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Z. Li et al. / Tetrahedron: Asymmetry 17 (2006) 590–597
1
5.49 (s, 1H), 3.78 (s, 3H), 3.69–3.52 (m, 2H), 3.14 (ddd,
J = 16.6, 10.6, 3.2 Hz, 1H), 2.92 (dt, J = 16.0, 3.6 Hz,
1H); 13C NMR (ppm) d 154.03, 143.95, 135.27, 133.87,
131.53, 128.91, 127.90, 127.81, 127.35, 126.98, 125.97,
122.92, 120.06, 114.24, 88.38, 85.44, 55.61, 54.42,
44.27, 29.12; MS (EI) m/z (%) 339 (100), 338, 327,
267, 253, 236, 204, 203, 202, 191, 178, 165, 147, 135,
120, 96, 73; HRMS calcd for C24H21NO: 339.1623;
found: 339.1620.
692 cmꢀ1; H NMR (ppm) d 7.34–7.31 (m, 1H), 7.30–
7.26 (m, 2H), 7.21–7.16 (m, 4H), 7.15–7.12 (m, 1H),
7.08 (d, J = 8.0 Hz, 2H), 6.84 (dd, J = 7.6, 7.6 Hz,
1H), 6.69 (dt, J = 8.8, 2.4 Hz, 2H), 5.60 (s, 1H), 3.73–
3.60 (m, 2H), 3.68 (s, 3H), 3.09 (ddd, J = 16.0, 9.6,
6.0 Hz, 1H), 2.92 (dt, J = 16.0, 4.0 Hz, 1H); 13C NMR
(ppm) d 159.10, 149.32, 135.40, 134.14, 132.93, 128.92,
128.70, 127.23, 126.94, 126.04, 119.34, 116.46, 114.95,
113.54, 87.03, 84.52, 55.17, 52.25, 43.41, 28.95; MS
(EI) m/z (%) 369, 368, 338 (100), 262, 247, 220, 191,
189, 165, 115, 91, 77, 63.
4.2.3.7. rac-2-(4-Methoxy-phenyl)-1-oct-1-ynyl-1,2,3,4-
tetrahydroisoquinoline 4g. Isolated by thin layer
chromatography (hexane/methylene chloride/diethyl
ether = 100:60:1, Rf = 0.4). HPLC (Daicel Chiralcel
OD-H, hexane/isopropanol = 95:5, flow rate = 0.5 mL/
min) tR = 11.6 min, tR = 13.1 min, ee = 0%; IR (neat
liquid): mmax 2953, 2930, 2856, 2832, 2252, 1579, 1511,
1464, 1441, 1376, 1261, 1243, 1201, 1182, 1122,
4.2.3.10. rac-1-(4-Bromo-phenylethynyl)-2-(2-methoxy-
phenyl)-1,2,3,4-tetrahydroisoquinoline 4j. Isolated yield
by thin layer chromatography (hexane/methylene chlo-
ride/diethyl ether = 100:60:1, Rf = 0.7). HPLC (Daicel
Chiralcel OD-H, hexane/isopropanol = 95:5, flow rate =
0.5 mL/min) tR = 12.9 min, tR = 14.9 min, ee = 0%; IR
(neat liquid): mmax 3065, 3029, 2921, 2833, 2393, 1902,
1597, 1504, 1485, 1451, 1393, 1377, 1354, 1286, 1261,
1
1039 cmꢀ1; H NMR (ppm) d 7.26–7.25 (m, 1H), 7.18–
7.13 (m, 3H), 7.03 (d, J = 8.8 Hz, 2H), 6.85 (d, J =
9.2 Hz, 2H), 5.27 (s, 1H), 3.77 (s, 3H), 3.57–3.49 (m,
2H), 3.09 (ddd, J = 16.4, 10.0, 6.4 Hz, 1H), 2.88 (dt,
J = 16.4, 3.2 Hz, 1H), 2.07 (dt, J = 7.2, 2.0 Hz, 2H),
1.37–1.32 (m, 2H), 1.26–1.17 (m, 6H), 0.85 (t, J =
6.0 Hz, 3H); 13C NMR (ppm) d 153.78, 144.05, 136.10,
133.63, 128.80, 127.23, 126.72, 125.83, 119.79, 114.13,
85.98, 78.86, 55.56, 53.79, 44.06, 31.39, 29.09, 28.78,
28.45, 22.65, 18.88, 14.18; MS (EI) m/z (%) 347 (100),
346, 276, 262, 236, 194, 169, 155, 142, 141, 129, 128,
115, 92, 91, 77, 55; HRMS calcd for C24H29NO:
347.2249; found: 347.2242.
1205, 1153, 1070, 1011 cmꢀ1 1H NMR (300 MHz,
;
ppm) d 7.35–7.29 (m, 4H), 7.24–7.15 (m, 4H), 7.14–
7.07 (m, 4H), 6.87 (dt, J = 7.2, 1.2 Hz, 1H), 5.61 (s,
1H), 3.77–3.58 (m, 2H), 3.13 (ddd, J = 15.6, 9.9,
5.7 Hz, 1H), 2.95 (dt, J = 15.9, 4.2 Hz, 1H); 13C NMR
(75 MHz, ppm) d 149.29, 134.93, 134.26, 133.06,
131.20, 129.04, 128.85, 127.26, 127.20, 126.20, 122.11,
121.81, 119.64, 116.58, 89.78, 83.67, 52.35, 43.47,
28.94; MS (EI) m/z (%) 418, 416, 402, 388 (100), 386
(100), 373, 355, 341, 327, 312, 297, 262, 207, 203, 193,
152, 135, 105, 91, 73, 51.
