C–H Bond Functionalization of Arylpyrimidines by RuII Catalysis
(dd, J = 7.2, 8.1 Hz, 1 H, Ar), 8.41 (d, J5,6 = 5.1 Hz, 1 H, 6-Pym), CDCl3): δ = 2.90 (s, 12 H, 4 Me), 6.53 (AAЈBBЈ, J = 8.7 Hz, 4 H,
8.94 (d, J2,5 = 1.2 Hz, 1 H, 2-Pym) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 111.0, 118.3, 123.7, 129.6, 130.1, 130.2, 131.8, 135.7,
140.1, 145.0, 156.2, 158.2, 165.4 ppm. HRMS (ESI+): calcd. for
C24H15N4, [M + H]+ 359.1297; found 359.1289.
Ar), 6.92 (dd, J2,5 = 1.5 Hz, J5,6 = 5.2 Hz, 1 H, 5-Pym), 6.94
(AAЈBBЈ, J = 8.7 Hz, 4 H, Ar), 7.376 (d, J = 8.4 Hz, 1 H, Ar),
7.378 (d, J = 6.6 Hz, 1 H, Ar), 7.48 (dd, J = 6.6, 8.4 Hz, 1 H, Ar),
8.35 (d, J5,6 = 5.2 Hz, 1 H, 6-Pym), 8.97 (d, J2,5 = 1.5 Hz, 1 H, 2-
Pym) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 40.4, 111.9, 124.4,
128.8, 128.9, 130.2, 135.7, 141.6, 149.1, 155.3, 158.0, 168.3 (one
signal is hidden) ppm. HRMS (ESI+): calcd. for C26H27N4 [M +
H]+ 395.2236; found 395.2234.
2Ј-(Pyrimidin-4-yl)biphenyl-2-carbonitrile (2f) and 2Ј-Pyrimidin-4-
yl-1,1Ј:3Ј,1ЈЈ-terphenyl-2,2ЈЈ-dicarbonitrile (3f): The representative
procedure was applied by using 2-bromobenzonitrile (191 mg,
1.05 mmol), see Table 2, Entry 6. Radial chromatography (petro-
leum ether/EtOAc, 5:1) afforded 2f (41 mg, 32%) and 3f (34 mg,
19%). Data for 2f: 1H NMR (300 MHz, CDCl3): δ = 7.08 (dd, J2,5
= 1.4 Hz, J5,6 = 5.2 Hz, 1 H, 5-Pym), 7.25 (dd, J = 1.4, 7.7 Hz, 1
H, Ar), 7.39 (dt, J = 1.4, 7.7 Hz, 1 H, Ar), 7.45–7.53 (m, 2 H, Ar),
7.57–7.63 (m, 2 H, Ar), 7.65 (dd, J = 1.4, 7.7 Hz, 1 H, Ar), 7.79
4-(3,3ЈЈ-Dimethoxy-1,1Ј:3Ј,1ЈЈ-terphenyl-2Ј-yl)pyrimidine (3i): The
representative procedure was applied by using 3-bromoanisol
(196 mg, 1.05 mmol), see Table 2, Entry 9. Radial chromatography
(petroleum ether/EtOAc, 5:1) afforded 3i (164 mg, 89%). 1H NMR
(300 MHz, CDCl3): δ = 3.63 (s, 6 H, 2 Me), 6.63 (dd, J = 1.6,
2.5 Hz, 2 H, Ar), 6.69 (ddd, J = 0.9, 1.6, 7.6 Hz, 2 H, Ar), 6.74
(m, 1 H, Ar), 8.53 (d, J5,6 = 5.2 Hz, 1 H, 6-Pym), 9.08 (d, J2,5
=
1.4 Hz, 1 H, 2-Pym) ppm. 13C NMR (75.5 MHz, CDCl3): δ =
112.6, 117.9, 121.6, 127.7, 129.3, 129.9, 130.3, 131.06, 131.15,
132.4, 133.0, 137.2, 137.4, 144.8, 156.4, 158.6, 165.6 ppm. HRMS
(ESI+): calcd. for C17H12N3 [M + H]+ 258.1031; found 258.1029.
Data for 3f: 1H NMR (300 MHz, CDCl3): δ = 6.95 (br., 1 H, 5-
Pym), 7.16 (br., 2 H, Ar), 7.28–7.43 (m, 4 H, Ar), 7.55–7.73 (m, 5
H, Ar), 8.32 (d, J5,6 = 5.2 Hz, 1 H, 6-Pym), 8.82 (d, J2,5 = 1.5 Hz,
1 H, 2-Pym) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 112.9, 117.9,
123.8, 127.8, 129.2, 130.9, 131.2, 132.0, 132.7, 137.0, 138.1, 144.0,
155.8, 157.9, 164.9 ppm. HRMS (ESI+): calcd. for C24H15N4 [M
+ H]+ 359.1297; found 359.1296.
