Subscribe to RSS
DOI: 10.1055/s-2007-966017
2-(Trimethylsilyl)ethyl Sulfoxides as a Convenient Source of Sulfenate Anions
Publication History
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.
Key words
sulfoxides - sulfenate salts - silicon - fluorine - alkylation
- 1 For a recent review:
O’Donnell JS.Schwan AL. J. Sulfur Chem. 2004, 25: 183 -
2a
Forman HJ.Fukuto JM.Torres M. Am. J. Physiol. Cell. Physiol. 2004, 287: C246 -
2b
Nagahara N.Katayama A. J. Biol. Chem. 2005, 280: 34569 -
3a
Sandrinelli F.Perrio S.Beslin P. J. Org. Chem. 1997, 62: 8626 -
3b
Sandrinelli F.Perrio S.Averbuch-Pouchot M.-T. Org. Lett. 2002, 4: 3619 -
3c
Sandrinelli F.Fontaine G.Perrio S.Beslin P. J. Org. Chem. 2004, 69: 6916 -
3d
Sandrinelli F.Boudou C.Caupène C.Averbuch-Pouchot M.-T.Perrio S.Metzner P. Synlett 2006, 3289 -
4a
Maezaki N.Yagi S.Ohsawa S.Ohishi H.Tanaka T. Tetrahedron 2003, 59: 9895 -
4b
Maezaki N.Yagi S.Yoshigami R.Maeda J.Suzuki T.Ohsawa S.Tsukamoto K.Tanaka T. J. Org. Chem. 2003, 68: 5550 -
4c
Maezaki N.Yagi S.Maeda J.Yoshigami R.Tanaka T. Heterocycles 2004, 62: 263 - 5
O’Donnell JS.Schwan AL. Tetrahedron Lett. 2003, 44: 6293 -
6a
Caupène C.Boudou C.Perrio S.Metzner P. J. Org. Chem. 2005, 70: 2812 -
6b
Maitro G.Prestat G.Madec D.Poli G. J. Org. Chem. 2006, 71: 7449 -
6c
Maitro G.Vogel S.Prestat G.Madec D.Poli G. Org. Lett. 2006, 8: 5951 -
7a
Oida T.Ohnishi A.Shimamaki T.Hayashi Y.Tanimoto S. Bull. Chem. Soc. Jpn. 1991, 64: 702 -
7b
Oida T.Nakamura M.Takashima Y.Hayashi Y. Bull. Inst. Chem. Res., Kyoto Univ. 1992, 70: 295 - Benzenesulfenic acid 2-(trimethylsilyl)ethyl ester was prepared by reaction of benzenesulfenyl chloride with 2-(trimethylsilyl)ethyl alcohol. By comparison, the analogous sulfoxides are readily available from commercial compounds according to:
-
8a
Schwan AL.Pippert MF. Tetrahedron: Asymmetry 1995, 6: 131 -
8b
Schwan AL.Brillon D.Dufault R. Can. J. Chem. 1994, 72: 325 - The reactivity of more sophisticated β-silyl sulfoxides with TBAF has previously been investigated by the group of Toru, but their attention was focused on the alkene product:
-
9a
Nakamura S.Watanabe Y.Toru T. J. Chem. Soc., Perkin Trans. 1 1999, 3403 -
9b
Nakamura S.Takemoto H.Ueno Y.Toru T.Kakumoto T.Hagiwara T. J. Org. Chem. 2000, 65: 469 -
9c
Nakamura S.Uchiyama Y.Ishikawa S.Fukinbara R.Watanabe Y.Toru T. Tetrahedron Lett. 2002, 43: 2381 -
9d
Nakamura S.Kusuda S.Kawamura K.Toru T. J. Org. Chem. 2002, 67: 640 -
9e
Nakamura S.Nakayama J.-i.Toru T. J. Org. Chem. 2003, 68: 5766 - Schwan also described a fluoride free deprotection of simple 2-(trimethylsilyl)ethyl sulfoxides by treatment with thionyl chloride to afford sulfinyl chlorides:
-
9f
Schwan AL.Strickler RR.Dunn-Dufault R.Brillon D. Eur. J. Org. Chem. 2001, 1643 -
10a
Huttunen KM.Kumpalainen H.Leppänen J.Rautio J.Järvinen T.Vepsäläinen J. Synlett 2006, 701 -
10b
Fustero S.García Sancho A.Chiva G.Sanz-Cervera JF.del Pozo C.Aceña JL. J. Org. Chem. 2006, 71: 3299 -
10c
Grecian SA.Hadida S.Warren SD. Tetrahedron Lett. 2005, 46: 4683 -
10d
Bottaro JC.Penwell PE.Schmitt RJ. J. Am. Chem. Soc. 1997, 119: 9405 -
10e
Varaprasad CVNS.Johnson F. Tetrahedron Lett. 2005, 46: 2163 -
10f
Thakkalapally A.Benin V. Tetrahedron 2005, 61: 4939 - For a review concerning the 2-(trimethylsilyl)ethyl group in synthesis, see:
-
11a
Chambert S.Désiré J.Décout J.-L. Synthesis 2002, 2319 - See also for deprotection of sulfides:
-
11b
Flatt AK.Dirk SM.Henderson JC.Shen DE.Su J.Reed MA.Tour JM. Tetrahedron 2003, 59: 8555 -
11c
Chatterji T.Kizil M.Keerthi K.Chowdhury G.Pospísil T.Gates KS. J. Am. Chem. Soc. 2003, 125: 4996 -
11d
Hamm ML.Cholera R.Hoey CL.Gill TJ. Org. Lett. 2004, 6: 3817 -
