A simple and efficient Suzuki reaction catalyzed by palladium-modified nanopore silica under solvent-free conditions

Wonghil Chang; Jihye Shin; Yunghee Oh; Byoung Joon Ahn

Journal of Industrial and Engineering Chemistry, Vol.14, No.4, 423-428, July, 2008

DOI10.1016/j.jiec.2008.02.004 Export Citation

A simple and efficient Suzuki reaction catalyzed by palladium-modified nanopore silica under solvent-free conditions

Wonghil Chang^†, Jihye Shin, Yunghee Oh¹, and Byoung Joon Ahn^{2, †}

Department of Herbal Cosmetology and Chemistry, and Research Institute of Health Science, Jeonju University, Jeonju 560-759, Republic of Korea
¹Department of Chemistry, Dongeui University, Busan 614-714, Republic of Korea
²Department of Chemistry Education, Institute of fusion science, Institute of Science Education, Chonbuk National University, Chonju 561-756, Republic of Korea

E-mail:,

In this paper our recent results of the Suzuki reaction using [Pd(NH3)4]2+ -modified nanopore silica under solvent-free conditions are described. [Pd(NH3)4]2+ -modified nanopore silica was prepared by impregnation using an aqueous solution of [Pd(NH3)4]Cl2 in water or in acetonitrile. The BET surface area, BJH mean pore diameter and pore volume are 138.8 m2/g, 8.7 nm, and 0.34 cm3/g, respectively, and the pore size distribution shows a single peak at around 5 nm in diameter. It has been shown that the Suzuki reaction is performed in excellent yield by using Pd-modified nanopore silica under solvent-free conditions heated at 90.100 8C for 3.5 h. It has been found that aryl bromides can be coupled with aryl boronic acids in excellent yield under solvent-free condition. Phenyl iodide was also coupled with phenyl boronic acids in excellent yield, whereas phenyl chloride gave product in poor yield. And KF, CsF or Bu4NF were also found to be a convenient base additive.

Keywords:Suzuki reaction;Heterogeneous catalyst;Pd-modified;Nanopore silica;Solvent-free conditions

[References]

Miyaura N, Suzuki A, Chem. Rev., 95(7), 2457 (1995)
Suzuki A, J. Organomet. Chem., 576, 147 (1999)
Kotha S, Lahiri K, Kashinath D, Tetrahedron, 58, 9633 (2002)
Ruiz JR, Jimenez-Sanchidrian C, Mora M, Tetrahedron, 62, 2922 (2006)
Cepanec I, Synthesis of Biaryls, Elsevier, Amsterdam, 2004
Miyaura N, Yanagi T, Suzuki A, Synth. Commun., 11, 513 (1985)
Chanthavong F, Leadbeatert NE, Tetrahedron Lett., 47, 1909 (2006)
Artok L, Bulut H, Tetrahedron Lett., 45, 3881 (2004)
de Meijere A, Diederich F (Eds.), Metal-Catalyzed Cross-Coupling Reactions, 2nd ed., Wiley-VCH, Weinheim, 2004
Bork JT, Lee JW, Chang YT, Tetrahedron Lett., 44, 6141 (2003)
Augustine RL, Heterogeneous Catalysis for the Synthetic Chemist, Marcel Dekker, New York, 1996
Chang W, Ahn BJ, Int. J. Nanotechnol., 2, 186 (2006)
Kim JG, Lee JH, Kim IT, Kim EH, J. Ind. Eng. Chem., 13(2), 292 (2007)
Ku HJ, Ahn BJ, Jeon BE, Chang W, J. Ind. Eng. Chem., 11(6), 841 (2005)
Gruber M, Chouzier S, Koehler K, Djakovitch L, Appl. Catal. A: Gen., 265(2), 161 (2004)
Bai L, Xian J, Zhang Y, Green Chem., 5, 615 (2003)
Rajagopal R, Jarikore DV, Srinivasan KV, Chem. Commun. (2002) 616
Mathews CJ, Smith PJ, Welton T, Chem. Commun. (2000) 1249
Gordon RS, Holmes AB, Chem. Commun. (2002) 640
Early TR, Gordon RS, Carroll MA, Holmes AB, Shute RE, McConvey IF, Chem. Commun. (2001) 1966
Blettner CG, Konig WA, Stenzel W, Schotten T, J. Org. Chem., 64, 3885 (1999)
Chanthavong F, Leadbeater NE, Tetrahedron Lett., 47, 1909 (2006)
Arvela RK, Leadbeater NE, Mack TL, Kormos CM, Tetrahedron Lett., 47, 217 (2006)
Doxsee KM, Hutchinson JE, Green Organic Chemistry, Brooks Cole, Singapore, 2004
Chang W, Shin J, Kim M, Ahn BJ, J. Ind. Eng. Chem., 7(1), 62 (2001)
Chang W, Shin J, Song JE, Ahn BJ, J. Korean Ind. Eng. Chem., 15(1), 146 (2004)
Wang HP, Lin KS, Huang YJ, Li MC, Tsaur LK, J. Hazard. Mater., 58, 147 (1998)
Han CS, Lee HY, Roh Y, Int. J. Nanotechnol. 2006 (2) (2006) 236
Han CS, Lee HY, Chon H, Proc. Ann. Meeting NanoSci. Technol. (2004) 185
Han CS, Lee HY, Kim MH, Mo HR, Lim MO, Kim JH, Lim EJ, Jung DY, Proc. Ann. Meeting Nanosci. Technol. (2004) 151
Ahn BJ, Gang MS, Chae K, Oh Y, Shin J, Chang W, J. Ind. Eng. Chem., 14, 000 (2008)
Chon H, Chon MJ, Han CS, Korean Patent 0396457 (2003)
Bulut H, Artok L, Yilmaz S, Tetrahedron Lett., 44, 289 (2003)
Djakovitch L, Koehler K, J. Mol. Catal. A: Chem., 142, 275 (1999)
Tanaka K, Solvent-free Organic Synthesis, Wiley-VCH, Weinheim, 2003
Wolfe JP, Buchwald SL(Eds.), Angew. Chem. Int., 38, 2413 (1999)
Wolfe JP, Singer RA, Yang BH, Buchwald SL, J. Am. Chem. Soc., 121(41), 9550 (1999)
Namboodiri VV, Varma RS, Green Chem., 3, 146 (2001)

