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

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.

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

References

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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.

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