11e
Pollack SK.Naciri J.Mastrangelo J.Patterson CH.Torres J.Moore M.Shashidhar R.Kushmerick JG. Langmuir 2004, 20: 1838 -
11f
Morales GM.Jiang P.Yuan S.Lee Y.Sanchez A.You W.Yu L. J. Am. Chem. Soc. 2005, 127: 10456 - For deprotection of sulfones:
-
11g
Lai M.-t.Oh E.Shih Y.Liu H.-w. J. Org. Chem. 1992, 57: 2471 -
11h
Palmer JT.Fuchs PL. Synth. Commun. 1988, 18: 233 - For deprotection of selenothioic acid S-esters:
-
11i
Murai T.Kamoto T.Kato S. J. Am. Chem. Soc. 2000, 122: 9850 -
11j
Niyomura O.Sakai K.Murai T.Kato S.Yamaguchi S.Tamao K. Chem. Lett. 2001, 968 -
11k
Kimura T.Murai T.Miwa A.Kurachi D.Yoshikawa H.Kato S. J. Org. Chem. 2005, 70: 5611 - For deprotection of phosphinoselenothioic acid S-esters:
-
11l
Kimura T.Murai T. Chem. Commun. 2005, 4077 -
12a
Bernhard W.Fleming I. J. Organomet. Chem. 1984, 271: 281 -
12b
Jones SL.Stirling CJM. J. Chem. Soc., Chem. Commun. 1988, 1153 - 13
Wagner M.Kunz H. Synlett 2000, 400 -
14a
Gornowicz GA.Ryan JW.Speier JL. J. Org. Chem. 1968, 33: 2918 -
14b
Mahadevan A.Li C.Fuchs PL. Synth. Commun. 1994, 24: 3099 -
14c
Menichetti S.Stirling CJM. J. Chem. Soc., Perkin Trans. 1 1996, 1511 -
15a
Bégué J.-P.Bonnet-Delpon D.Crousse B. Synlett 2004, 18 -
15b
Ravikumar KS.Kesavan V.Crousse B.Bonnet-Delpon D.Bégué J.-P. Org. Synth. Vol. 80: John Wiley & Sons; London: 2003. p.184 - 17 Silicon contains 4.7% 29Si isotope with nuclear spin I = and a gyromagnetic ratio γ = -(2π)8.46 × 106 s-1 T-1, see for example:
Fortis F.Barbe B.Pétraud M.Picard J.-P. Chem. Commun. 1999, 527 - 20 An intramolecular coordination between the oxygen atom of the sulfoxide group and the silicon center was previously detected at low temperature with the analogous electron deficient trifluorosilyl derivatives:
Pestunovich VA.Larin MF.Sorokin MS.Albanov AI.Voronkov MG. J. Organomet. Chem. 1985, 280: C17 - 21 Similar structural effects involving the 2-(trimethyl-silyl)ethyl system have already been mentioned with carboxylate and sulfenate esters:
Green AJ.Issa W.White JM. Aust. J. Chem. 1997, 50: 927 - 22 See for example:
Akazome M.Noguchi M.Tanaka O.Sumikawa A.Uchida T.Ogura K. Tetrahedron 1997, 53: 8315 -
23a
Hogg DR.Robertson A. J. Chem. Soc., Perkin Trans. 1 1979, 1125 -
23b
Kobayashi M.Toriyabe K. Sulfur Lett. 1985, 3: 117 - 25
Touaibia M.Desjardins M.-A.Provençal A.Audet D.Médard C.Morin M.Breau L. Synthesis 2004, 2283 -
26a
Lipshutz BM.Pegram JJ. Tetrahedron Lett. 1980, 21: 3343 -
26b
Edwards MP.Doherty AM.Ley SV.Organ HM. Tetrahedron 1986, 42: 3723 - A similar reluctance towards fluoridolysis was also observed with the analogous isopropyl derivative and also in the sulfide series:
-
28a
Anderson MB.Ranasinghe MG.Palmer JT.Fuchs PL. J. Org. Chem. 1988, 53: 3125 -
28b
Grundberg H.Andergran M.Nilsson UJ. Tetrahedron Lett. 1999, 40: 1811 - 29
Kofron WG.Baclawski LM. J. Org. Chem. 1976, 41: 1879 - 30
Yu CJ.Chong Y.Kayyem JF.Gozin M. J. Org. Chem. 1999, 64: 2070 - 31
Kim YH.Yoon CD. Synth. Commun. 1989, 19: 1569 - 32
Seago A.Houghton J.McCague R.Foster AB.Coe PL.Falshaw A. Biochem. Pharmacol. 1987, 36: 400 - 33
Guo Y.Darmanyan AP.Jenks WS. Tetrahedron Lett. 1997, 38: 8619 - 34
Shaw E.Bernstein J.Losee K.Lott WA. J. Am. Chem. Soc. 1950, 72: 4362 - 35
Schwan AL.Lear Y. Sulfur Lett. 2000, 23: 111
References
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.
18Similar chemical shifts were observed either in CDCl3 or THF-d 8.
19Crystal 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.
24Spectral data are in agreement with those previously reported by us.6a
27The reaction was carried out with a mixture of both Z- and E-isomers but also the geometrically pure substrates.