2-(Trimethylsilyl)ethyl Sulfoxides as a Convenient Source of Sulfenate Anions

Abstract

The present report describes the novel and smooth generation of sulfenate salts by fluoride-mediated cleavage of 2-(tri­methylsilyl)ethyl sulfoxides. Efficiency of the process was elucidated through further reaction with alkyl halides to give stable sulfoxide end products.

Key words

sulfoxides - sulfenate salts - silicon - fluorine - alkylation

References

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16

Methyl sulfinate 4 was prepared by oxidative fragmentation of sulfoxide 1g (R¹ = t-Bu) using SO₂Cl₂ to give 2-(trimethylsilyl)ethanesulfinyl chloride,^9f followed by treatment with MeOH in the presence of Et₃N.

18

Similar chemical shifts were observed either in CDCl₃ or THF-d ₈.

19

Crystal structure determination of 1b: Single crystals of sulfoxide 1b suitable for X-ray crystallographic analysis were obtained by slow diffusion of pentane in CH₂Cl₂ soln. X-ray diffraction experiments for monocrystal of 1b were performed at 150 K with graphite-monochromatized MoK_α radiation on a Bruker-Nonius Kappa CCD area detector diffractometer. Formula C₁₁H₁₇BrOSSi, M _r 305.31, crystal system triclinic, space group P1, a = 6.5653 (3) Å, b = 10.1206 (4) Å, c = 11.8654 (5) Å, α = 66.082 (2)°, β = 78.256 (3)°, γ = 80.455 (3)°, V = 702.54 (5) ų, Z = 2, density calcd = 1.443 g/cm³, µ = 3.135 cm^-1, R = 0.0386, wR = 0.0997. Selected bond lengths (Å) and angles(deg): Br1-C1 1.8912 (14), S1-O1 1.4930 (13), S1-C4 1.7924 (13), S1-C7 1.8248 (14), Si1-C8 1.8792 (14), Si1-C9 1.8512 (18), Si1-C10 1.862 (2), Si1-C11 1.862 (2), C7-C8 1.512 (2), O1-S1-C4 106.27 (7), O1-S1-C7 106.60 (7), C4-S1-C7 97.78 (6), C11-Si1-C8 106.90 (8), C9-Si1-C8 109.56 (9), C10-Si1-C8 110.30 (10). Program(s)used to solve structure: SHELXS97. Program(s)used to refine structure: SHELXL97. Software used to prepare material for publication: SHELXL97. Crystallographic data for compound 1b have been deposited at the Cambridge Crystallographic Data Centre, CCDC No 629340. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK; [phone]; E-mail: [e-mail] or http://www.ccdc.cam.ac.uk.

24

Spectral data are in agreement with those previously reported by us.^6a

27

The reaction was carried out with a mixture of both Z- and E-isomers but also the geometrically pure substrates.