Synlett 2004(7): 1227-1230  
DOI: 10.1055/s-2004-825579
LETTER
© Georg Thieme Verlag Stuttgart · New York

Preparation of Vinylsilanes through the Reaction of Polyhalides with α-Halogen Substituted Allylsilanes Catalyzed by Copper(I) Chloride

Michiharu Mitani*, Masayuki Masuda, Akihiko Inoue
Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano 380-8553, Japan
Fax: +81(26)2695424; e-Mail: mitanim@gipwc.shinshu-u.ac.jp;
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Publikationsverlauf

Received 13 January 2004
Publikationsdatum:
10. Mai 2004 (online)

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.

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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.