Synthesis 2007(9): 1315-1324  
DOI: 10.1055/s-2007-966017
PAPER
© Georg Thieme Verlag Stuttgart · New York

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

Florian Foucoina, Caroline Caupènea, Jean-François Lohiera, Jana Sopkova de Oliveira Santosb, Stéphane Perrio*a, Patrick Metznera
a Laboratoire de Chimie Moléculaire et Thio-Organique (UMR CNRS 6507), ENSICAEN, Université de Caen-Basse Normandie, 6 Boulevard du Maréchal Juin, 14050 Caen, France
Fax: +33(2)31452877; e-Mail: perrio@ensicaen.fr;
b Centre d"Etudes et de Recherche sur le Médicament de Normandie (UPRES EA 3915), Université de Caen Basse-Normandie, 5 Rue Vaubénard, 14032 Caen, France
Further Information

Publication History

Received 9 February 2007
Publication Date:
18 April 2007 (online)

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.

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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.

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

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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 MoKα 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) Å3, 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; +44 (1223)336408; E-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk.

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

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