M. Yoshimatsu, M. Sakai, E. Moriura
FULL PAPER
C15H15O2SCl (294.80): calcd. C 61.11, H 5.13; found C 60.89, H
5.10.
(C–Cl), 535 cm–1. H NMR (500 MHz, CDCl3): δ = 3.86 (s, 3 H,
OMe), 6.58–6.60 (m, 1 H, 4-H), 6.94–6.98 (m, 2 H, 3-H and ArH),
7.37 (d, J = 3 Hz, 1 H, olefinic H), 7.69 (t, J = 1 Hz, 1 H, 5-H),
7.84–7.92 (m, 3 H, ArH) ppm. 13C NMR (100 MHz, CDCl3): δ =
55.41 (q), 112.25 (d), 114.12 (dϫ2), 120.57 (d), 125.70 (s), 126.65
(s), 132.95 (dϫ2), 137.98 (d), 147.14 (d), 150.91 (s), 161.35 (s),
176.86 (s) ppm. MS: m/z = 262 [M]+, 227 [M – Cl]+. C14H11O3Cl
(262.69): calcd. C 64.01, H 4.22; found C 63.72, H 4.26.
1
(E)-2-[2-Chloro-1-ethoxy-3-(p-methoxyphenyl)-3-hydroxyprop-1-en-
yl]furan (9h): To a THF (2.0 mL) solution of (E)-2-(2-chloro-1-
ethoxyethenyl)furan (2h)(95 mg, 0.55 mmol) was added nBuLi
(2.6 solution in n-hexane, 0.21 mL, 0.55 mmol) at –78 °C under
an Ar atmosphere. After stirring for 10 min, a THF (1.0 mL) solu-
tion of p-methoxybenzaldehyde (50 mg, 0.37 mmol) was added
dropwise to the mixture. The mixture was stirred for 10 min and
then poured into water (50 mL). The usual work up produced title
(Z)-2-[2-Chloro-1,1-diethoxy-3-(p-methoxyphenyl)prop-2-enyl]pyrid-
ine (10k). Typical Procedure: To an EtOH (2.0 mL) solution of 9k
(57 mg, 0.18 mmol) was added ethyl orthoformate (0.13 g,
0.89 mmol) and p-toluenesulfonic acid (3.00 mg, 0.02 mmol) at
room temperature. The mixture was stirred for 30 min and poured
into a saturated NaHCO3 (30.0 mL). The work up procedure af-
forded title compound 10k (46 mg, 74%) as a yellow oil. IR (KBr):
compound 9h (0.11 g, 65%) as a yellow oil. IR (KBr): ν = 3443
˜
(OH), 2932, 1612, 1511 (furyl), 1248, 1172, 1068, 1032 (C–O), 830,
748 (C–Cl) cm–1. 1H NMR (500 MHz, CDCl3): δ = 1.31 (t, J =
7 Hz, 3 H, Me), 2.84 (d, J = 7 Hz, 1 H, OH), 3.77 (s, 3 H, OMe),
3.79–3.89 (m, 2 H, OCH2), 6.15 (d, J = 7 Hz, 2 H, ArH), 6.46 (dd,
J = 2 and 3 Hz, 1 H, ArH), 6.86–6.88 (m, 3 H, ArH), 7.38 (d, J =
8 Hz, 2 H, ArH), 7.47 (d, J = 2 Hz, 1 H, ArH) ppm. 13C NMR
(100 MHz, CDCl3): δ = 15.17 (qϫ2), 55.14 (q), 68.54 (t), 69.53 (d),
111.11 (d), 113.59 (dϫ2), 113.85 (d), 124.04 (s), 127.10 (dϫ2),
132.94 (s), 142.62 (d), 142.92 (s), 146.51 (s) 158.96 (s) ppm. MS:
m/z = 303 [M – 5]+.
ν = 2982, 2937, 2896, 2363, 1603, 1510, 1285, 1250, 1184, 1069,
˜
833 cm–1. 1H NMR (500 MHz, CDCl3): δ = 1.28 (t, J = 7 Hz, 6 H,
Me), 3.36–3.42 (m, 2 H, OCH2), 3.53–3.60 (m, 2 H, OCH2), 3.80
(s, 3 H, OMe), 6.87 (d, J = 8 Hz, 2 H, ArH), 7.20 (dd, J = 5 and
8 Hz, 1 H, ArH), 7.55 (s, 1 H, olefinic H), 7.70–7.72 (m, 1 H, ArH),
7.71 (d, J = 8 Hz, 2 H, ArH), 7.86 (br. d, J = 8 Hz, 1 H, ArH), 8.63
(br. d, J = 6 Hz, 1 H, ArH) ppm. 13C NMR (100 MHz, CDCl3): δ
= 15.08 (qϫ2), 55.15 (q), 57.87 (tϫ2), 102.04 (s), 113.40 (dϫ2),
122.85 (d), 123.20 (d), 126.78 (d), 126.93 (s), 129.51 (s), 131.04
(dϫ2), 135.94 (d), 149.09 (d), 158.29 (s), 159.23 (s) ppm. MS: m/z
= 347 [M]+. C19H22ClNO3 (347.84): calcd. C 65.61, H 6.38, N 4.03;
found C 65.37, H 6.33, N 4.02.
