Expanded Heterogeneous Suzuki–Miyaura Coupling Reactions
FULL PAPERS
oxoiminopropyltriethoxysilane 1 (0.30 g, 1.0 mmol) in THF References
(
10 mL). After stirring for 2 h at room temperature, a solu-
tion of [Pd
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(PPh )MeCl] (0.51 g, 0.6 mmol) in THF (5 mL)
[1] For reviews of metal-catalyzed cross-couplings, see:
a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457;
b) A. Suzuki, J. Organomet. Chem. 1999, 575,147; c) F.
Diederich, P. J. Stang, Metal-Catalyzed Cross-Coupling
Reactions, Wiley-VCH, New York, 1998; d) L. A. Agro-
foglio, I. Gillaizeau, Y. Saito, Chem. Rev. 2003, 103,
1875; e) M. Beller, C. Bolm, Transition Metals for Or-
ganic Synthesis, 2nd edn., Wiley-VCH, Weinheim,
2004; f) U. Christmann, R. Vilar, Angew. Chem. 2005,
117, 370; Angew. Chem. Int. Ed. 2005, 44, 366; g) K. C.
Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. 2005,
117, 4516; Angew. Chem. Int. Ed. 2005, 44, 4442.
3
2
was dropwise added to the mixture. After 2 h, the mixture
was filtered through celite on a frit. The solvent was re-
moved under reduced pressure and the residue was washed
with hexane (30 mL) and extracted with dichloromethane
(
10 mL). Removal of the solvent gave Pd complex 2 as a
1
light brown crude solid; yield: 0.56 g (82%). H NMR
400 MHz, CDCl ): d=7.79–7.52 (m, 5H), 7.49–7.27 (m,
(
3
1
2
0H), 4.70 (s, 1H), 3.83 (q, 6H, J=6.8 Hz), 3.45 (m, 2H),
.00 (s, 3H), 1.75 (m, 2H), 1.52 (s, 3H), 1.22 (m, 6H), 0.63
1
3
(
(
t, 2H, J=7.2 Hz), 0.097 (d, 3H, J=2.8 Hz); C NMR
100 MHz, CDCl ): d=176.86, 163.95, 134.74, 134,63, 132.00,
3
1
1
1
31.91, 131.78, 131.37, 130.90, 129.83, 128.43, 128.30, 128.05,
27.76, 127.66, 97.94, 67.93, 58.43, 58.33, 58.16, 26.14, 25.64,
8.59, 18.39, 18.34, 7.69, À2.21; P NMR (162 MHz, CDCl ):
[
2] a) A. Zapf, A. Ehrentraut, M. Beller, Angew. Chem.
2
000, 112, 4315; Angew. Chem. Int. Ed. 2000, 39, 4153;
3
1
3
b) A. F. Littke, G. C. Fu, Angew. Chem. 2002, 114,
4350; Angew. Chem. Int. Ed. 2002, 41, 4176; c) K. W.
Anderson, S. L. Buchwald, Angew. Chem. 2005, 117,
d=43.88; anal. calcd. For C H NO PPdSi: C 57.76, H 6.76,
3
3
46
4
N 2.04; found: C 57.74, H 6.53, N 2.10.
6
329; Angew. Chem. Int. Ed. 2005, 44, 6173; d) T.
Synthesis of MP-LTA-Supported b-
Oxoiminatophosphanylpalladium Complex 3
Brenstrum, J. Clattenburg, J. Britten, S. Zavorine, J.
Dyck, A. J. Robertson, J. McNulty, A. Capretta, Org.
Lett. 2006, 8, 103; e) H. Ohta, M. Tokunaga, Y. Obora,
T. Iwai, T. Iwasawa, T. Fujihara, Y. Tsuji, Org. Lett.
Mesoporous-microporous hierarchical LTA zeolite (MP-
LTA) (1.0 g) was added to a solution of compound 2 (0.24 g,
2
007, 9, 89; f) O. Diebolt, P. Braunstein, S. P. Nolan,
0.35 mmol) in toluene (10 mL) and the mixture was refluxed
C. S. J. Cazin, Chem. Commun. 2008, 3190; g) D.-H.
Lee, J.-Y. Jung, I. M. Lee, M.-J. Jin, Eur. J. Org. Chem.
for 12 h. After filtration, the powder was washed several
times with dichloromethane and dried under vacuum at
2
008, 356.
708C to give MP-LTA-supported b-oxoiminatophosphanyl-
[
[
3] a) N. T. S. Phan, M. V. D. Sluys, C. W. Jones, Adv.
