LETTER
Direct Alkenylation of 2-Methylquinolines with Aldehydes
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(10) General Procedure
To an 8 mL screw-capped reaction vial equipped with a
magnetic stirrer bar, CoCl2 (1.3 mg, 2.0 mol%), 2-methyl-
quinoline (0.5 mmol), aldehyde (1.0 mmol), and H2O (0.3
mL) were added. The resulting mixture was placed into a
preheated oil bath at 120 °C with vigorous stirring. After 24
h, the reaction mixture was removed from the oil bath,
allowed to cool to r.t. and poured into H2O (10 mL). The
mixture was then extracted with EtOAc (3 × 20 mL), washed
with brine (40 mL), dried over Na2SO4, filtered, and the
solvent removed under reduced pressure. The crude product
was then loaded onto a column of silica gel suspended in
hexane. Purification by flash chromatography (hexane–
EtOAc = 95:5, v/v) then gave the pure alkenylation product.
(E)-2-(4-Bromostyryl)quinoline (3ad)
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Pale yellow solid in 91% yield (141.8 mg). 1H NMR (400
MHz, CDCl3): δ = 8.08 (d, J = 8.4 Hz, 2 H), 7.76 (d, J = 8.0
Hz, 1 H), 7.70 (t, J = 7.62 Hz, 1 H), 7.62–7.58 (m, 2 H),
7.51–7.45 (m, 5 H), 7.35 (d, J = 16.4 Hz, 1 H). 13C NMR
(100 MHz, CDCl3): δ = 155.6, 148.3, 136.5, 135.5, 133.1,
132.0, 129.9, 129.7, 129.3, 128.7, 127.5, 127.4, 126.3,
122.6, 119.4. ESI-HRMS: m/z calcd for C17H13BrN [M + H]:
310.0231; found: 310.0234.
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Chem. Rev. 2012, 112, 2642.
(E)-2-[2-(Pyridin-3-yl)vinyl]quinoline (5ad)
Pale yellow solid in 86% yield (100.2 mg). 1H NMR (400
MHz, CDCl3): δ = 8.83 (s, 1 H), 8.54 (s, 1 H), 8.10 (dd, J1 =
8.4 Hz, J2 = 12.2 Hz, 2 H), 7.92 (d, J = 8.0 Hz, 1 H), 7.78–
7.61 (m, 4 H), 7.50 (t, J = 7.4 Hz, 1 H), 7.42 (d, J = 16.4 Hz,
1 H), 7.30 (dd, J1 = 5.2 Hz, J2 = 8.0 Hz 1 H). 13C NMR (100
MHz, CDCl3): δ = 155.2, 149.4, 149.2, 148.2, 136.6, 133.3,
132.3, 130.9, 130.6, 129.9, 129.3, 127.55, 127.52, 126.5,
123.7, 119.4. ESI-HRMS: m/z calcd for C16H13N2 [M + H]:
233.1078; found: 233.1075.
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(E)-8-Chloro-2-styrylquinoline (3da)
This compound was prepared in a similar procedure to the
general procedure with 5.0 mol% CoCl2 at 140 °C for 48 h
to afford a pale yellow solid in 84% yield (111.3 mg). 1H
NMR (400 MHz, CDCl3): δ = 8.09 (d, J = 8.8 Hz, 1 H), 7.81
(dd, J1 = 1.0 Hz, J2 = 7.4 Hz, 1 H), 7.75 (d, J = 16.4 Hz, 1 H),
7.70–7.64 (m, 4 H), 7.48–7.32 (m, 5 H). 13C NMR (100
MHz, CDCl3): δ = 156.6, 144.4, 136.6, 136.3, 135.3, 133.3,
129.8, 128.8, 128.75, 128.73, 128.5, 127.4, 126.6, 125.9,
120.0. ESI-HRMS: m/z calcd for C17H13ClN [M + H]:
266.0736; found: 266.0739.
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Synlett 2014, 25, 2049–2053