K. Beydoun, H. Doucet / Journal of Organometallic Chemistry 696 (2011) 1749e1759
1757
(d, J ¼ 8.4 Hz, 2H), 7.34 (s, 1H), 6.06 (s, 1H), 4.11 (m, 4H), 3.04
(q, J ¼ 7.5 Hz, 2H), 1.24 (t, J ¼ 7.5 Hz, 3H). 13C NMR (50 MHz, CDCl3):
152.8, 143.9, 137.5, 133.5, 130.9, 130.5, 129.4, 129.2, 115.6,106.8, 99.5,
65.9. Elemental analysis: calcd (%) for C14H11BrO3S (339.21): C
49.57, H 3.27; found: C 49.79, H 3.14.
d
200.2, 153.0, 144.1, 137.8, 129.4, 129.3, 128.2, 115.6, 106.8, 99.5,
65.9, 32.4, 8.6. Elemental analysis: calcd (%) for C16H15BrO3S
(367.26): C 52.33, H 4.12; found: C 52.17, H 4.01.
4.2.28. 3-(3-Bromo-5-[1,3]dioxolan-2-yl-thiophen-2-yl)-
benzonitrile (31)
4.2.23. 4-(3-Bromo-5-[1,3]dioxolan-2-yl-thiophen-2-yl)-
benzophenone (26)
The reaction of 3-bromobenzonitrile (0.182 g, 1 mmol), 2-(4-
bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀC during 4 h affords the product 31 in 86% (0.289 g) isolated
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol), 2-(4-
bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀC during 4 h affords the product 26 in 85% (0.353 g) isolated
yield. 1H NMR (200 MHz, CDCl3):
d
8.00 (d, J ¼ 7.8 Hz, 1H), 7.96 (s,
1H), 7.75 (d, J ¼ 7.8 Hz, 1H), 7.60 (t, J ¼ 7.8 Hz, 1H), 7.37 (s, 1H), 6.09
(s, 1H), 4.13 (m, 4H). 13C NMR (50 MHz, CDCl3):
151.4, 144.5, 133.5,
yield. 1H NMR (200 MHz, CDCl3):
d
7.98e7.80 (m, 6H), 7.70e7.45 (m,
3H), 7.38 (s,1H), 6.09 (s,1H), 4.13 (m, 4H). 13C NMR (50 MHz, CDCl3):
196.0, 153.2, 144.1, 138.8, 137.5, 133.2, 131.3, 130.5, 129.4, 128.9,
d
132.2, 131.5, 130.7, 129.2, 118.2, 115.3, 114.2, 107.4, 99.4, 65.9.
Elemental analysis: calcd (%) for C14H10BrNO2S (336.20): C 50.01, H
3.00; found: C 50.10, H 3.11.
d
128.0, 115.7, 106.9, 99.6, 65.9. Elemental analysis: calcd (%) for
C20H15BrO3S (415.30): C 57.84, H 3.64; found: C 57.98, H 3.80.
4.2.29. 2-(4-Bromo-5-naphthalen-2-yl-thiophen-2-yl)-[1,3]
dioxolane (32)
4.2.24. 2-[4-Bromo-5-(4-trifluoromethylphenyl)-thiophen-2-yl]-
[1,3]dioxolane (27)
The reaction of 4-(trifluoromethyl)bromobenzene (0.225 g,
1mmol), 2-(4-bromothiophen-2-yl)-[1,3]dioxolane(0.470g, 2mmol)
and KOAc (0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in
DMAc at 100 ꢀC during 4 h affords the product 27 in 84% (0.319 g)
The reaction of 2-bromonaphthalene (0.207 g, 1 mmol), 2-(4-
bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀCduring4haffordstheproduct32in90%(0.325g)isolatedyield.
1HNMR(200MHz,CDCl3):
d
8.27(s,1H), 8.00e7.80(m, 4H),7.60e7.52
(m, 2H), 7.37 (s, 1H), 6.10 (s, 1H), 4.13 (m, 4H). 13C NMR (50 MHz,
CDCl3): 154.9, 142.8, 134.0, 133.6, 129.6, 129.3, 129.0, 128.2, 127.8,
isolatedyield.1HNMR (200 MHz,CDCl3):
d
7.87 (d, J ¼ 8.3 Hz, 2H), 7.75
(d, J ¼ 8.3 Hz, 2H), 7.38 (s, 1H), 6.09 (s, 1H), 4.13 (m, 4H). 13C NMR
d
(50 MHz, CDCl3):
d
152.5, 144.2, 132.0 (q, J ¼ 32.5 Hz), 129.3, 128.5,
127.7,127.5,125.3,116.2,106.0, 99.7, 65.9. Elemental analysis:calcd (%)
for C17H13BrO2S (361.25): C 56.52, H 3.63; found: C 56.67, H 3.50.
126.7 (q, J ¼ 3.8 Hz), 124.0 (q, J ¼ 272.3 Hz), 115.5, 107.2, 99.5, 65.9.
Elemental analysis: calcd (%) for C14H10BrF3O2S (379.19): C 44.34, H
2.66; found: C 44.47, H 2.51.
