Deprotonative Metalation
FULL PAPER
(Furan-2-yl)(4-methoxyphenyl)methanol (6d): Yellow liquid; 1H NMR
(CDCl3, 300 MHz): d=2.46 (d, J=4.3 Hz, 1H), 3.81 (s, 3H), 5.77 (d, J=
3.9 Hz, 1H), 6.11 (td, J=0.8, 3.2 Hz, 1H), 6.32 (dd, J=1.8, 3.2 Hz, 1H),
6.90 (d, J=8.8 Hz, 2H), 7.35 (d, J=8.4 Hz, 2H), 7.39 ppm (dd, J=0.8,
1.8 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d=55.3, 69.8, 107.2, 110.2,
113.8 (2C), 127.9 (2C), 133.1, 142.4, 156.2, 159.4 ppm. These data are
consistent with the literature.[26]
75 MHz): d=119.0, 122.1, 125.6, 136.7, 145.9, 149.6, 152.3 ppm. These
data are consistent with the literature.[33]
4,6-Di(thiophen-2-yl)pyrimidine (3i): Yellow solid; m.p. 1428C; 1H NMR
(CDCl3, 300 MHz): d=7.19 (dd, J=3.8, 5.0 Hz, 2H), 7.55 (dd, J=1.1,
5.0 Hz, 2H), 7.81 (d, J=1.4 Hz, 1H), 7.84 (dd, J=1.1, 3.8 Hz, 2H),
9.05 ppm (d, J=1.4 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d=109.0,
127.5 (2C), 128.6 (2C), 130.4 (2C), 142.3, 159.2, 159.3 ppm. These data
are consistent with the literature.[34]
2,6-Di(thiophen-2-yl)pyrazine (3j): Yellow solid; m.p. 1858C; 1H NMR
(CDCl3, 300 MHz): d=7.16 (dd, J=3.7, 5.1 Hz, 2H), 7.49 (dd, J=1.1,
5.1 Hz, 2H), 7.73 (dd, J=1.1, 3.7 Hz, 2H), 8.75 ppm (s, 2H); 13C NMR
(CDCl3, 75 MHz): d=126.1 (2C), 128.4 (2C), 129.2 (2C), 137.9 (2C),
141.4, 147.5 ppm. These data are consistent with the literature.[35] The
structure was identified unequivocally by X-ray structure analysis from
crystals obtained by evaporating a CH2Cl2 solution.
[2-(4-Methoxybenzyloxy)pyridin-3-yl](4-methoxyphenyl)methanone (4d):
1
Yellow liquid; H NMR (CDCl3, 300 MHz): d=3.77 (s, 3H), 3.87 (s, 3H),
5.31 (s, 2H), 6.75 (d, J=8.8 Hz, 2H), 6.88 (d, J=9.0 Hz, 2H), 7.00 (dd,
J=5.0, 7.3 Hz, 1H), 7.08 (d, J=8.8 Hz, 2H), 7.72 (dd, J=2.0, 7.3 Hz,
1H), 7.74 (d, J=9.0 Hz, 2H), 8.30 ppm (dd, J=2.0, 5.0 Hz, 1H);
13C NMR (CDCl3, 75 MHz): d=55.2, 55.5, 67.2, 113.5 (2C), 113.6 (2C),
116.7, 123.3, 128.9 (2C), 129.0, 130.4 (2C), 132.1, 138.8, 148.9, 159.0,
160.4, 163.7, 193.5 ppm. HRMS (ESI) calcd for C21H19NO4 [M+Na]+:
372.1212; found: 372.1215.
