5
NMR (101 MHz, d -DMSO): δ 164.92, 161.0
1
A
7,
31.42, 130.38, 128.37, 120.39, 118.43, 116.38 ppm. Anal. Calcd
for C H N Na O S ꢀ2H O, %: C, 43.17; H, 3.26; N, 5.03; S,
C
14
C
2.4
E
6
P
, 1
T
40
E
.1
D
2, MA12
N
0.
U
59
S
,
C
11
RI
9.
4
P
6, 110.58, 110.30. HRMS (ESI): calcd. for
T
6
+
C H N O [M+H] 364.1212; found 364.1209.
4
2
16
2
2
20
14
2
2
8
2
2
1
8
d: 3-(3-methoxyphenyl)-9-phenyl-9H-carbazole: H NMR
(400 MHz, CDCl ): δ 8.34 (d, J = 1.4 Hz, 1H), 8.18 (d, J = 7.7
Hz, 1H), 7.62 (m, 5H), 7.47–7.36 (m, 5H), 7.33–7.28 (m, 2H),
1
1.52; Found, %: C, 43.06; H, 3.20; N, 5.09; S, 11.76. MS (ESI):
−
−
1
3
m/z [(M-Na)] , calculated: 497.0; found, 497.0. IR (KBr, cm ):
3
387 (-OH), 1616 (-C=N), 1111 (-SO Na).
13
3
7
.25 (s, 1H), 6.90 (dd, J = 8.1, 2.5 Hz, 1H), 3.90 (s, 3H);
C
1
Ligand 2: yield 70%. H NMR (400 MHz, d -DMSO): δ 13.59
NMR (101 MHz, CDCl ): δ 160.14, 143.70, 141.49, 140.60,
6
3
(
s, 2H, OH), 8.67 (s, 2H), 7.68 (d, J = 2.4 Hz, 2H), 7.52 (dd, J =
137.78, 133.46, 129.97, 127.67, 127.21, 126.28, 125.63, 123.97,
1
2
.4 Hz, J = 8.8 Hz, 2H), 6.79 (d, J = 8.8 Hz, 2H), 3.90 (s, 4H)
123.60, 120.50, 120.13, 119.00, 113.28, 112.04, 110.08, 55.50.
2
13
+
ppm. C NMR (101 MHz, d -DMSO): δ 167.10, 161.20, 139.43,
HRMS (ESI): calcd. for C H NO [M+H] 349.1467; found
6
25 19
1
30.37, 128.83, 117.37, 116.11, 59.22 ppm. Anal. Calcd for
349.1463.
C H N Na O S ꢀ2H O, %: C, 40.68; H, 2.99; N, 5.93; S, 13.57;
1
16
14
2
2
8
2
2
8
e: 3-(2-methoxyphenyl)-9-phenyl-9H-carbazole: H NMR
Found, %: C, 40.96; H, 2.95; N, 6.05; S, 13.26. MS (ESI): m/z
−
−1
(400 MHz, CDCl ): δ 8.28 (s, 1H), 8.14 (d, J = 7.8 Hz, 1H), 7.58
s, 5H), 7.41 (m, 5H), 7.29 (m, 2H), 7.09–7.00 (m, 2H), 3.82 (s,
H). C NMR (101 MHz, CDCl ): δ 141.35, 140.26, 139.16,
3
[
(
(M−Na)] , calculated: 449.0; found, 449.1. IR (KBr, cm ): 3460
(
3
-OH), 1635 (-C=N), 1188 (-SO Na).
13
3
3
4
.3. Synthesis of complex 1
137.74, 136.27, 133.48, 129.93, 129.89, 129.54, 127.50, 127.22,
1
1
27.20, 127.18, 127.09, 126.10, 125.40, 123.89, 123.54, 120.39,
To a solution of ligand 1 (1.0 mmol) in 50% EtOH (20 mL)
20.04, 118.60, 109.99, 109.92, 21.14. HRMS (ESI): calcd. for
was added Pd(OAc) (1.0 mmol). The mixture was stirred at 60
+
2
C H NO [M+H] 349.1467; found 349.1465.