4.2.30. 2-(3-Bromo-5-[1,3]dioxolan-2-yl-thiophen-2-yl)-
benzonitrile (33)
4.2.25. 2-[4-Bromo-5-(4-fluorophenyl)-thiophen-2-yl]-[1,3]
dioxolane (28)
The reaction of 4-bromofluorobenzene (0.175 g, 1 mmol), 2-(4-
bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀC during 4 h affords the product 28 in 84% (0.277 g) isolated
The reaction of 2-bromobenzonitrile (0.182 g, 1 mmol), 2-(4-
bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc
at 100 ꢀC during 4 h affords the product 33 in 85% (0.286 g)
isolated yield. 1H NMR (200 MHz, CDCl3):
d
7.85 (d, J ¼ 7.4 Hz,
1H), 7.80e7.55 (m, 3H), 7.40 (s, 1H), 6.12 (s, 1H), 4.13 (m, 4H). 13C
NMR (50 MHz, CDCl3): 147.7, 144.5, 133.1, 132.2, 130.1, 129.2,
yield. 1H NMR (200 MHz, CDCl3):
d
7.73 (dd, J ¼ 8.5, 4.8 Hz, 2H), 7.32
(s, 1H), 7.19 (d, J ¼ 8.5 Hz, 2H), 6.07 (s, 1H), 4.11 (m, 4H). 13C NMR
d
126.8, 116.2, 113.3, 111.6, 109.1, 98.0, 64.5. Elemental analysis: calcd
(%) for C14H10BrNO2S (336.20): C 50.01, H 3.00; found: C 50.07, H
2.84.
(50 MHz, CDCl3):
d
163.4 (d, J ¼ 250.9 Hz), 153.0, 142.5, 129.7
(d, J ¼ 8.5 Hz), 128.6, 127.4 (d, J ¼ 3.4 Hz), 116.3 (d, J ¼ 22.0 Hz),
105.5, 98.9, 65.4. Elemental analysis: calcd (%) for C13H10BrFO2S
(329.19): C 47.43, H 3.06; found: C 47.32, H 3.19.
4.2.31. 3-(3-Bromo-5-[1,3]dioxolan-2-yl-thiophen-2-yl)-pyridine (34)
The reaction of 3-bromopyridine (0.158 g, 1 mmol), 2-(4-bro-
mothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀC during 4 h affords the product 34 in 78% (0.243 g) isolated
4.2.26. [4-(3-Bromo-5-[1,3]dioxolan-2-yl-thiophen-2-yl)-phenyl]-
acetonitrile (29)
The reaction of 4-bromophenylacetonitrile (0.196 g, 1 mmol), 2-
(4-bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀC during 4 h affords the product 29 in 84% (0.294 g) isolated
yield. 1H NMR (200 MHz, CDCl3):
d
8.93 (s, 1H), 8.70 (d, J ¼ 4.2 Hz,
1H), 8.12 (d, J ¼ 7.9 Hz, 1H), 7.46 (dd, J ¼ 7.9, 4.2 Hz, 1H), 7.42 (s, 1H),
6.09 (s, 1H), 4.14 (m, 4H). 13C NMR (50 MHz, CDCl3):
151.2, 150.5,
yield. 1H NMR (200 MHz, CDCl3):
d
7.75 (d, J ¼ 8.2 Hz, 2H), 7.45
(d, J ¼ 8.2 Hz, 2H), 7.33 (s, 1H), 6.06 (s, 1H), 4.11 (m, 4H), 3.82 (s, 2H).
13C NMR (50 MHz, CDCl3):
153.2, 142.8, 131.7, 128.9, 128.7, 128.4,
d
148.8, 144.2, 135.2, 129.2, 124.3, 115.4, 107.4, 99.5, 65.9. Elemental
analysis: calcd (%) for C12H10BrNO2S (312.18): C 46.17, H 3.23;
found: C 46.04, H 3.11.
d
117.3, 115.4, 105.9, 99.2, 65.5, 23.5. Elemental analysis: calcd (%) for
C15H12BrNO2S (350.23): C 51.44, H 3.45; found: C 51.30, H 3.40.
4.2.32. 5-(3-Bromo-5-[1,3]dioxolan-2-yl-thiophen-2-yl)-
pyrimidine (35)
4.2.27. 3-(3-Bromo-5-[1,3]dioxolan-2-yl-thiophen-2-yl)-
benzaldehyde (30)
The reaction of 5-bromopyrimidine (0.159 g, 1 mmol), 2-(4-
bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀC during 4 h affords the product 35 in 69% (0.216 g) isolated
The reaction of 3-bromobenzaldehyde (0.185 g, 1 mmol), 2-(4-
bromothiophen-2-yl)-[1,3]dioxolane (0.470 g, 2 mmol) and KOAc
(0.196 g, 2 mmol) with Pd(OAc)2 (1.12 mg, 0.005 mmol) in DMAc at
100 ꢀC during 4 h affords the product 30 in 87% (0.295 g) isolated
yield. 1H NMR (200 MHz, CDCl3):
d
9.30 (s, 1H), 9.10 (s, 2H), 7.42
(s, 1H), 6.10 (s, 1H), 4.10 (m, 4H). 13C NMR (50 MHz, CDCl3):
d
159.5,
yield. 1H NMR (200 MHz, CDCl3):
d
10.07 (s, 1H), 8.18 (s, 1H), 8.03
(d, J ¼ 7.8 Hz, 1H), 7.96 (d, J ¼ 7.8 Hz, 1H), 7.67 (t, J ¼ 7.7 Hz, 1H), 7.35
(s, 1H), 6.06 (s, 1H), 4.11 (m, 4H). 13C NMR (50 MHz, CDCl3):
191.7,
155.4, 146.1,145.8, 129.3, 114.8, 108.9, 99.3, 66.0. Elemental analysis:
calcd (%) for C11H9BrN2O2S (313.17): C 42.19, H 2.90; found: C 42.02,
H 2.77.
d