Sonogashira Reaction of Aryl Halides with Terminal Alkynes Catalyzed by Cobalt Hollow Nanospheres

Abstract

Sonogashira reaction catalyzed by cobalt hollow nanospheres has been developed. Coupling of alkynes with aryl iodide or aryl bromide in the presence of potassium carbonate, triphen­ylphosphine, and cuprous iodide provides the corresponding products with moderate to good yields, which reveals obvious advantages such as low-cost catalyst, the recyclability of the catalyst, and simple experimental operation.

cobalt hollow nanospheres - catalysis - Sonogashira reaction - cross-coupling - alkynes

References and Notes

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<A NAME="RW01008ST-15">15</A>

Typical Experimental Procedure To NMP (2 mL) were added aryl halide (1 mmol) and terminal alkyne (1 mmol), then cobalt nanoparticles (0.03 mmol, 3 mol%), Ph₃P (0.1 mmol, 10 mol%), CuI (0.02 mmol, 2 mol%), and K₂CO₃ (1.5 mmol) were added in turn. The mixture was heated at 120 °C (for aromatic alkyne) or 80 °C (for aliphatic alkyne) with stirring under a nitrogen atmosphere for the appropriate time (see Table [1] , monitored by TLC) until the reaction was complete, then centrifuged. The solution was separated and the precipitate was washed with Et₂O (3 × 5 mL). The solutions were combined and washed with H₂O, dried over anhyd Na₂SO₄, and purified by column chromatography on SiO₂ with hexane-EtOAc (100:1) as eluent to yield the products. The precipitate was further washed sufficiently with MeOH and Et₂O, then dried, and the cobalt nanoparticles were recovered. After being reused three times, the yield of the product did not obviously decrease.
1-Methyl-4-phenylethynylbenzene: mp 71 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.53-7.56 (m, 2 H), 7.45 (d, J = 8.0 Hz, 2 H), 7.35-7.38 (m, 3 H), 7.18 (d, J = 8.0 Hz, 2 H), 2.39 (s, 3 H). IR (KBr): ν = 3018, 2235, 1630, 1547 cm^-1. MS: m/z (%) = 192 (100) [M⁺], 101 (32).
Hex-1-ynyl-benzene: light yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.42 (d, J = 8.0 Hz, 2 H), 7.28-7.32 (m, 3 H), 2.41 (t, J = 6.9 Hz, 2 H), 1.47-1.62 (m, 4 H), 0.95 (t, J = 6.9 Hz, 3 H). IR (neat): ν = 3025, 2988, 2225, 1620, 1526 cm^-1. MS: m/z (%) = 158 (27) [M⁺], 115 (100), 129 (59), 143 (44).