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.

Key words

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

References and Notes

• 1a Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  16:  4467 
• 1b Sonogashira K. Yatake T. Tohda Y. Takahashi S. Hagihara N. J. Chem. Soc., Chem. Commun.  1977,  291 
• 1c Sonogashira K. In Metal-Catalyzed Cross-Coupling Reactions   Stang PJ. Diederich F. Wiley-VCH; Weinheim: 1998.  p.203 
• 1d Sonogashira K. In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pergamon Press; New York: 1991.  p.521 
• 1e Rafael Chinchilla R. Nájera C. Chem. Rev.  2007,  107:  874 
• 1f Wang YF. Deng W. Liu L. Guo QX. Chin. J. Org. Chem.  2005,  25:  8 
• 2a Brandsma L. Synthesis of Acetylenes, Allenes and Cumulenes: Methods and Techniques   Elsevier; Oxford: 2004.  p.293 
• 2b Sonogashira K. In Metal-Catalyzed Cross-Coupling Reactions   Vol. 1:  Diederich F. de Meijere A. Wiley-VCH; Weinheim: 2004.  p.319 
• 2c Tykwinski RR. Angew. Chem. Int. Ed.  2003,  42:  1566 
• 2d Negishi E. Anastasia L. Chem. Rev.  2003,  103:  1979 
• 2e Díaz-Sanchez BR. Iglesias-Arteaga MA. Melgar-Fernandez R. Juaristi E. J. Org. Chem.  2007,  72:  4822 
• 2f Sasabe H. Inomoto N. Kihara N. Suzuki Y. Ogawa A. Takata T. J. Polym. Sci., Part A: Polym. Chem.  2007,  45:  4154 
• 3a Buchmeiser MR. Wurst K. J. Am. Chem. Soc.  1999,  121:  11101 
• 3b Gil-Moltó J. Karlstrom S. Nájera C. Tetrahedron  2005,  61:  12168 
• 3c Gronnow MJ. Luque R. Macquarrie DJ. Clark JH. Green Chem.  2005,  7:  552 
• 3d Li P. Wang L. Adv. Synth. Catal.  2006,  348:  681 
• 4 Arques A. Aunon D. Molina P. Tetrahedron Lett.  2004,  45:  4337 
• 5 Nishide K. Liang H. Ito S. Yoshifuji M. J. Organomet. Chem.  2005,  690:  4809 
• 6a Herrmann WA. Angew. Chem. Int. Ed.  2002,  41:  1290 
• 6b Peris E. Crabtree RH. Coord. Chem. Rev.  2004,  248:  2239 
• 6c Crudden CM. Allen DP. Coord. Chem. Rev.  2004,  248:  2247 
• 6d Gholap AR. Venkatesan K. Pasricha R. Daniel T. Lahoti RJ. Srinivasan KV. J. Org. Chem.  2005,  70:  4869 
• 6e Dhudshia B. Thadani AN. Chem. Commun.  2006,  668 
• 6f Kim JH. Lee DH. Jun BH. Lee YS. Tetrahedron Lett.  2007,  48:  7079 
• 7a Moreno-Mañas M. Pleixats R. Acc. Chem. Res.  2003,  36:  638 
• 7b Thathagar MB. ten Elshof JE. Rothenberg G. Angew. Chem. Int. Ed.  2006,  45:  2886 
• 8 Caló V. Nacci A. Monopoli A. Montingelli F. J. Org. Chem.  2005,  70:  6040 
• 9 Son SU. Jang Y. Park J. Na HB. Park HM. Yun HJ. Lee J. Hyeon T. J. Am. Chem. Soc.  2004,  126:  5026 
• 10 Li Y. Zhou P. Dai Z. Hu Z. Sun P. Bao J. New J. Chem.  2006,  30:  832 
• 11a Beletskaya IP. Latyshev GV. Tsvetkov AV. Lukashev NV. Tetrahedron Lett.  2003,  44:  5011 
• 11b Wang L. Li P. Zhang Y. Chem. Commun.  2004,  514 
• 12 Zhou P. Li Y. Sun P. Zhou J. Bao J. Chem. Commun.  2007,  1418 
• 13 Thorand S. Krause N. J. Org. Chem.  1998,  63:  8551 
• 14 Siemsen P. Livingston RC. Diederich F. Angew. Chem. Int. Ed.  2000,  39:  2632 

15

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).