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DOI: 10.1055/s-2004-825579
Preparation of Vinylsilanes through the Reaction of Polyhalides with α-Halogen Substituted Allylsilanes Catalyzed by Copper(I) Chloride
Publikationsverlauf
Publikationsdatum:
10. Mai 2004 (online)
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Abstract
(1-Halo-2-propenyl)trimethylsilanes underwent the addition of polyhalides or α-haloesters under catalysis by the copper(I) ethanolamine or N,N,N′,N′-tetramethylethylenediamine complex to bring about vinylsilane derivatives through dehalogenation accompanying the migration of the carbon-carbon double bond.
Key words
addition reaction - silicon - copper catalysis - dehalogenation - carbon-carbon double bond
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1a
Hosomi A.Sakurai H. Tetrahedron Lett. 1976, 1295 -
1b
Hosomi A.Sakurai H. J. Am. Chem. Soc. 1977, 99: 1673 -
1c
Pillot JP.Dunogues J.Calas R. Tetrahedron Lett. 1976, 1871 -
1d
Hosomi A.Endo M.Sakurai H. Chem. Lett. 1976, 941 -
1e
Fleming I.Paterson I. Synthesis 1979, 446 -
1f
Sasaki T.Usuki A.Ohno M. Tetrahedron Lett. 1978, 4925 - 2
Sakurai H.Hosomi A.Kumada M. J. Org. Chem. 1969, 34: 1764 - 3
Kosugi M.Kurata H.Kawata K.Migita T. Chem. Lett. 1991, 1327 -
4a
Burton DJ.Kehoe LJ. J. Org. Chem. 1971, 36: 2596 -
4b
Iqbal J.Bhatia B.Nayyar NK. Chem. Rev. 1994, 94: 519 -
4c
Giese B.Kopping B.Göbel T.Dickhault J.Thoma G.Kulicke KJ.Trach F. Org. React. 1996, 48: 301 - 5
Mitani M.Hujita S. Bull. Chem. Soc. Jpn. 1997, 70: 3055 -
6a
Colvin EW. Silicon Reagents in Organic Synthesis Academic Press; London: 1988. p.14 -
6b
Fleming I.Dunogués J.Smithers R. Org. React. 1989, 37: 57 -
6c
Chan TH.Fleming I. Synthesis 1979, 761 -
6d
Fleming I.Barbero A.Walter D. Chem. Rev. 1997, 97: 2063 -
6e
Parnes ZN.Bolestova GI. Synthesis 1984, 991 -
7a
Chan TH.Lau PWK.Mychajlowskij W. Tetrahedron Lett. 1977, 3317 -
7b
Fleming I.Peace A. J. Chem. Soc., Perkin Trans. 1 1980, 2485 -
7c
Nakanishi S.Kumeta K.Takata T. Inorg. Chim. Acta 1999, 29: 231 -
8a
Seyferth D.Wursthorn KR.Mammarella RE. J. Org. Chem. 1977, 42: 3104 -
8b
Fleming I.Newton TW. J. Chem. Soc., Perkin Trans. 1 1984, 1805 -
8c
Na Y.Chang S. Org. Lett. 2000, 2: 1887 -
8d
Sudo T.Asao N.Yamamoto Y. J. Org. Chem. 2000, 65: 8919 -
9a
Chan TH.Baldassave A.Massuda D. Synthesis 1976, 801 -
9b
Taylor RT.Degenhardt CR.Melega WP.Paquette LA. Tetrahedron Lett. 1977, 159 -
9c
Chamberin AR.Stemke JF.Bond FT. J. Org. Chem. 1978, 43: 147 -
9d
Barluenga J.Fernandez-Simon JL.Concellon JM.Yus M. Synthesis 1988, 234 -
9e
Petasis NA.Akritopoulou I. Synlett 1992, 665 -
9f
Itami K.Nokami T.Yoshida J. Tetrahedron 2001, 57: 5045 -
10a
Neumann H.Seebach D. Chem. Ber. 1978, 111: 2785 -
10b
Hudrlik PF.Kulkarni AK.Jain S.Hudrlik AM. Tetrahedron 1983, 39: 877 - 11
Hosomi A.Ando M.Sakurai H. Chem. Lett. 1984, 1385 - 13
Murai T.Yamamoto M.Kondo S.Kato S. J. Org. Chem. 1993, 58: 7440 - 14
Udding JH.Tuijp KCJM.van Zanden MN.Hiemsta H.Speckamp WN. J. Org. Chem. 1994, 59: 1993 - 15
Kharasch MS.Jensen EV.Urry WH. J. Am. Chem. Soc. 1947, 69: 1100 - 16
Sakurai H.Hosomi A.Kumada M. J. Org. Chem. 1969, 34: 1764
References
General Procedure for the Reaction of α-Halogen Substituted Allylsilanes with Polyhalides: A solution comprising (1-bromo-2-propenyl)trimethylsilane (1b, 0.386 g, 2 mmol), a polyhalide (4 mmol), 2-aminoethanol (0.611 g, 10 mmol), CuCl (0.02 g, 0.2 mmol), and t-BuOH (5 mL) was stirred under reflux. The reaction mixture was then poured into H2O and extracted with Et2O. After the solvent was evaporated under reduced pressure, the product was isolated from the residue by preparative GC or column chromatography on silica gel. Compound 2a: a colorless oil. IR (neat): 3082, 1624 cm-1. 1H NMR (400 MHz, CDCl3): δ = 6.08 (dt, J = 18.6, J = 6.0, 1 H, CH2-CH=CH), 5.96 (d, J = 18.6, 1 H, CH=CH-SiMe3), 3.42 (d, J = 6.0 Hz, 2 H, CH 2 CH=CH), -0.08 (s, 9 H, SiMe 3 ). 13C NMR (100 MHz, CDCl3): δ = 138.90, 136.64, 76.48, 61.05, -1.48. MS (EI): m/z (%) = 232 (0.1) [M + 2]+, 230 (0.1) [M+], 217 (9), 215 (9), 181 (9), 179 (9), 113 (79), 95 (90), 93 (100), 73 (91). HRMS: m/z calcd for C6H10Cl3Si (M - CH3): 214.9616; found: 214.9622.