(E)-2-[2-Chloro-1-ethoxy-3-hydroxy-3-(p-methoxyphenyl)prop-1-en-
yl]pyridine (9k): To a THF (4.0 mL) solution of (E)-2-(2-chloro-1-
ethoxyethenyl)pyridine (2k) (0.20 g, 1.09 mmol) was added nBuLi
(2.6 solution in n-hexane, 0.42 mL, 1.09 mmol) at –78 °C under
an Ar atmosphere. After stirring for 10 min, a THF (1.0 mL) solu-
tion of p-methoxybenzaldehyde (0.10 g, 0.73 mmol) was added
dropwise to the mixture. The mixture was stirred for 10 min and
then poured into water (50 mL). The usual work up produced title
Acknowledgments
compound 9k (0.14 g, 59%) as a yellow oil. IR (KBr): ν = 3422
˜
(OH), 3205, 1614, 1589, 1509, 1468, 1434, 1299, 1242, 1084,
750 cm–1. 1H NMR (500 MHz, CDCl3): δ = 1.24 (t, J = 7 Hz, 3 H,
Me), 3.59 (d, J = 4 Hz, 1 H, OH), 3.61–3.71 (m, 2 H, OCH2), 3.78
(s, 3 H, OMe), 6.29 (d, J = 4 Hz, 1 H, CHO), 6.89 (d, J = 9 Hz, 2
H, ArH), 7.24–7.27 (m, 1 H, ArH), 7.48 (d, J = 9 Hz, 2 H, ArH),
7.57 (d, J = 8 Hz, 1 H, ArH), 7.70–7.74 (m, 1 H, ArH), 8.68–8.69
(m, 1 H, ArH) ppm. 13C NMR (100 MHz, CDCl3): δ = 15.01 (q),
55.08 (q), 66.44 (t), 69.14 (d), 113.48 (dϫ2), 123.38 (d), 124.55 (s),
125.58 (d), 127.13 (dϫ2), 133.18 (s), 136.09 (d), 149.36 (d), 149.75
(s), 151. 78 (s), 158.81 (s) ppm. MS: m/z = 319 (small
[M]+). C17H18ClNO3 (319.79): calcd. C 63.85, H 5.67, N 4.38;
found C 63.68, H 5.63, N 4.35.
We thank Gifu University for financial support of part of this
work.
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(Z)-1-Chloro-2-phenylethenyl 2-Thienyl Ketone (10d). Typical Pro-
cedure: TMSOTf (72 mg, 0.32 mmol) was added dropwise to a
CH2Cl2 (2.0 mL) solution of 9d (84 mg, 0.032 mmol) at –78 °C un-
der an Ar atmosphere. The usual work up provided title compound
10d (70 mg, 87%) as a yellow oil. IR (KBr): ν = 1641, 1411 (thi-
˜
enyl), 1605, 1262, 1510, 1491, 1447, 1201, 763 (C–Cl), 730,
691 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.17 (dd, J = 4 and
5 Hz, 1 H, 4-H), 7.42–7.47 (m, 3 H, ArH), 7.66 (s, 1 H, olefinic
H), 7.74 (dd, J = 1 and 5 Hz, 1 H, 5-H), 7.85–7.87 (m, ArH, 3 H,
3-H) ppm. 13C NMR (100 MHz, CDCl3): δ = 127.95 (d), 128.56
(dϫ2), 129.01 (s), 130.20 (d), 130.50 (dϫ2), 132.85 (s), 134.54 (d),
134.74 (d), 137.07 (d), 141.49 (s), 182.25 (s) ppm. MS: m/z = 248
[M]+, 213 [M – Cl]+. C13H9SCl (232.73): calcd. C 62.78, H 3.65;
found C 62.64, H 3.56.
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(Z)-1-Chloro-2-(p-methoxyphenyl)ethenyl 2-Furyl Ketone (10h):
TMSOTf (69.0 mg, 0.31 mmol) was added dropwise to a CH2Cl2
(2.0 mL) solution of 9h (95 mg, 0.31 mmol) at –78 °C under an Ar
atmosphere. The usual work up produced title compound 10h
[10] Chlorination of aryl methyl ketone: a) J. Dubac, A. Gaset, M.
Maraval, Synth. Commun. 1991, 21, 11–16; b) S. Yakabe, M.
Hirano, T. Morimoto, Synth. Commun. 1998, 28, 131–138; c)
A. Guy, M. Lemaire, J.-P. Guette, Synthesis 1982, 1018–1020;
d) S. Kajigaeshi, T. Kakinami, M. Moriwaki, S. Fujisaki, K.
Maeno, T. Okamoto, Synthesis 1988, 545–546; e) J. C. Lee, J. Y.
(70 mg, 87%) as a yellow oil. IR (KBr): ν = 3435, 3133, 2934, 2839,
˜
1644, 1597 (furyl), 1509, 1462, 1258, 1180, 1094, 1027 (C–O), 793
506
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