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Organic & Biomolecular Chemistry
propen-1-one 1u (1.0 mmol) as a shiny brown solid (0.218 g, 2H), 7.55 (d, J = 8.1 Hz, 2H), 7.37 (d, J = 8.1 Hz, 2H), 7.31
84% yield); mp 244–247 °C; 1H NMR (400 MHz, DMSO-d6) δ (d, J = 7.9 Hz, 2H), 7.16 (d, J = 1.0 Hz, 1H), 6.91 (d, J = 8.9 Hz,
11.39 (br s, 1H, exchangeable with D2O), 7.87 (dd, J = 18.5, 3.1 2H), 3.87 (s, 3H), 2.48 (s, 3H), 2.43 (s, 3H); 13C NMR (125 MHz,
Hz, 2H), 7.71 (dd, J = 21.8, 4.9 Hz, 2H), 7.29 (s, 1H), 7.23–7.17 CDCl3) δ 160.8, 157.6, 156.1, 153.6, 144.9, 139.8, 134.6, 134.5,
(m, 2H), 6.65 (s, 1H); 13C NMR (100 MHz, DMSO-d6) δ 164.1, 130.3, 129.9, 129.5, 128.8, 128.3, 126.9, 115.9, 113.9, 110.5,
145.2, 140.6, 129.2, 128.9, 128.8, 127.4, 126.8, 115.9, 104.7 55.4, 21.7, 21.3; MS (ESI): m/z = 445.3.
(13C NMR (100 MHz, DMSO-d6) δ 164.1, 145.2, 140.6, 129.2,
6-(Benzo[d][1,3]dioxol-5-yl)-4-phenylpyridin-2-yl
4-methyl
128.9, 128.8, 127.4, 126.8, 115.9, 104.7); IR (KBr): 3448.61, benzenesulfonate (6d). 1H NMR (400 MHz, CDCl3) δ 7.96 (d,
1637.58 cm−1; HRMS (ESI): calcd for C13H10NOS2 [M + H]+, J = 8.3 Hz, 2H), 7.72 (s, 1H), 7.64 (dd, J = 7.8, 1.5 Hz, 2H), 7.50
260.0198; found: 260.0217.
Ethyl 2-nitro-5-oxo-3,5-diphenylpentanoate
(d, J = 7.6 Hz, 3H), 7.39 (d, J = 8.1 Hz, 2H), 7.31 (dd, J = 8.2, 1.7
(3). White Hz, 1H), 7.20 (s, 1H), 7.11 (d, J = 1.6 Hz, 1H), 6.82 (d, J = 8.2
solid (30% yield); mp 114–116 °C (lit.10 116–117 °C); H NMR Hz, 1H), 6.02 (s, 2H), 2.49 (s, 3H); 13C NMR (125 MHz, CDCl3)
1
(400 MHz, CDCl3)
δ
7.92–7.81 (m, 2H), 7.56–7.49 δ 156.5, 154.9, 152.7, 147.8, 147.1, 144.1, 136.3, 133.4, 130.9,
(m, 1H), 7.43–7.38 (m, 2H), 7.29–7.20 (m, 5H), 5.55 (d, J = 128.6, 128.1, 127.7, 126.0, 120.0, 115.3, 110.1, 107.1, 106.3,
8.0 Hz, 1H), 4.53–4.46 (m, 1H), 4.24–4.03 (m, 2H), 3.74–3.51 (m, 100.3, 20.6; MS (ESI): m/z = 445.1.
2H), 1.09 (t, J = 8.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 196.2,
6-Phenyl-4-(3,4,5-trimethoxyphenyl)pyridin-2-yl
163.2, 136.9, 136.3, 133.4, 128.9, 128.7, 128.4, 128.3, 128.1, benzenesulfonate (6e). 1H NMR (400 MHz, CDCl3) δ 7.99 (d,
128.0, 91.6, 63.0, 41.8, 40.4, 13.6; MS (ESI): m/z = 342 (M + H)+.
J = 8.2 Hz, 2H), 7.77 (s, 1H), 7.76–7.72 (m, 2H), 7.43–7.40 (m,
4-methyl
3,4-Dihydro-3-nitro-4,6-diphenylpyridin-2(1H)-one (4). Shiny 3H), 7.38 (d, J = 8.2 Hz, 2H), 7.21 (s, 1H), 6.83 (s, 2H), 3.96 (s,
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yellow solid (23% yield); mp 244–245 °C; H NMR (400 MHz, 6H), 3.92 (s, 3H), 2.49 (s, 3H); 13C NMR (125 MHz, CDCl3)
DMSO-d6) δ 10.58 (br s, 1H, exchangeable with D2O), 7.85–7.56 δ 157.6, 156.4, 153.8, 153.7, 145.1, 139.3, 137.4, 134.4, 133.0,
(m, 3H), 7.41–7.36 (m, 7H), 6.27 (d, J = 12 Hz, 1H), 5.46 (s, 1H), 129.6, 128.8, 128.6, 127.0, 116.9, 111.5, 104.3, 60.9, 56.3, 21.7;
4.67 (d, J = 16 Hz, 1H); 13C NMR (100 MHz, DMSO-d6) δ 162.3, MS (ESI): m/z = 491.4.
138.3, 136.7, 133.19, 128.9, 128.8, 128.4, 127.83, 126.7, 125.6,
6-(4-Methoxyphenyl)-4-(3,4,5-trimethoxyphenyl)pyridin-2-yl
105.0, 89.6, 43.2; MS (ESI): m/z = 295 (M + H)+.