(ddd, J = 0.9, 2.5, 8.4 Hz, 2 H, Ar), 6.92 (dd, J2,5 = 1.5 Hz, J5,6
=
5.2 Hz, 1 H, 5-Pym), 7.10 (t, J = 7.6 Hz, 2 H, Ar), 7.465 (d, J =
8.7 Hz, 1 H, Ar), 7.468 (d, J = 6.3 Hz, 1 H, Ar), 7.55 (dd, J = 6.3,
8.7 Hz, 1 H, Ar), 8.35 (d, J5,6 = 5.2 Hz, 1 H, 6-Pym), 8.94 (d, J2,5
= 1.5 Hz, 1 H, 2-Pym) ppm. 13C NMR (75.5 MHz, CDCl3): δ =
55.0, 112.9, 114.8, 122.0, 124.0, 128.9, 129.0, 129.5, 135.9, 141.5,
142.0, 155.5, 157.9, 159.0, 167.2 ppm. HRMS (ESI+): calcd. for
C24H21N2O2 [M + H]+ 369.1603; found 369.1610.
4-[2,6-Bis(thiophen-2-yl)phenyl]pyrimidine (3j): The representative
procedure was applied by using 2-bromothiophene (171 mg,
1.05 mmol), see Table 2, Entry 10. Radial chromatography (petro-
leum ether/EtOAc, 7:1) afforded 3j (109 mg, 68%). 1H NMR
(300 MHz, CDCl3): δ = 6.66 (dd, J = 1.2, 3.5 Hz, 2 H, thiophene),
6.84 (dd, J = 3.5, 5.1 Hz, 2 H, thiophene), 7.09 (dd, J2,5 = 1.5 Hz,
J5,6 = 5.1 Hz, 1 H, 5-Pym), 7.19 (dd, J = 1.2, 5.1 Hz, 2 H, thio-
phene), 7.50 (dd, J = 6.1, 9.0 Hz, 1 H, Ar), 7.567 (d, J = 6.1 Hz, 1
H, Ar), 7.572 (d, J = 9.0 Hz, 1 H, Ar), 8.50 (d, J5,6 = 5.1 Hz, 1 H,
6-Pym), 9.13 (d, J2,5 = 1.5 Hz, 1 H, 2-Pym) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 123.7, 126.2, 127.0, 127.6, 129.1, 130.5,
134.3, 136.4, 141.6, 156.2, 158.3, 166.8 ppm. HRMS (ESI+): calcd.
for C18H13N2S2 [M + H]+ 321.0520; found 321.0525.
4-(4Ј-Methoxybiphenyl-2-yl)pyrimidine (2g) and 4-(4,4ЈЈ-Dimethoxy-
1,1Ј:3Ј,1ЈЈ-terphenyl-2Ј-yl)pyrimidine (3g): The representative pro-
cedure was applied by using 4-bromoanisol (196 mg, 1.05 mmol),
see Table 2, Entry 7. Radial chromatography (petroleum ether/
EtOAc, 5:1) afforded 2g (38 mg, 29%) and 3g (66 mg, 36%). Data
1
for 2g: H NMR (300 MHz, CDCl3): δ = 3.80 (s, 3 H, Me), 6.82
(AAЈBBЈ, J = 9.0 Hz, 2 H, Ar), 6.85 (dd, J2,5 = 1.3 Hz, J5,6
=
5.4 Hz, 1 H, 5-Pym), 7.08 (AAЈBBЈ, J = 9.0 Hz, 2 H, Ar), 7.41–
7.55 (m, 3 H, Ar), 7.76 (m, 1 H, Ar), 8.40 (d, J5,6 = 5.4 Hz, 1 H,
6-Pym), 9.24 (d, J2,5 = 1.3 Hz, 1 H, 2-Pym) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 55.2, 113.9, 122.4, 127.5, 129.9, 130.3,
130.68, 130.75, 132.8, 136.6, 140.7, 155.5, 159.0, 159.1, 166.6 ppm.
HRMS (ESI+): calcd. for C17H15N2O [M + H]+ 263.1184; found
4-[2-(Pyrimidin-5-yl)phenyl]pyrimidine (2k) and 5,5Ј-[-2-(Pyrimidin-
4-yl)-1,3-phenylene]dipyrimidine (3k): The representative procedure
was applied by using 5-bromopyrimidine (167 mg, 1.05 mmol), see
Table 2, Entry 11. Radial chromatography (petroleum ether/
EtOAc, 5:1Ǟ3:1) afforded 2k (28 mg, 24%) and 3k (8 mg, 5%).
