Benzimidazolium-Pyrazole-Palladium(II) Complexes: New and Efficient Catalysts
FULL PAPERS
3
3
1
998.9(1) ; Z=4; crystal size 0.440.180.16 mm ;
in a 15-mL tube. A DMA solution of Pd-NN complex
(3 mL) was then added in the given quantity (see Table 4,
Table 5, and Table 6). The reaction mixture was stirred at
1308C or 1008C for the specified duration. After coolingto
room temperature, the reaction mixture was diluted with
CH Cl (10 mL) and washed with water (10 mL). The organ-
GOF=1.052; reflections collected: 13783; independent re-
flections: 4587 [Rint =0.0215]; R =0.0304; wR =0.0779. De-
pository number: CCDC 690476.
: yield: 366 mg(82%); mp 331.0–332.0 8C; H NMR
300 MHz, CDCl ): d=8.11 (d, J=7.2 Hz, 1H), 7.86–7.79
1
2
1
6
(
3
2
2
(
m, 1H), 7.46–7.37 (m, 2H), 6.30 (d, J=16.4 Hz, 1H,), 6.18–
ic extract was dried over MgSO , filtered, and the resultant
4
5
1
.99 (m, 2H), 4.72–4.42 (m, 2H), 2.62–2.46 (m, 6H), 1.83-
mixture analyzed by GC-MS.
1
3
.70 (m, 2H), 0.94 (t, J=7.2 Hz, 3H);
C NMR
(
75.47 MHz, CD SOCD ): d=152.46, 147.24, 143.96, 138.20,
3 3
1
2
4
33.40, 124.79, 124.00, 119.60, 112.61, 108.15, 46.27, 44.04,
3.73, 15.11, 11.81, 11.11; anal. calcd. for C H N PdCl : C
1
6
20
4
2
Acknowledgements
3.12, H 4.52, N 12.57; found: C 43.00, H 4.53, N 12.61; MS
+
(
ESI): +m/z=452 {[Pd
A
H
R
U
G
A
H
R
U
G
3
This work was supported by the Agency for Science, Technol-
ogy & Research (Singapore) (R143–000–277–305 and R143–
000–364–305) and the National University of Singapore. We
thank the staff at the CMMAC of NUS for technical assis-
tance.
N) Cl ] .
2
3
Crystal data for 6: formula C H Cl N Pd, yellow crystal,
1
6
20
2
4
monoclinic space group P2 /c; a=9.341(5), b=19.782(1), c=
9
size 0.400.300.06 mm ; GOF=1.060; reflections collect-
1
3
.950(5) ; b=112.542(1)8; V=1698.3(2) ; Z=4; crystal
3
ed: 11897; independent reflections: 3895 [Rint =0.0253]; R =
1
0
.0267; wR =0.0633. Depository number: CCDC 690477.
2
1
References
7
: yield: 419 mg(79%); mp 246.0–247.0 8C; H NMR
(
(
(
300 MHz, CD SOCD ): d=8.29–8.21 (m, 1H), 7.85–7.74
m, 1H), 7.49–7.44 (m, 2H), 6.40 (d, J=14.8 Hz, 0.4H), 6.16
s, 1.2H) 6.13 (s, 0.4H), 6.06 (s, 0.6H), 5.92 (d, J=14.5 Hz,
3
3
[
1] Some representative reviews for the Suzuki cross-cou-
plingand its applications, see: a) A. Suzuki, N.
Miyaura, Chem. Rev. 1995, 95, 2457; b) A. Suzuki, J.
Organomet. Chem. 1999, 576, 147; c) S. R. Chemler, D.
Trauner, S. J. Danishefsky, Angew. Chem. Int. Ed. 2001,
0
9
.4H) 4.31–4.10 (m, 2H), 1.63–1.44 (m, 9H), 1.15–1.06 (m,
13
H), 0.87–0.75 (m, 3H);
C NMR (125.77 MHz,
CD SOCD ): d=159.72, 152.56, 149.75, 142.00, 125.68,
3
3
4
0, 4544; d) S. Kotha, K. Lahiri, D. Kashinath, Tetrahe-
124.68, 124.01, 119.93, 112.34, 101.14, 49.13, 46.76; anal.
dron 2002, 58, 9633; e) F. Bellina, A. Carpita, R. Rossi,
Synthesis 2004, 2419; f) A. Suzuki, Chem. Commun.
2005, 4759; g) N. T. S. Phan, M. van der Sluys, C. W.