4-methylbenzenesulfonate (6f). 1H NMR (400 MHz, CDCl3)
Synthesis of 4,6-diarylated/heterylated pyridin-2-yl sulfo- δ 7.82 (d, J = 8.3 Hz, 2H), 7.59 (s, 1H), 7.57 (d, J = 1.9 Hz, 2H),
nates 6a–h (general procedure B). 4,6-Disubstituted pyridin-2 7.23 (d, J = 8.1 Hz, 2H), 6.97 (d, J = 1.0 Hz, 1H), 6.77 (d, J = 8.9
(1H)-ones (100 mg, 0.404 mmol), p-toluenesulfonyl chloride Hz, 2H), 6.69 (s, 2H), 3.81 (s, 6H), 3.79 (s, 3H), 3.70 (s, 3H),
(92.3 mg, 0.485 mmol), triethylamine (112.2 µL, 0.809 mmol) 2.33 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 160.9, 157.5, 156.2,
and 4-(N,N-dimethylamino) pyridine (1.3 mg, 0.012 mmol) 153.7, 145.0, 139.3, 134.5, 133.1, 130.0, 129.6, 128.7, 128.3,
were added into a 25 mL round-bottom flask containing 1 mL 115.9, 113.9, 110.6, 104.4, 60.9, 56.3, 55.3, 21.7; MS (ESI): m/z =
of analytical-grade CH2Cl2. After stirring at 25 °C for 10–15 h, 521.2.
the reaction mixture was diluted with water (50 mL) and
4-(Furan-2-yl)-6-phenylpyridin-2-yl 4-methylbenzenesulfonate
extracted with Et2O (50 mL × 2). The organic extracts were (6g). 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 8.3 Hz, 2H),
dried over Na2SO4 and then concentrated on a rotary evapor- 7.87 (s, 1H), 7.73 (dd, J = 6.7, 3.0 Hz, 2H), 7.58 (d, J = 1.2 Hz,
ator. The resulting residue was purified by silica gel flash 1H), 7.42–7.39 (m, 3H), 7.36 (d, J = 8.2 Hz, 2H), 7.32–7.21
chromatography (ethyl acetate/hexane 1 : 5 to 1 : 3) to afford (m, 1H), 6.95 (d, J = 3.4 Hz, 1H), 6.56 (dd, J = 3.4, 1.8 Hz,
the title compound (80–90%) (6a–h).
1H), 2.47 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 157.7,
4,6-Diphenylpyridin-2-yl 4-methylbenzenesulfonate (6a). 1H 156.6, 150.5, 145.0, 144.3, 142.3, 137.4, 134.3, 129.6, 129.6,
NMR (400 MHz, CDCl3) δ 7.98 (d, J = 8.2 Hz, 2H), 7.83 (s, 1H), 128.8, 128.6, 126.9, 112.9, 112.3, 109.9, 107.7, 21.7; MS (ESI):
7.76 (dd, J = 6.5, 2.9 Hz, 2H), 7.65 (d, J = 6.4 Hz, 2H), 7.50 m/z = 391.3.
(m, 3H), 7.42–7.39 (m, 3H), 7.37 (d, J = 8.2 Hz, 2H), 7.25
4,6-Di(thiophen-2-yl)pyridin-2-yl 4-methylbenzenesulfonate
(s, 1H), 2.48 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 157.7, (6h). 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.3 Hz, 2H), 7.66
156.5, 153.8, 145.0, 137.5, 137.4, 134.4, 129.6, 129.6, 129.2, (d, J = 1.0 Hz, 1H), 7.56–7.50 (m, 2H), 7.49–7.44 (m, 1H), 7.39
128.8, 128.6, 127.1, 127.0, 117.0, 111.6, 21.7; MS (ESI): m/z = (dd, J = 8.1, 4.3 Hz, 3H), 7.18–7.14 (m, 1H), 7.14 (d, J = 1.0 Hz,
401.2.
1H), 7.08 (dd, J = 4.9, 3.8 Hz, 1H), 2.47 (s, 3H); 13C NMR
6-(4-Chlorophenyl)-4-phenylpyridin-2-yl 4-methyl benzene (125 MHz, CDCl3) δ 157.6, 152.0, 146.4, 145.1, 142.9, 139.9,
sulfonate (6b). 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.3 Hz, 134.1, 129.6, 128.9, 128.6, 128.44, 128.0, 126.3, 125.8, 113.6,
2H), 7.71 (s, 1H), 7.67 (dd, J = 6.6, 2.9 Hz, 2H), 7.52 (d, J = 8.5 109.3, 21.7; MS (ESI): m/z = 413.12.
Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.37–7.28 (m, 5H), 7.16 (s, 1H),
Synthesis of 2,4,6-triaryl/heteryl pyridine derivatives 7a–i
2.41 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 156.7, 155.7, 151.4, (general procedure C). A sealed tube (50.0 mL), fitted with a
144.1, 136.3, 134.9, 134.7, 133.3, 128.7, 128.5, 128.4, 127.8, septum, containing Pd(OAc)2 (7.2 mg, 0.1 mmol) and XPhos
127.6, 127.3, 125.9, 115.7, 110.4, 20.7; MS (ESI): m/z = 436.1.
(15.5 mg, 0.1 mmol) was evacuated and purged with nitrogen.
6-(4-Methoxyphenyl)-4-(4-methylphenyl)pyridin-2-yl 4-methyl 2,4-Diarylated pyridine-2-yl sulfonate (1.0 mmol), arylboronic
benzenesulfonate (6c). 1H NMR (400 MHz, CDCl3) δ 7.97 acid (1.2 mmol), NaOH (2.0 equiv.), and nBuOH/EtOH/H2O
(d, J = 8.3 Hz, 2H), 7.74 (d, J = 1.1 Hz, 1H), 7.71 (d, J = 8.9 Hz, (6/1/1, 1.0 mL) were added to the system and the reaction
Org. Biomol. Chem.
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