[Referenced By]

[1] Miyaura N, Suzuki A, Chem. Rev., 95(7), 2457 (1995)

[2] Suzuki A, J. Organomet. Chem., 576, 147 (1999)

[3] Kotha S, Lahiri K, Kashinath D, Tetrahedron, 58, 9633 (2002)

[4] Ruiz JR, Jimenez-Sanchidrian C, Mora M, Tetrahedron, 62, 2922 (2006)

[5] Cepanec I, Synthesis of Biaryls, Elsevier, Amsterdam, 2004

[6] Miyaura N, Yanagi T, Suzuki A, Synth. Commun., 11, 513 (1985)

[7] Chanthavong F, Leadbeatert NE, Tetrahedron Lett., 47, 1909 (2006)

[8] Artok L, Bulut H, Tetrahedron Lett., 45, 3881 (2004)

[9] de Meijere A, Diederich F (Eds.), Metal-Catalyzed Cross-Coupling Reactions, 2nd ed., Wiley-VCH, Weinheim, 2004

[10] Bork JT, Lee JW, Chang YT, Tetrahedron Lett., 44, 6141 (2003)

[11] Augustine RL, Heterogeneous Catalysis for the Synthetic Chemist, Marcel Dekker, New York, 1996

[12] Chang W, Ahn BJ, Int. J. Nanotechnol., 2, 186 (2006)

[13] Kim JG, Lee JH, Kim IT, Kim EH, J. Ind. Eng. Chem., 13(2), 292 (2007)

[14] Ku HJ, Ahn BJ, Jeon BE, Chang W, J. Ind. Eng. Chem., 11(6), 841 (2005)

[15] Gruber M, Chouzier S, Koehler K, Djakovitch L, Appl. Catal. A: Gen., 265(2), 161 (2004)

[16] Bai L, Xian J, Zhang Y, Green Chem., 5, 615 (2003)

[17] Rajagopal R, Jarikore DV, Srinivasan KV, Chem. Commun. (2002) 616

[18] Mathews CJ, Smith PJ, Welton T, Chem. Commun. (2000) 1249

[19] Gordon RS, Holmes AB, Chem. Commun. (2002) 640

[20] Early TR, Gordon RS, Carroll MA, Holmes AB, Shute RE, McConvey IF, Chem. Commun. (2001) 1966

[21] Blettner CG, Konig WA, Stenzel W, Schotten T, J. Org. Chem., 64, 3885 (1999)

[22] Chanthavong F, Leadbeater NE, Tetrahedron Lett., 47, 1909 (2006)

[23] Arvela RK, Leadbeater NE, Mack TL, Kormos CM, Tetrahedron Lett., 47, 217 (2006)

[24] Doxsee KM, Hutchinson JE, Green Organic Chemistry, Brooks Cole, Singapore, 2004

[25] Chang W, Shin J, Kim M, Ahn BJ, J. Ind. Eng. Chem., 7(1), 62 (2001)

[26] Chang W, Shin J, Song JE, Ahn BJ, J. Korean Ind. Eng. Chem., 15(1), 146 (2004)

[27] Wang HP, Lin KS, Huang YJ, Li MC, Tsaur LK, J. Hazard. Mater., 58, 147 (1998)

[28] Han CS, Lee HY, Roh Y, Int. J. Nanotechnol. 2006 (2) (2006) 236

[29] Han CS, Lee HY, Chon H, Proc. Ann. Meeting NanoSci. Technol. (2004) 185

[30] Han CS, Lee HY, Kim MH, Mo HR, Lim MO, Kim JH, Lim EJ, Jung DY, Proc. Ann. Meeting Nanosci. Technol. (2004) 151

[31] Ahn BJ, Gang MS, Chae K, Oh Y, Shin J, Chang W, J. Ind. Eng. Chem., 14, 000 (2008)

[32] Chon H, Chon MJ, Han CS, Korean Patent 0396457 (2003)

[33] Bulut H, Artok L, Yilmaz S, Tetrahedron Lett., 44, 289 (2003)

[34] Djakovitch L, Koehler K, J. Mol. Catal. A: Chem., 142, 275 (1999)

[35] Tanaka K, Solvent-free Organic Synthesis, Wiley-VCH, Weinheim, 2003

[36] Wolfe JP, Buchwald SL(Eds.), Angew. Chem. Int., 38, 2413 (1999)

[37] Wolfe JP, Singer RA, Yang BH, Buchwald SL, J. Am. Chem. Soc., 121(41), 9550 (1999)

[38] Namboodiri VV, Varma RS, Green Chem., 3, 146 (2001)