0.22 mmol/g was measured by inductively coupled plasma (ICP)
analysis.
Angew. Chem., Int. Ed., 2001, 40, 4544–4568; (c) S. Kotha, K. Lahiri
and D. Kashinath, Tetrahedron, 2002, 58, 9633–9695; (d) K. C.
Nicolaou, P. G. Bulger and D. Sarlah, Angew. Chem., Int. Ed, 2005,
44, 4442–4489; (e) M. G. Banwell, T. E. Goodwin, S. Ng, J. A. Smith
and D. J. Wong, Eur. J. Org. Chem., 2006, 3043–3060; (f) N. T. S.
Phan, M. V. D. Sluys and C. W. Jones, Adv. Synth. Catal., 2006,
348, 609–679; (g) S. Kotha and K. Lahiri, Eur. J. Org. Chem., 2007,
1221–1236.
2 (a) J. P. Wolfe, R. A. Singer, B. H. Yang and S. L. Buchwald, J. Am.
Chem. Soc., 1999, 121, 9550–9561; (b) A. D. Littke, C. Dai and
G. C. Fu, J. Am. Chem. Soc., 2000, 122, 4020–4028; (c) M. R.
Netherton, C. Dai, K. Neuschutz and G. C. Fu, J. Am. Chem. Soc.,
2001, 123, 10099–10100; (d) J. Yin, M. P. Rainka, X.-X. Zhang and
S. L. Buchwald, J. Am. Chem. Soc., 2002, 24, 1162–1163; (e) R. B.
Bedford, C. S. J. Cazin and S. L. Hazelwood, Angew. Chem., Int.
Ed., 2002, 41, 4120–4122; (f) F Churruca, R SanMartin, B Ine´s,
I Tellitu and E Dom´ınguez, Adv. Synth. Catal., 2006, 348, 1836–
1840.
General procedure for heterogeneous Suzuki reaction
Aryl halide (1.0 mmol), phenylboronic acid (134 mg, 1.1 mmol),
K3PO4 (424 mg, 2.0 mmol), TBAB (129 mg, 0.4 mmol),
dodecane (40 mg, internal standard) and catalyst 2 (13.5 mg,
0.22 mmol/g, 0.3 mol%) were mixed in H2O (3.0 mL). The
mixture was stirred at 65 ◦C in an air atmosphere. The crude
was analysed by GC/GC-MS. The reaction mixture was filtered
and washed with H2O and Et2O. The organic phase was
separated and dried over MgSO4, and the solvent was evaporated
under reduced pressure. The product was purified by column
chromatography on silica gel.
3 For reviews, see: (a) N. E. Leadbeater and M. Marco, Chem. Rev.,
2002, 102, 3217–3274; (b) L. Yin and J. Liebscher, Chem. Rev., 2007,
107, 133–173.
The reuse of MFI zeolite-supported catalyst 2
4 (a) L. Djakovitch and K. Koehler, J. Am. Chem. Soc., 2001, 123,
5990–5999; (b) Y. M. A. Yoichi, K. Takeda, H. Takahashi and S.
Ikegami, Org. Lett., 2002, 20, 3371–3374; (c) S. Paul and J. H. Clark,
Green Chem., 2003, 5, 635–638; (d) A. Corma, H. Carcia, A. Leiva
and A. Primo, Appl. Catal. A: Gen., 2003, 247, 41–49; (e) A. Corma,
H. Garcia, A. Leiva and A. Primo, Appl. Catal. A: Gen., 2004, 257,
77–83; (f) J. J. E. Hardy, S. Hubert, D. J. Macquarrie and A. J. Wilson,
Green Chem., 2004, 6, 53–56.
5 (a) P. Wasserscheid and W. Keim, Angew. Chem., Int. Ed., 2000,
39, 3772–3789; (b) J. Dupont, R. F. de Souza and P. A. Z. Suarez,
Chem. Rev., 2002, 102, 3667–3691; (c) N. Jain, A. Kumar, S. Chauhan
and S. M. S. Chauhan, Tetrahedron, 2005, 61, 1015–1060; (d) T.
