wechselwirkungen in Molekülkristallen, 144. ortho-Benzol-Derivate mit ineinander verzahnten Trimethylsilyl- Substituenten: Strukturvergleich mit Benzol-1,2-disulfonat-Salzen und Rotationsenthalpie-Hyperflächen/ Interactions in Molecular Crystals, 144, ortho-Benzene Derivatives with Meshed Cogwheel Trimethylsilyl Substituents: Structural Comparison with Benzene-1,2-disulfonate Salts and Rotation Enthalpy Hypersurfaces
  5. Kristallstruktur von Cs2[B6H5(SCN)]/ Crystal Structure of Cs2[B6H5(SCN)]
  6. Darstellung, spektroskopische Charakterisierung und Kristallstruktur von Dicyclopentadienylcobalt-hexahydro-closo-hexaborat [(C5H5)Co(C5H4)B6H5Hfac]/ Synthesis, Spectroscopic Characterization and Crystal Structure of Dicyclopentadienyl- cobalt-hexahydro-closo-hexaborate [(C5H5)Co(C5H4)B6H5Hfac]
  7. Kristallstrukturen, Schwingungsspektren und Normalkoordinaten- analysen von trans-[OsO2(ox)2]2– und trans-[OsO2(mal)2]2–/ Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of trans-[OsO2(ox)2]2– and trans -[OsO2(mal)2]2–
  8. Darstellung, 11B-und 19F-NMR-Spektren des Monofluoropentaiodo- closo-hexaboratanions sowie Kristallstruktur von (CH2Py2)[B6FI5]/ Synthesis, 11B and 19F NMR Spectra of the Monofluoropentaiodo-closo-hexaborate Anion and the Crystal Structure of (CH2Py2)[B6FI5]
  9. Synthesis and X-Ray Structure of 1,3,5-Tri(phenylethynyl)benzene
  10. Synthesis, IR and X-Ray Studies of Tetra(N,N′-tetraethyl-N″-benzoyl- phosphorictriamide)-tetra(μ-3-methoxo)-tetra(methanol)tetra-NickeI(II)
  11. A New Synthesis of Tetrakis(C-methyl)octakis(hydroxyethyl)calix[4]- resorcinarene via an Ethoxy-Tethered Trimethylsiloxy Precursor
  12. Kohlensäurebis(trimethylsilyl)ester: Spektroskopische Charakterisierung und verbesserte Darstellung/ The Bis(trimethylsilyl)ester of Carbonic Acid: Spectroscopic Characterization and Improved Preparation
  13. Photooxidation of Dicyanoaurate(I) Induced by Metal-to-Ligand Charge Transfer Excitation
  14. Halogeno(acylphenolato)cobalt(III)-Verbindungen mit Trimethylphosphan-Liganden/ Halogeno(acylphenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands
  15. Reaktion von [Co(But2PH)2I2] mit [Ru3(CO)12]: Synthese und Röntgenkristallstrukturanalyse von [Ru3(CO)6(μ-H)(μ-I)2(μ-PBut2)(But2PH)]/ Reaction of [Co(But2PH)2I2] with [Ru3(CO)12]: Synthesis and X-Ray Crystal Structure of [Ru3(CO)6(μ-H)(μ-I)2(μ-PBut2)(But2PH)]
  16. Crystal Structure and Spectroscopic Behaviour of a Binuclear Copper(II) Complex of Mefenamic Acid and Dimethylsulfoxide
  17. Electrochemical Study of Tricarbonyl(η6-cyclooctatetraene)metal(0) Complexes of the Group 6 Elements
  18. Zur Reaktion von 2,3-Dihydroimidazol-2-ylidenen mit Pentafluorpyridin: Carbene als Reaktionspartner in der nucleophilen aromatischen Substitution/ On the Reaction of 2,3-Dihydroimidazol-2-ylidenes with Pentafluoropyridine: Carbenes as Reactants in Nucleophilic Aromatic Substitution
