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109
128.4, 127.4 (2C), 123.8; MS (EI, 70 eV): m/z 155 (100, M+Å),
4.7.12. 2-Phenylthiophene (4n) [64] (CAS: 825-55-8)
154(39), 127(12).
Compound 4n was obtained from 2-bromothiophene as a white
solid after purification by flash chromatography (petroleum ether/
ethyl acetate 85:15; Rf = 0.75): 72%. 1H NMR: d 7.46–7.55 (m, 2H),
7.13–7.38 (m, 5H), 6.95–7.0 (m, 1H); 13C NMR: d 143.4, 133.3,
127.8, 127.7 (2C), 127.0, 126.2, (2C), 124.9, 123.7; MS (EI, 70 eV):
m/z 160.0 (100, M+Å), 115(27). mp 35 °C (from hexane, lit. [64],
35–36 °C)
4.7.6. 4-Phenylpyridine (4g) [68] (CAS: 939-23-1)
Compound 3g was prepared from 4-bromopyridine hydrochlo-
ride using diisopropylamine as a base. For this purpose 0.47 mmol
of diisopropylamine was added to obtain 4-bromopyridine and the
mixture was subsequently submitted to usual cross-coupling reac-
tion conditions. The product 3g was obtained as a white solid after
purification by flash chromatography (petroleum ether/ethyl ace-
tate 7:3, Rf = 0.47): 73%. 1H NMR: d 8.66 (d, 2H, 3J 4.6,), 7.64 (m,
2H), 7.42–7.53 (m, 5H); 13C NMR: d 150.3 (2C), 148.4, 138.2,
129.2 (3C), 127.1 (2C), 121.7 (2C); MS (EI, 70 eV): m/z 155 (100,
M+Å), 154(44), 128(10), 127(12), 115(8), 102(8), 77(9); mp 73 °C
(from hexane, lit. [67], 73–74 °C).
4.7.13. 5-Phenylthiophene-2-carbaldehyde (4o) [73] (CAS: 19163-21-
4)
Compound 4o was obtained from 5-bromothiophene-2-carbal-
dehyde as a light green solid after purification by flash chromatog-
raphy (petroleum ether/ethyl acetate 85:15; Rf = 0.72): 81%. 1H
NMR: d 9.89 (s, 1H), 7.74 (d, 1H, 3J 3.9), 7.67 (m, 2H), 7.38–7.47
(m, 4H); 13C NMR: d 183.0, 154.5, 142.6, 137.5, 133.2, 129.6,
129.4 (2C), 126.6 (2C), 124.2; IR (KBr): 3095, 3060, 1652, 1443,
1234, 1065, 819, 759, 752, 680. MS (EI, 70 eV): m/z 188 (80, M+Å),
187(100), 115(86). mp 81 °C (from hexane, lit. [74], 80–81 °C).
4.7.7. 6-Phenylpyridine-2-carbaldehyde (4h) [69] (CAS: 157402-44-3)
Compound 4h was obtained from 6-bromopyridine-2-carbalde-
hyde as a yellow liquid after purification by flash chromatography
(petroleum ether/ethyl acetate 9:1, Rf = 0.6): 75%. 1H NMR: d 10.2
(s, 1H), 8.10 (dd, 2H, 3J 6.9, 4J 1.7), 7.91–7.97 (m, 3H), 7.47–7.55
(m, 3H); 13C NMR: d 193.9, 157.9, 152.8, 138.1, 137.8, 129.7,
129.0 (2C), 127.0 (2C), 124.5, 119.8; IR(neat): 3063, 3036, 2830,
1707, 1587, 1451, 1301, 1217, 760, 693. MS(CI, NH3): m/z 184
(100, M+H)+.
4.7.14. 3-Phenylthiophene (4p) [64,75] (CAS: 2404-87-7)
Compound 4p was obtained from 3-bromothiophene as a color-
less solid after purification by flash chromatography (petroleum
ether/ethyl acetate 85:15; Rf = 0.75): 55%. 1H NMR: d 7.62 (m,
2H), 7.3–7.53 (m, 6H). 13C NMR: d 141.4, 136.0, 128.9 (2C), 127.3,
126.6 (2C), 126.5, 126.3, 120.4; MS (EI, 70 eV): m/z 160 (100,
M+Å), 159(12), 134(10), 128(16), 115(43), 89(14). mp 89 °C. (from
EtOH, lit. [64], 89–91 °C).
4.7.8. 2-[1,3]-Dioxolan-2-yl-6-phenylpyridine (4i) [63] (CAS: 897943-
06-5)
Compound 4i was obtained from 6-bromo-[1,3]-dioxolan-2-
ylpyridine as a colorless oil after purification by flash chromatogra-
phy (petroleum ether/ethyl acetate 8:2, Rf = 0.6): 84%. 1H NMR: d
8.04 (m, 2H), 7.80 (t, 3J 7.8), 7.72 (dd, 3J 7.9, 4J 1.1), 7.35–7.55 (m,
4H), 5.94 (s, 1H), 4.12–4.25 (m, 4H); 13C NMR: d 156.0, 138.0,
136.5, 128.4, 128.1, 127.9 (2C), 126.1 (2C), 119.7, 117.8; 103.1,
64.6 (2C); MS (EI, 70 eV): m/z 227 (4, M+Å), 184(100), 154(27),
127(16), 73(70), 45(28).
4.8. Evaluation of tin and palladium contamination
The quantification of tin and palladium was measured as total
tin or total palladium contamination by ICP-AES or ICP-MS tech-
niques in UT2A Laboratory (Pau, France) after careful mineraliza-
tion of the samples according to
procedure [76,77].
a previously described
4.7.9. 2-Methoxy-6-phenylpyridine (4j) [70] (CAS: 35070-08-7)
Compound 4j was obtained from 2-bromo-6-methoxypyridine
as a colorless oil after purification by flash chromatography (petro-
leum ether, Rf = 0.28): 57%. 1H NMR: d 8.09 (dd, 2H, 3J 8.2, 4J 1.5),
7.63 (dd, 1H, 3J 7.6, 3J 8.1), 7.38–7.53 (m, 3H), 7.36 (d, 1H, 3J 7.6),
6.72 (d, 1H, 3J 8.1), 4.05 (s, 3H);. 13C NMR: d 163.8, 154.7, 139.2,
139.1, 128.9, 128.7 (2C), 126.8 (2C), 112.8, 109.3, 53.2; IR (KBr):
3061, 2946, 2926, 2852, 1635, 1599, 1589, 1576, 1499, 1449,
1256, 1151, 763, 693. MS (EI, 70 eV): m/z 185 (76, M+Å), 184(100),
155(39), 154(70), 127(15), 115(10), 77(22).
Acknowledgements
We are grateful to CNRS (Réseau de Recherche 2: ‘‘Aller vers une
Chimie Eco-compatible”) and to ANR (Grant No. JC07_209849) for
financial support. We wish also to acknowledge MENRT for a doc-
toral fellowship (G.K.) and Chemtura (Bergkamen) for the gift of
dibutyltin dichloride and tributyltin chloride.
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