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

Michiharu Mitani; Masayuki Masuda; Akihiko Inoue

doi:10.1055/s-2004-825579

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Synlett 2004(7): 1227-1230
DOI: 10.1055/s-2004-825579

LETTER

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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Publication History

Received 13 January 2004
Publication Date:
10 May 2004 (online)

Abstract
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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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12

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 ₂CH=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.