Jones, Adv. Synth. Catal. 2006, 348, 609.
calcd. for C H N PdCl : C 49.87, H 6.09, N 10.57; found: C
22
32
4
2
48.36, H 6.15, N 10.15; MS (ESI): m/z=536 {[Pd
ACHTREUNG
+
N)Cl] +CH CN}, 847 {Pd(N-N) Cl}.
A
H
R
U
G
3
2
3
24 35
2
5
[
2] Some representative reviews for the Heck reaction and
its applications, see: a) W. Cabri, I. Candiani, Acc.
Chem. Res. 1995, 28, 2; b) G. T. Crisp, Chem. Soc. Rev.
crystal, triclinic space group P-1; a=9.543(2), b=11.805(2),
c=12.659(2) ; a=76.419(4), b=102.075(1), g=71.520(3)8;
V=1310.5(4) ; Z=2; crystal size 0.360.200.10 mm ;
GOF=1.071; reflections collected: 11838; independent re-
flections: 3777 [Rint =0.0421]; R =0.0349; wR =0.0802. De-
3
3
1
998, 27, 427; c) I. P. Beletskaya, A. V. Cheprakov,
Chem. Rev. 2000, 100, 3009; d) N. J. Whitcombe, K. K.
Hii, S. E. Gibson, Tetrahedron 2001, 57, 7449; e) A. B.
Dounay, L. E. Overman, Chem. Rev. 2003, 103, 2945;
f) P. J. Guiry, D. Kiely, Current Org. Chem. 2004, 8, 781;
g) N. Miyaura, Adv. Synth. Catal. 2004, 346, 1522; h) M.
Shibasaki, E. M. Vogl, T. Ohshima, Adv. Synth. Catal.
1
2
pository number: CCDC 690478.
General Procedure for Suzuki–Miyaura Cross
Coupling Reaction
2
3
004, 346, 1533; i) V. Farina, Adv. Synth. Catal. 2004,
46, 1553; j) A. M. Trzeciak, J. J. Ziolkowski, Coord.
Water (1.0 mL), aryl or heteroaryl halide (0.5 mmol), boron-
ic acid (0.6 mmol), and K CO (1.2 mmol) were introduced
into a 15-mL tube. An MeOH solution of the Pd-NN com-
plex of interest with a specified catalyst loading(see
Table 1, Table 2, and Table 3) was injected. The reaction
mixture was stirred at room temperature for 10 min-15 h
2
3
Chem. Rev. 2005, 249, 2308; k) F. Alonso, I. P. Belet-
skaya, M. Yus, Tetrahedron 2005, 61, 11771.
[
[
[
3] Some representative reviews for the Sonogashira reac-
tion and its applications, see: a) K. Sonogashira, J. Or-
ganomet. Chem. 2002, 653, 46; b) R. R. Tykwinski,
Angew. Chem. Int. Ed. 2003, 42, 1566; c) E. Negishi, L.
Anastasia, Chem. Rev. 2003, 103, 1979; d) R. Chinchil-
la, C. Nµjera, Chem. Rev. 2007, 107, 874.
4] a) Z. Q. Weng, S. H. Teo, L. L. Koh, T. S. A. Hor, Orga-
nometallics 2004, 23, 3603; b) S. H. Teo, Z. Q. Weng,
T. S. A. Hor, Organometallics 2006, 25, 1199; c) Z. Q.
Weng, S. H. Teo, T. S. A. Hor, Acc. Chem. Res. 2007,
(
(
see tables). The resultant mixture was diluted with CH Cl
10 mL) and washed with water (10 mL). The water phase
2 2
was extracted by CH Cl (5 mL) two times. The organic ex-
tracts were combined and dried over MgSO , filtered, and
concentrated in vacuum. The product was analyzed by GC-
MS and also isolated by column chromatography (silica gel,
hexane/ethyl acetate 20:1).
2
2
4
4
0, 676; d) S. K. Yen, L. L. Koh, H. V. Huynh, T. S. A.
Hor, Dalton Trans. 2007, 35, 3952.
General Procedure for Mizoroki–Heck and
Sonogashira Coupling Reactions
5] Some latest references for phosphine ligands applied in
the CÀC cross-couplingreactions, see: a) M. J. Burns,
Aryl bromide (0.5 mmol), olefin or phenylacetylene
I. J. S. Fairlamb, A. R. Kapdi, P. Sehnal, R. J. K. Taylor,
(
0.75 mmol), and NaOAc or K CO (1.0 mmol) were placed
Org. Lett. 2007, 9, 5397; b) A. S. Guram, X. Wang,
2
3
Adv. Synth. Catal. 2008, 350, 2391 – 2400
ꢀ 2008 Wiley-VCH VerlagGmbH & Co. KGaA, Weinheim
2399