  19. Über die Reaktion von Bis(t-butylamino)dimethylsilan mit Titantetrachlorid. Kristallstrukturen des Imido-Komplexes [TiCl2(N-CMe3)(H2 N-CMe3)(CH3CN)]2 und des Ketimido-Komplexes [TiCl3 {NC(Me)N(H)CMe3}(CH3CN)2]/ On the Reaction of Bis(t-butylamino)dimethylsilane with Titanium Tetrachloride. Crystal Structures of the Imido Complex [TiCl2(N-CMe3)(H2N-CMe3)(CH3CN)]2 and of the Ketimido Complex [TiCl3{NC(Me)N(H)CMe3}(CH3CN)2]
  20. Tuning the Steric and Electronic Properties of Chiral Rhenium Thiolate Complexes
  21. Zur Kristallstruktur von Ho2Se3/ On the Crystal Structure of Ho2Se3
  22. Metal Ion-Binding Properties in Aqueous Solution of the Nucleoside Analogue, 5,6-Dichloro-1-(β-ᴅ-ribofuranosyl)benzimidazole (DRB)
  23. Synthesis of Some Chromanone Derivatives and the Use of DNA in Evaluation of their Biological Activity
  24. [R2S-CH2-OTf]+ OTf– as a Reagent with an Optionally Mono-or Biselectrophilic Csp3 Center
  25. Notizen: Preparation, Structures and Optical Properties of [H3N(CH2)6NH3]BiX5 (X=I, Cl) and [H3N(CH2)6NH3]SbX5 (X=I, Br)
https://doi.org/10.1515/znb-1998-0824
Keywords for this article
Geminal Bisonium Salts; SN-Reaction; Synthesis; Regioselectivity; X -Ray Data

Articles in the same Issue

  1. Variations in the Chain Structure of Cationic (Phosphine)gold(I) Dialkyldithiophosphate Complexes
  2. The Solution and Solid State Structure of L-Carnitine L-Tartrate
  3. Wechselwirkungen in Molekülkristallen, 143. ortho-Benzol-Derivate mit ineinander verzahnten Chlormethyl-und Methylamino-Substituenten: Strukturen und Rotationsenthalpie-Hyperflächen/ Interactions in M olecular Crystals, 143. ortho-Benzene Derivatives with M eshed Cogwheel Chlorom ethyl and Methylamino Substituents: Structures and Rotation Enthalpy Hypersurfaces
  4. Wechselwirkungen in Molekülkristallen, 144. ortho-Benzol-Derivate mit ineinander verzahnten Trimethylsilyl- Substituenten: Strukturvergleich mit Benzol-1,2-disulfonat-Salzen und Rotationsenthalpie-Hyperflächen/ Interactions in Molecular Crystals, 144, ortho-Benzene Derivatives with Meshed Cogwheel Trimethylsilyl Substituents: Structural Comparison with Benzene-1,2-disulfonate Salts and Rotation Enthalpy Hypersurfaces
  5. Kristallstruktur von Cs2[B6H5(SCN)]/ Crystal Structure of Cs2[B6H5(SCN)]
  6. Darstellung, spektroskopische Charakterisierung und Kristallstruktur von Dicyclopentadienylcobalt-hexahydro-closo-hexaborat [(C5H5)Co(C5H4)B6H5Hfac]/ Synthesis, Spectroscopic Characterization and Crystal Structure of Dicyclopentadienyl- cobalt-hexahydro-closo-hexaborate [(C5H5)Co(C5H4)B6H5Hfac]
  7. Kristallstrukturen, Schwingungsspektren und Normalkoordinaten- analysen von trans-[OsO2(ox)2]2– und trans-[OsO2(mal)2]2–/ Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of trans-[OsO2(ox)2]2– and trans -[OsO2(mal)2]2–