25
19
ºC for 2 h, and stand a period time at room temperature, the solid
was filtrated and washed twice with EtOH to give the complex 1.
1
8f: 9-(4'-methoxy-[1,1'-biphenyl]-3-yl)-9H-carbazole:
H
NMR (400 MHz, CDCl ): δ 8.34 (s, 1H), 8.22 (d, J = 8.4 Hz, 1H),
1
3
Complex 1: yield 65%. H NMR (400 MHz, d -DMSO): δ
6
7
8
1
1
.66 (m, 7H), 7.54–7.44 (m, 4H), 7.37–7.31 (m, 1H), 7.06 (d, J =
9
7
.29 (s, 2H), 8.44-8.41 (m, 2H), 8.11 (s, 2H), 7.63-7.60 (m, 2H),
13
.8 Hz, 2H), 3.91 (s, 3H); C NMR (101 MHz, CDCl ): δ 159.69,
13
3
.45-7.42 (m, 2H), 6.96 (d, J = 8.0 Hz, 2H) ppm. C NMR (101
42.82, 141.02, 138.29, 132.72, 130.33, 128.33, 126.09, 125.77,
MHz, d -DMSO): δ 166.50, 155.69, 143.60, 136.39, 134.52,
6
25.33, 123.51, 120.45, 120.06, 114.51, 109.98, 55.49. HRMS
1
33.72, 128.76, 120.36, 119.75, 117.87 ppm. Anal. Calcd for
+
(ESI): calcd. for C H NO [M+H] 349.1467; found 349.1465.
25
19
C H N Na O PdS , %: C, 38.44; H, 1.94; N, 4.48; S, 10.26;
2
0
12
2
2
8
2
4
.5. Catalyst recycling for the Suzuki-Miyaura reaction
Found, %: C, 38.36; H, 1.96; N, 4.52; S, 10.18. MS (ESI): m/z
+
[
M-2Na+3H] calculated: 580.9306, found, 580.9299.
When the reaction was completed, the mixture was cooled to
room temperature and extracted with ethyl ether (2 mL). NaOH
4
.4. General procedure for salen-Pd complex 1 catalyzed the
Suzuki-Miyaura reaction
(1 mmol), p-bromoacetophenone (0.5 mmol), ortho-tolylboronic
acid (0.75 mmol) were added to the aqueous phase that was
separated from the previous catalytic run, and reacted at 100 °C.
A solution of aryl bromide (0.5 mmol), arylboronic acid (0.75
mmol), NaOH (1.0 mmol), and complex 1 (0.5 mol%) in H O
2
(
1.0 mL) was stirred at 100 °C for 5 h. The reaction mixture was
Acknowledgments
quenched with water (10 mL) and extracted with EtOAc (3 × 10
mL). The combined EtOAc extracts were dried over anhydrous
Na SO , filtrated, and then the solvent was removed under
reduced pressure. The residue was purified by flash column
chromatography on silica gel with PE or PE/EtOAc as the eluent
to obtain the desired products.
We gratefully acknowledge financial support of this work by
the National Natural Science Foundation of China (No.
2
4
2
1563025, No. 21463022), Shihezi University Training
Programme for Distinguished Youth Scholars (No.
014ZRKXJQ05), and Start-Up Foundation for Young Scientists
2
1
8
a: 3-(4-methoxyphenyl)-9-phenyl-9H-carbazole: H NMR
of Shihezi University (RCZX201408).