1
3,6-Di(thiophen-2-yl)pyridazine (3k): Yellow solid; m.p. 1728C; H NMR
(CDCl3, 300 MHz): d=7.15 (dd, J=3.7, 5.0 Hz, 2H), 7.48 (dd, J=1.1,
5.0 Hz, 2H), 7.65 (dd, J=1.1, 3.7 Hz, 2H), 7.74 ppm (s, 2H); 13C NMR
(CDCl3, 75 MHz): d=122.6 (2C), 126.1 (2C), 128.2 (2C), 129.4 (2C),
140.8, 153.5 ppm. These data are consistent with the literature.[36]
4-(Pyridin-2-yl)pyrimidine (5g): White solid; m.p. 78–808C; 1H NMR
(CDCl3, 300 MHz): d=7.41 (ddd, J=1.2, 4.8, 7.6 Hz, 1H), 7.87 (td, J=
1.8, 7.7 Hz, 1H), 8.36 (dd, J=1.4, 5.3 Hz, 1H), 8.48 (dt, J=1.1, 8.0 Hz,
1H), 8.72 (ddd, J=0.9, 1.7, 4.8 Hz, 1H), 8.86 (d, J=5.3 Hz, 1H),
9.28 ppm (d, J=1.3 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d=117.4,
121.7, 125.5, 137.2, 149.6, 153.7, 158.0, 158.7, 162.7 ppm. These data are
consistent with the literature.[37]
4,4’-Bipyrimidine (5h): Yellow liquid; 1H NMR (CDCl3, 300 MHz): d=
8.44 (dd, J=1.5, 5.0 Hz, 2H), 8.97 (d, J=5.0 Hz, 2H), 9.36 ppm (d, J=
1.5 Hz, 2H); 13C NMR (CDCl3, 75 MHz): d=118.0, 158.9, 159.1,
160.8 ppm. These data are consistent with the literature.[37,38]
4-(Furan-2-yl)benzonitrile (6i): White solid; m.p. 54–568C; 1H NMR
(CDCl3, 300 MHz): d=6.53 (dd, J=1.8, 3.5 Hz, 1H), 6.81 (dd, J=0.7,
3.5 Hz, 1H), 7.54 (dd, J=0.7, 1.8 Hz, 1H), 7.65 (d, J=8.8 Hz, 2H),
7.74 ppm (d, J=8.8 Hz, 2H); 13C NMR (CDCl3, 75 MHz): d=108.1,
110.2, 112.2, 118.9, 123.9 (2C), 132.5 (2C), 134.6, 143.6, 151.9 ppm. These
data are consistent with the literature.[39]
2,5-Di(4-cyanophenyl)furan (6j): Yellow solid; m.p.>2508C; 1H NMR
(CDCl3, 300 MHz): d=6.95 (s, 2H), 7.71 (d, J=8.8 Hz, 4H), 7.83 ppm (d,
J=8.8 Hz, 4H); 13C NMR (CDCl3, 75 MHz): d=110.6 (2C), 110.9 (2C),
118.7 (2C), 124.1 (4C), 132.7 (4C), 133.8 (2C), 152.8 ppm (2C). These
data are consistent with the literature.[40]
2,2’-Bifuran: Colorless liquid; 1H NMR (CDCl3, 300 MHz): d=6.45 (dd,
J=1.8, 3.4 Hz, 2H), 7.55 (d, J=3.1 Hz, 2H), 7.41 ppm (d, J=1.8 Hz,
2H); 13C NMR (CDCl3, 75 MHz): d=105.0 (2C), 111.3 (2C), 141.7 (2C),
146.6 ppm (2C). These data are consistent with the literature.[41]
The preparation of 2-iodoanisole (1b),[42] 2-iodobenzonitrile (2b),[42] 2,5-
diiodothiophene (3b’),[42] 4-iodopyrimidine (5b),[42] 5-iodopyrimidine
(5b’),[10c] (2-methoxyphenyl)[4-(trifluoromethyl)phenyl]methanol (1c),[12]
2-(phenylthio)anisole (1e),[12] 2-allylanisole (1 f),[12] 2-allylbenzonitrile
(2 f),[12] 2-(thiophen-2-yl)pyridine (3g),[12] 2-fluoro-3-(pyridin-2-yl)pyri-
dine (4g),[12] and 2-(4-methoxyphenyl)furan (6k)[43] has been previously
described.
(4-Methoxyphenyl)(pyrimidin-4-yl)methanone (5d): Inseparable mixture
with reduced aldehyde. 1H NMR (CDCl3, 300 MHz): d=3.91 (s, 3H),
7.00 (d, J=9.0 Hz, 2H), 7.88 (dd, J=1.4, 5.1 Hz, 1H), 8.15 (d, J=9.0 Hz,
2H), 9.00 (d, J=5.1 Hz, 1H), 9.38 ppm (d, J=1.4 Hz, 1H); 13C NMR
(CDCl3, 75 MHz): d=55.3, 113.9 (2C), 120.5, 127.6, 133.5 (2C), 157.9,
158.7, 162.0, 164.3, 190.4 ppm; HRMS (ESI) calcd for C12H11N2O2:
215.0821 [M+H]+ and 237.0640 [M+Na]+; found: 215.0833 [M+H]+ and
237.0639 [M+Na]+.