Synth. Catal. 2006, 348, 609; b) L. Yin, J. Liebscher,
Chem. Rev. 2007, 107, 133.
4] a) C. Baleiz¼o, A. Corma, H. Garcꢁa, A. Leyva, Chem.
Commun. 2003, 606; b) A. Corma, D. Das, H. Garcꢁa,
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nabeꢂ, C. C. Tzschucke, W. Bannwarth, R. Haag, Adv.
Synth. Catal. 2005, 347, 1389; d) J. Lemo, K. Heuzeꢂ, D.
Astruc, Org. Lett. 2005, 7, 2253; e) J. D. Webb, S. Mac-
Quarrie, K. McEleney, C. M. Crudden, J. Catal. 2007,
palladium (Pd/MP-LTA) 3. The product was filtered,
washed with CH Cl (10 mL) three times, and dried under
2
2
À1
vacuum at 808C. The Pd content of 0.30 mmolg was mea-
sured by inductively coupled plasma (ICP) analysis.
General Procedure for the Suzuki–Miyaura Coupling
Reaction
The reaction was carried out by using a glass vial equipped
with a Teflon screw cap. Aryl halide (1.0 mmol), arylboronic
acid (1.2 mmol), K CO (276 mg, 2.0 mmol) and catalyst 3
2
52, 97; f) R. Sayah, K. Glegola, E. Framery, V.
2
3
À1
Dufaud, Adv. Synth. Catal. 2007, 349, 373; g) S. Schwei-
zer, J.-M. Becht, C. L. Drian, Org. Lett. 2007, 9, 3777;
h) H. Qiu, S. M. Sarkar, D.-H. Lee, M.-J. Jin, Green
Chem. 2008, 10, 37.
(
33.3 mg, 0.30 mmolg , 1 mol%) were mixed in EtOH-H O
2
(
2.0 mL, 1:1, v/v). The reaction mixture was stirred at 50 8C
and monitored by GC/GC-MS. GC/GC-MS analyses were
performed on an Agilent 6890N GC coupled to an Agilent
[
5] a) L. Artok, H. Bulut, Tetrahedron Lett. 2004, 45, 3881;
b) T. Maegawa, Y. Kitamura, S. Sako, T. Udzu, A. Sa-
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Kurita, A. Kozaki, Y. Monguchi, H. Sajiki, Chem. Eur.
J. 2007, 13, 5937; c) Y. Kitamura, A. Sakurai, T. Udzu,
T. Maegawa, Y. Monguchi, H. Sajiki, Tetrahedron 2007,
5975 Network mass selective detector. EtOH solvent was re-
moved under reduced pressure. After diethyl ether (5 mL)
and water (2 mL) was added, the mixture was filtered. The
layers were separated and the aqueous layer was extracted
with diethyl ether. The combined organic layers were dried
(
MgSO ) and filtered, and the solvent was removed. The
4
6
3, 10596; d) S. Proch, Y. Mei, J. M. R. Villanueva, Y.
Lu, A. Karpov, M. Ballauff, Adv. Synth. Catal. 2008,
50, 493; e) M. Trilla, G. Borja, R. Pleixats, M. W. C.
Man, C. Bied, J. J. E. Moreau, Adv. Synth. Catal. 2008,
50, 2566; f) K. Kçhler, R. G. Heidenreich, S. S.
residue was purified by short column chromatography on
silica gel to afford the desired product. The filtered catalyst
was reused without further purification.
3
3
Soomro, S. S. Prçckl, Adv. Synth. Catal. 2008, 350,
2930; g) A. Gniewek, J. J. Ziꢃłkowski, A. M. Trzeciak,
M. Zawadzki, H. Grabowska, J. Wrzyszcz, J. Catal.
2008, 254, 121; h) Y. Mpnguchi, Y. Fujita, K. Endo, S.
Takao, M. Yoshimura, Y. Takagi, T. Maegawa, H,
Sajiki, Chem. Eur. J. 2009, 15, 834.
Acknowledgements
This work was supported by Korea Ministry of Education,
Science and Technology through the National Honor Scientist
Program. M.-J. Jin also thanks the financial support from the
National Research Foundation of Korea (Grant: 2009-
[6] a) M. T. Reetz, E. Westermann, Angew. Chem. 2000,
0072013).
112, 170; Angew. Chem. Int. Ed. 2000, 39, 165; b) S.-W.
Adv. Synth. Catal. 2009, 351, 2912 – 2920
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2919