(400 MHz, CDCl ): δ 8.22–8.18 (m, 2H), 7.79 (m, 1H), 7.71–
3
7
2
.66 (m, 2H), 7.64–7.59 (m, 2H), 7.56–7.43 (m, 5H), 7.33 (m,
13
H), 7.05–7.00 (m, 2H), 3.89 (s, 3H); C NMR (101 MHz,
References and notes
CDCl ): δ 158.80, 141.44, 140.16, 137.84, 134.78, 133.32,
1. Stanforth, S. P. Tetrahedron. 1998, 54, 263-303.
3
1
1
30.02, 128.43, 127.57, 127.17, 126.19, 125.35, 123.99 (s),
2.
(a) Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981,
1
1, 513-519; (b) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95,
23.61, 120.47, 120.11, 118.46, 114.37, 110.05, 55.52. HRMS
+
2457-2483; (c) Suzuki, A. J. Organomet. Chem. 1999, 576, 147-
(ESI): calcd. for C H NO [M+H] 349.1467; found 349.1463.
25
19
1
68; (d) Suzuki, A. J. Organomet. Chem. 2002, 653, 83-90.
1
3
.
(a) Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J.
Am. Chem. Soc. 1999, 121, 9550-9561; (b) Yin, J.; Rainka, M. P.;
Zhang, X. X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124,
8
b: 9-phenyl-3-(p-tolyl)-9H-carbazole: H NMR (400 MHz,
CDCl ): δ 8.33 (s, 1H), 8.18 (d, J = 7.7 Hz, 1H), 7.65–7.58 (m,
7
3
13
H), 7.47–7.40 (m, 4H), 7.29 (m, 3H), 2.42 (s, 3H). C NMR
1
162-1163; (c) Billingsley, K. L.; Anderson, K. W.; Buchwald, S.
(101 MHz, CDCl ): δ 141.35, 140.26, 139.16, 137.74, 136.27,
L. Angew. Chem. 2006, 118, 3564-3568; Angew. Chem. Int. Ed.,
2006, 45, 3484-3488; (d) Bruno, N. C.; Tudge, M. T.; Buchwald,
S. L. Chem. Sci. 2013, 4, 916-920.
(a) Littke, A. F.; Fu, G. C. Angew. Chem. 1998, 110, 3586-3587;
Angew. Chem. Int. Ed., 1998, 37, 3387-3388; (b) Littke, A. F.;
Dai, C.; Fu, G. C. J. Am. Chem. Soc. 2000, 122, 4020-4028; (c)
Liu, S. Y.; Choi, M. J.; Fu, G. C. Chem. Commun. 2001, 2408-
3
1
1
1
3
33.48, 129.93, 129.89, 129.54, 127.50, 127.22, 127.20, 127.18,
27.09, 126.10, 125.40, 123.89, 123.54, 120.39, 120.04, 118.60+,
4.
5.
09.99, 109.92, 21.14. HRMS (ESI): calcd. for C H N [M+H]
25
19
33.1517; found 333.1514.
1
8
c: 3-(4-nitrophenyl)-9-phenyl-9H-carbazole: H NMR (400
2
409; (d) Kudo, N.; Perseghini, M.; Fu, G. C. Angew. Chem.
MHz, CDCl ): δ 8.40 (d, J = 1.6 Hz, 1H), 8.32 (d, J = 8.8 Hz,
2
5
CDCl ): δ 148.58, 146.58, 141.67, 141.35, 137.40, 130.80,
1
3
2006, 118, 1304-1306; Angew. Chem. Int. Ed. 2006, 45, 1282-
1284.
(a) Grasa, G. A.; Hillier, A. C.; Nolan, S. P. Org. Lett. 2001, 3,
H), 8.20 (d, J = 7.8 Hz, 1H), 7.85 (d, J = 8.9 Hz, 2H), 7.63 (m,
13
H), 7.53–7.41 (m, 4H), 7.34 (m, 1H); C NMR (101 MHz,
1
077-1080; (b) Grasa, G. A.; Viciu, M. S.; Huang, J.; Zhang, C.;
3
Trudell, M. L.; Nolan, S. P. Organometallics. 2002, 21, 2866-
30.17, 127.99, 127.72, 127.20, 126.75, 125.51, 124.29, 123.30,