N-(4-Methoxybenzoyl)-2,2,6,6-tetramethylpiperidine (7): Inseparable
mixture with aldehyde. 1H NMR (CDCl3, 300 MHz): d=1.34 (s, 12H),
1.76 (s, 6H), 3.81 (s, 3H), 6.84 (d, J=8.8 Hz, 2H), 7.4 ppm (d, J=8.8 Hz,
2H); 13C NMR (CDCl3, 75 MHz): d=15.1, 30.5 (2C), 37.1 (2C), 55.2
(2C), 56.3, 113.0 (2C), 129.6 (2C), 135.8, 160.7, 177.1 ppm. These data
are consistent with the literature.[27]
2-(Phenylthio)benzonitrile (2e): Yellow liquid; 1H NMR (CDCl3,
300 MHz): d=7.13 (ddd, J=0.4, 1.1, 8.1 Hz, 1H), 7.26 (dt, J=1.2, 7.6 Hz,
1H), 7.39 (m, 2H), 7.40 (m, 2H), 7.48 (m, 2H), 7.64 ppm (m, 1H);
13C NMR (CDCl3, 75 MHz): d=112.9, 116.9, 126.4, 128.9, 129.7 (2C),
129.9, 131.8, 132.7, 133.5 (2C), 133.6, 142.3 ppm. These data are consis-
tent with the literature.[28]
2-(Phenylthio)furan (6e): Colorless liquid; 1H NMR (CDCl3, 300 MHz):
d=6.57 (dd, J=2.0, 3.2 Hz, 1H), 6.84 (dd, J=0.8, 3.2 Hz, 1H), 7.23–7.28
(m, 3H), 7.33 (m, 2H), 7.67 ppm (dd, J=0.9, 2.0 Hz, 1H); 13C NMR
(CDCl3, 75 MHz): d=111.9, 119.5, 126.3, 127.5 (2C), 129.0 (2C), 136.3,
143.1, 146.5 ppm. These data are consistent with the literature.[29]
2-(4-Methoxyphenyl)pyridine (1g): Colorless liquid; 1H NMR (CDCl3,
300 MHz): d=3.86 (s, 3H), 7.00 (dd, J=0.9, 8.3 Hz, 1H), 7.08 (dt, J=1.1,
7.5 Hz, 1H), 7.21 (ddd, J=1.3, 4.9, 7.4 Hz, 1H), 7.38 (ddd, J=1.8, 7.4,
8.3 Hz, 1H), 7.71 (ddd, J=1.9, 7.4, 8.0 Hz, 1H), 7.76 (dd, J=1.8, 7.6 Hz,
1H), 7.81 (td, J=1.1, 8.0 Hz, 1H), 8.71 ppm (ddd, J=0.9, 1.8, 4.9 Hz,
1H); 13C NMR (CDCl3, 75 MHz): d=55.6, 111.3, 121.0, 121.7, 125.1,
129.0, 129.9, 131.1, 135.7, 149.3, 156.1, 156.9 ppm. These data are consis-
tent with the literature.[30]
6-(2-Methoxyphenyl)-2,2’-bipyridine (1h):[31] Inseparable mixture with
1g. 1H NMR (CDCl3, 300 MHz): d=3.89 (s, 3H), 7.06 (d, J=1.1 Hz,
1H), 7.13 (ddd, J=1.1, 7.5, 7.5 Hz, 1H), 7.30 (ddd, J=1.2, 4.8, 7.5 Hz,
1H), 7.41 (dd, J=1.8, 8.2 Hz, 1H), 7.80–7.85 (m, 2H), 7.92 (dd, J=1.1,
7.9 Hz, 1H), 8.01 (dd, J=1.8, 7.6 Hz, 1H), 8.34 (dd, J=1.1, 7.6 Hz, 1H),
8.58 (ddd, J=1.1, 1.1, 8.0 Hz, 1H), 8.70 ppm (ddd, J=0.9, 1.8, 5.0 Hz,
1H); 13C NMR (CDCl3, 75 MHz): d=55.6, 111.5, 118.8, 121.3, 123.5,
125.2, 129.0, 129.1, 129.9, 131.4, 136.5, 136.8, 149.0, 155.0, 155.5, 156.5,
157.2 ppm.
2-(Furan-2-yl)pyridine (6g):[32] Colorless liquid; 1H NMR (CDCl3,
300 MHz): d=6.53 (m, 1H), 7.06 (d, J=3.3 Hz, 1H), 7.15 (m, 1H), 7.53
(m, 1H), 7.70 (m, 2H), 8.60 ppm (d, J=3.8 Hz, 1H); 13C NMR (CDCl3,
75 MHz): d=108.5, 111.9, 118.5, 121.8, 136.5, 143.2, 149.2, 149.5,
153.4 ppm.
2,5-Di(pyridin-2-yl)thiophene (3h): Yellow solid; m.p. 1408C; 1H NMR
(CDCl3, 300 MHz): d=7.17 (ddd, J=2.6, 4.9, 5.9 Hz, 2H), 7.63 (s, 2H),
7.66–7.70 (m, 4H), 7.60 ppm (dt, J=1.5, 4.9 Hz, 2H); 13C NMR (CDCl3,
Acknowledgements
The authors gratefully acknowledge the financial support of Rꢀgion Bre-
tagne (to K.S.) and Agence Nationale de la Recherche (ACTIVATE pro-
gram) (to K.S. and M.U.). We thank Sourisak Sinbandhit for his contribu-
tion to this study. The calculations were performed by using the RIKEN
Cluster of Clusters (RICC) facility.
Chem. Eur. J. 2010, 16, 8191 – 8201
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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