  8. Darstellung, 11B-und 19F-NMR-Spektren des Monofluoropentaiodo- closo-hexaboratanions sowie Kristallstruktur von (CH2Py2)[B6FI5]/ Synthesis, 11B and 19F NMR Spectra of the Monofluoropentaiodo-closo-hexaborate Anion and the Crystal Structure of (CH2Py2)[B6FI5]
  9. Synthesis and X-Ray Structure of 1,3,5-Tri(phenylethynyl)benzene
  10. Synthesis, IR and X-Ray Studies of Tetra(N,N′-tetraethyl-N″-benzoyl- phosphorictriamide)-tetra(μ-3-methoxo)-tetra(methanol)tetra-NickeI(II)
  11. A New Synthesis of Tetrakis(C-methyl)octakis(hydroxyethyl)calix[4]- resorcinarene via an Ethoxy-Tethered Trimethylsiloxy Precursor
  12. Kohlensäurebis(trimethylsilyl)ester: Spektroskopische Charakterisierung und verbesserte Darstellung/ The Bis(trimethylsilyl)ester of Carbonic Acid: Spectroscopic Characterization and Improved Preparation
  13. Photooxidation of Dicyanoaurate(I) Induced by Metal-to-Ligand Charge Transfer Excitation
  14. Halogeno(acylphenolato)cobalt(III)-Verbindungen mit Trimethylphosphan-Liganden/ Halogeno(acylphenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands
  15. Reaktion von [Co(But2PH)2I2] mit [Ru3(CO)12]: Synthese und Röntgenkristallstrukturanalyse von [Ru3(CO)6(μ-H)(μ-I)2(μ-PBut2)(But2PH)]/ Reaction of [Co(But2PH)2I2] with [Ru3(CO)12]: Synthesis and X-Ray Crystal Structure of [Ru3(CO)6(μ-H)(μ-I)2(μ-PBut2)(But2PH)]
  16. Crystal Structure and Spectroscopic Behaviour of a Binuclear Copper(II) Complex of Mefenamic Acid and Dimethylsulfoxide
  17. Electrochemical Study of Tricarbonyl(η6-cyclooctatetraene)metal(0) Complexes of the Group 6 Elements
  18. Zur Reaktion von 2,3-Dihydroimidazol-2-ylidenen mit Pentafluorpyridin: Carbene als Reaktionspartner in der nucleophilen aromatischen Substitution/ On the Reaction of 2,3-Dihydroimidazol-2-ylidenes with Pentafluoropyridine: Carbenes as Reactants in Nucleophilic Aromatic Substitution
  19. Über die Reaktion von Bis(t-butylamino)dimethylsilan mit Titantetrachlorid. Kristallstrukturen des Imido-Komplexes [TiCl2(N-CMe3)(H2 N-CMe3)(CH3CN)]2 und des Ketimido-Komplexes [TiCl3 {NC(Me)N(H)CMe3}(CH3CN)2]/ On the Reaction of Bis(t-butylamino)dimethylsilane with Titanium Tetrachloride. Crystal Structures of the Imido Complex [TiCl2(N-CMe3)(H2N-CMe3)(CH3CN)]2 and of the Ketimido Complex [TiCl3{NC(Me)N(H)CMe3}(CH3CN)2]
  20. Tuning the Steric and Electronic Properties of Chiral Rhenium Thiolate Complexes
  21. Zur Kristallstruktur von Ho2Se3/ On the Crystal Structure of Ho2Se3
  22. Metal Ion-Binding Properties in Aqueous Solution of the Nucleoside Analogue, 5,6-Dichloro-1-(β-ᴅ-ribofuranosyl)benzimidazole (DRB)
  23. Synthesis of Some Chromanone Derivatives and the Use of DNA in Evaluation of their Biological Activity
  24. [R2S-CH2-OTf]+ OTf– as a Reagent with an Optionally Mono-or Biselectrophilic Csp3 Center
  25. Notizen: Preparation, Structures and Optical Properties of [H3N(CH2)6NH3]BiX5 (X=I, Cl) and [H3N(CH2)6NH3]SbX5 (X=I, Br)
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