1
263.1181. Data for 3g: H NMR (300 MHz, CDCl3): δ = 3.74 (s, 6
H, 2 Me), 6.72 (AAЈBBЈ, J = 8.7 Hz, 4 H, Ar), 6.87 (dd, J2,5
=
Data for 2k: 1H NMR (300 MHz, CDCl3): δ = 7.14 (dd, J2,5
1.5 Hz, J5,6 = 5.1 Hz, 1 H, 5-Pym), 7.46 (m, 1 H, Ar), 7.63 (m, 2
H, Ar), 7.74 (m, 1 H, Ar), 8.56 (s, 2 H, 4,6-PymЈ), 8.63 (d, J5,6
=
1.2 Hz, J5,6 = 5.1 Hz, 1 H, 5-Pym), 6.99 (AAЈBBЈ, J = 8.7 Hz, 4
H, Ar), 7.402 (d, J = 8.2 Hz, 1 H, Ar), 7.404 (d, J = 6.9 Hz, 1 H,
Ar), 7.51 (dd, J = 6.9, 8.2 Hz, 1 H, Ar), 8.34 (d, J5,6 = 5.1 Hz, 1
H, 6-Pym), 8.94 (d, J2,5 = 1.2 Hz, 1 H, 2-Pym) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 55.1, 113.3, 124.2, 128.9, 129.3, 130.5,
133.1, 136.0, 141.2, 155.5, 158.0, 158.4, 167.5 ppm. HRMS (ESI+):
calcd. for C24H21N2O2 [M + H]+ 369.1603; found 369.1604.
=
5.1 Hz, 1 H, 6-Pym), 9.14 (s, 2 H, 2-Pym and 2-PymЈ) ppm. 13C
NMR (75.5 MHz, CDCl3): δ = 121.6, 129.5, 130.4, 130.8, 130.9,
133.7, 134.5, 137.3, 156.6, 157.0, 157.2, 158.9, 165.4 ppm. HRMS
(ESI+): calcd. for C14H11N4, [M + H]+ 235.0984; found 235.0988.
Data for 3k: 1H NMR (300 MHz, CDCl3): δ = 6.87 (dd, J2,5
=
4-[4Ј-(Dimethylamino)biphenyl-2-yl]pyrimidine (2h) and 4-[4,4ЈЈ-
Bis(dimethylamino)-1,1Ј:3Ј,1ЈЈ-terphenyl-2Ј-yl]pyrimidine (3h): The
representative procedure was applied by using 4-bromo-N,N-di-
methylaniline (210 mg, 1.05 mmol), see Table 2, Entry 8. Radial
chromatography (petroleum ether/EtOAc, 5:1) afforded 2h (14 mg,
10%) and 3h (124 mg, 63%). Data for 2h: 1H NMR (300 MHz,
CDCl3): δ = 2.95 (s, 6 H, 2 Me), 6.63 (AAЈBBЈ, J = 8.7 Hz, 2 H,
Ar), 6.88 (dd, J2,5 = 1.3 Hz, J5,6 = 5.4 Hz, 1 H, 5-Pym), 7.02
1.3 Hz, J5,6 = 5.1 Hz, 1 H, 5-Pym), 7.568 (d, J = 8.2 Hz, 1 H, Ar),
7.569 (d, J = 7.3 Hz, 1 H, Ar), 7.76 (dd, J = 7.3, 8.2 Hz, Ar), 8.48
(d, J5,6 = 5.1 Hz, 1 H, 6-Pym), 8.54 (s, 4 H, 4,6-PymЈ), 9.05 (d,
J2,5 = 1.3 Hz, 1 H, 2-Pym), 9.09 (s, 2 H, 2-PymЈ) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 123.7, 130.2, 131.1, 133.8, 135.1, 137.0,
156.6, 157.0, 157.5, 158.8, 164.3 ppm. HRMS (ESI+): calcd. for
C18H13N6 [M + H]+ 313.1202; found 313.1192.
(AAЈBBЈ, J = 8.7 Hz, 2 H, Ar), 7.40–7.52 (m, 3 H, Ar), 7.75 (m, 1 4-[2-(Pyridine-3-yl)phenyl]pyrimidine (2l) and 4-[2,6-Bis(pyridine-3-
H, Ar), 8.38 (d, J5,6 = 5.4 Hz, 1 H, 6-Pym), 9.25 (d, J2,5 = 1.3 Hz, yl)phenyl]pyrimidine (3l): The representative procedure was applied
1 H, 2-Pym) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 40.4, 112.2, by using 3-bromopyridine (166 mg, 1.05 mmol), see Table 2, En-
122.5, 127.0, 128.1, 129.8, 130.3, 130.4, 130.7, 136.4, 141.3, 149.7,
155.4, 159.1, 167.0 ppm. HRMS (ESI+): calcd. for C18H18N3 [M
try 12. After 48 h at 150 °C, radial chromatography (petroleum
ether/EtOAc, 5:1) afforded 2l (11 mg, 9%) and 3l (87 mg, 56%).
+ H]+ 267.1501; found 267.1503. Data for 3h: 1H NMR (300 MHz, Data for 2l: 1H NMR (300 MHz, CDCl3): δ = 6.94 (dd, J2,5
=
Eur. J. Org. Chem. 2011, 3474–3481
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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