Akiyama, A. Suzuki and K. Fuchibe, Synlett, 2005, 1024–1026;
(e) B. C. Ranu, S. Banerjee and R. Jana, Tetrahedron, 2007, 63, 776–
782.
In the recycling experiment, the reaction was performed by
using a mixture of aryl halide (1.0 mmol), phenylboronic acid
(134 mg, 1.1 mmol), K3PO4 (424 mg, 2.0 mmol), TBAB (129 mg,
0.4 mmol) and catalyst 2 (13.5 mg, 0.3 mol%) in H2O (3.0 mL)
at 65 ◦C for 0.5 h. After completion of the reaction, the catalyst
in the reaction mixture was separated from the solution by a
centrifuge. The solution was worked up as described above. The
separated catalyst was successively reused for the next reaction
without any pretreatment.
Conclusions
6 (a) C. P. Mehnert, R. A. Cook, N. C. Dispenziere and M. Afeworki,
J. Am. Chem. Soc., 2002, 124, 12932–129336; (b) S. Breitenlechner,
M. Fleck, T. E. Mu¨ller and A. Suppan, J. Mol. Catal. A, 2004, 214,
175–179; (c) C. P. Mehnert, Chem. Eur. J., 2005, 11, 50–56; (d) H.
Hagiwara, K. H. Ko, T. Hoshi and T. Suzuki, Chem. Commun., 2007,
2238–2840.
7 M. Choi, H. S. Cho, R. Srivastava, C. Venkatesan, D.-H. Choi and
R. Ryoo, Nat. Mater., 2006, 5, 718–723.
8 D.-H. Lee, M. Choi, B.-W. Yu and R. Ryoo, Chem. Commun., 2009,
74–76.
In conclusion, hierarchical MFI zeolite was used as a support for
immobilization of Pd(OAc)2-ionic liquid matrix. In this work,
ionic liquid fragments were anchored on the mesopore walls
of the zeolite. An ionic liquid phase with Pd(OAc)2 was then
immobilized into the covalently grafted ionic liquid framework.
The resulting catalyst exhibited excellent catalytic activity and
high stability for Suzuki coupling reactions in water. This
catalyst was recycled four times without a significant loss in
the catalytic activity. Hierarchical MFI zeolite was proven to be
a promising support for the supported ionic liquid catalysis.
9 V. N. Shetti, J. Kim, R. Srivastava, M. Choi and R. Ryoo, J. Catal,
2008, 254, 296–303.
10 (a) B. Gadenne, P. Hesemann and J. J. E. Moreau, Chem. Commun.,
2004, 1768–1769; (b) S. Brenna, T. Posset, J. Furrer and J. Blumel,
Chem. Eur. J., 2006, 12, 2880–2888.
11 (a) D. Zhao, Q. Huo, J. Feng, B. F. Chemlka and G. D Stucky, J. Am.
Chem. Soc., 1998, 120, 6024–603611; (b) A. P. Wight and M. E. Davis,
Chem. Rev., 2002, 102, 3586–3613; (c) G. Du, S. Lim, M. Pinault, C.
Wang, F. Fang, L. Pfefferle and G. L. Haller, J. Catal., 2008, 253,
74–90.
12 (a) M. K. Richmond, S. L. Scott and H. Alper, J. Am. Chem. Soc.,
2001, 123, 10521–1052512; (b) C. Baleizao, A. Corma, H. Garcia and
A. Leyva, Chem. Commun., 2003, 606–607; (c) P.-H. Li and L. Wang,
Adv. Synth. Catal., 2006, 348, 681–685.
Acknowledgements
This work was supported by the National Honor Scientist
Program of the Ministry of Education, Science and Technology
in Korea.
References
13 J. G. Huddleston, A. E. Visser, W. M. Reichert, H. D. Willauer, G. A.
Broker and R. D. Rogers, Green Chem., 2001, 53, 156–164.
1 For reviews, see: (a) N. Miyaura and A. Suzuki, Chem. Rev., 1995,
95, 2457–2483; (b) S. R. Chemler, D. Trauner and S. J. Danishefsky,
This journal is
The Royal Society of Chemistry 2009
Green Chem., 2009, 11, 309–313 | 313
©