Download PDF
Synlett 2004(15): 2756-2760  
DOI: 10.1055/s-2004-835644
LETTER
© Georg Thieme Verlag Stuttgart · New York

The Three-Component Joining Reaction of Primary Amines, Electron-Deficient Olefins, and α-Halogen-Substituted Allylsilanes Catalyzed by Copper(I) Chloride

Makoto Kozuka*, Akihiko Inoue, Teruko Tsuchida, Michiharu Mitani*
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;
Further Information

Publication History

Received 30 August 2004
Publication Date:
08 November 2004 (online)

    Permissions and Reprints All articles of this category

Abstract

Tertiary amines with three different substituents were straightforwardly obtained by the copper(I) chloride-catalyzed ­reaction of α-halogen substituted allylsilanes, electron-deficient olefins, and primary amines. This reaction was more effectively performed by the addition of chloroacetone to the reaction system.

Key words

amines - silicon - copper catalysis - C-N coupling - three-component coupling

9

General Procedure for the Three-Component Joining Reaction of Amines with α-Chlorine-Substituted Allylsilanes and Electron-Eeficient Olefins: To an amine (10 mmol) in a flask were added CuCl (0.02 g, 0.2 mmol) and t-BuOH (3 mL). This mixture was treated with ultrasonic wave irradiation until the mixture becomes transparent. Then, a t-BuOH (2 mL) solution containing (1-chloro-2-propenyl)trimethylsilane (1b, 0.386 g, 2 mmol), an electron-deficient olefin (3 mmol), and chloroacetone (0.37 g, 4 mmol) were further added. The resulting solution was stirred under reflux. The reaction mixture was then poured into H2O and extracted with Et2O. The solvent was evaporated under reduced pressure, and then the product was isolated from the residue by preparative GC or TLC. Compound 3a: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 0.06 (s, 9 H, SiMe3), 2.11 (s, 1 H, OH), 2.41 (t, J = 7.19 Hz, 2 H, CH2CN), 2.69 (t, J = 5.40 Hz, 2 H, HOCH2CH2), 2.77 (t, J = 7.19 Hz, 2 H, CNCH2CH2), 3.15 (d, J = 5.60, 2 H, CH2C=C), 3.53 (t, J = 5.40 Hz, 2 H, HOCH2), 5.81 (d, J = 18.38, 1 H, C=CHSiMe3), 5.93 (dt, 2 J = 18.38, 3 J = 5.60, 1 H, CH2CH=C). 13C NMR (100 MHz, CDCl3): δ = 142.1, 134.8, 117.0, 59.3, 59.0, 55.6, 49.4, 16.7, -1.2. IR (neat): 3439, 2249 cm-1. MS (70 eV): m/z (%) = 226 (5) [M+], 195 (72), 113 (78), 85 (68), 73 (52), 59 (100). HRMS: m/z calcd for C11H22N2OSi: 226.1500. Found: 226.1518.