4.2.3.8.
rac-2-(2-Methoxy-phenyl)-1-phenylethynyl-
4.2.3.11.
rac-2-(2-Methoxy-phenyl)-1-pyridin-2-yl-
1,2,3,4-tetrahydroisoquinoline 4h. Isolated by thin layer
chromatography (hexane/methylene chloride/diethyl
ether = 100:60:1, Rf = 0.3). HPLC (Daicel Chiralcel
OD-H, hexane/isopropanol = 95:5, flow rate = 0.5 mL/
min) tR = 12.4 min, tR = 21.2 min, ee = 0%; IR (neat
liquid): mmax 3062, 3022, 3006, 2958, 2925, 2834, 2384,
2349, 1712, 1595, 1500, 1490, 1463, 1454, 1442, 1374,
1273, 1253, 1241, 1217, 1199, 1179, 1138, 1106,
ethynyl-1,2,3,4-tetrahydroisoquinoline 4k. Isolated by
thin layer chromatography (hexane/ethyl acetate = 5:1,
Rf = 0.3). HPLC (Daicel Chiralcel OD-H, hexane/
isopropanol = 95:5, flow rate = 0.5 mL/min) tR =
12.9 min, tR = 14.9 min, ee = 0%; IR (neat liquid): mmax
3065, 3029, 2921, 2833, 2393, 1902, 1597, 1504, 1485,
1451, 1393, 1377, 1354, 1286, 1261, 1205, 1153, 1070,
1
1011 cmꢀ1; H NMR (300 MHz, ppm) d 7.35–7.29 (m,
1
1028 cmꢀ1; H NMR (ppm) d 7.32–7.30 (m, 1H), 7.22–
4H), 7.24–7.15 (m, 4H), 7.14–7.07 (m, 4H), 6.87 (dt,
J = 7.2, 1.2 Hz, 1H), 5.61 (s, 1H), 3.77–3.58 (m, 2H),
3.13 (ddd, J = 15.6, 9.9, 5.7 Hz, 1H), 2.95 (dt,
J = 15.9, 4.2 Hz, 1H); 13C NMR (75 MHz, ppm) d
149.29, 134.93, 134.26, 133.06, 131.20, 129.04, 128.85,
127.26, 127.20, 126.20, 122.11, 121.81, 119.64, 116.58,
89.78, 83.67, 52.35, 43.47, 28.94; MS (EI) m/z (%) 340,
339, 309 (100), 294, 281, 262, 233, 218, 205, 204, 191,
176, 155, 133, 120, 92, 76, 51, 50.
7.15 (m, 9H), 7.05 (dt, J = 7.6, 1.6 Hz, 1H), 6.96 (dt,
J = 7.6, 1.6 Hz, 1H), 6.89 (dd, J = 8.0, 0.8 Hz, 1H),
5.74 (s, 1H), 3.87 (s, 3H), 3.68 (dt, J = 11.6, 4.0 Hz,
1H), 3.43 (dd, J = 11.6, 11.6 Hz, 1H), 3.24 (ddd,
J = 16.8, 11.2, 5.6 Hz, 1H), 2.90 (dt, J = 16.4, 2.4 Hz,
1H); 13C NMR (ppm) d 159.10, 149.32, 135.40, 134.14,
132.93, 128.92, 128.70, 127.23, 126.94, 126.04, 119.34,
116.46, 114.95, 113.54, 87.03, 84.52, 55.17, 52.25,
43.41, 28.95; MS (EI) m/z (%) 339, 338, 322, 308
(100), 293, 262, 246, 232, 217, 203, 202, 189, 165, 152,
115, 92, 91, 77, 64; HRMS calcd for C24H20NO:
339.1623; found: 339.1627.
4.2.3.12. rac-2-(2-(2-Methoxyethoxy)phenyl)-1,2,3,4-
tetrahydro-1-(2-phenylethynyl)isoquinoline 4l. Isolated
by thin layer chromatography (methylene chloride,
Rf = 0.4) HPLC (Daicel Chiralcel OD-H, hexane/
isopropanol = 95:5, flow rate = 0.5 mL/min) tR =
20.1 min, tR = 23.7 min, ee = 0%; IR (neat liquid): mmax
3059, 3022, 2923, 2878, 2832, 1595, 1499, 1450, 1371,
4.2.3.9. rac-2-(2-Methoxy-phenyl)-1-(4-methoxy-phen-
ylethynyl)-1,2,3,4-tetrahydroisoquinoline 4i. Isolated by
thin layer chromatography (hexane/methylene chloride/
diethyl ether = 100:60:1, Rf = 0.4). HPLC (Daicel Chi-
ralcel OD-H, hexane/isopropanol = 95:5, flow rate =
0.5 mL/min) tR = 16.1 min, tR = 18.8 min, ee = 0%; IR
(neat liquid): mmax 3061, 3025, 2932, 2836, 2206, 1600,
1499, 1374, 1246, 1172, 1106, 1033, 832, 756,
1241, 1198, 1128 cmꢀ1 1H NMR (500 MHz, ppm) d
;
7.32–7.30 (m, 1H), 7.24–7.15 (m, 9H), 7.03–6.97 (m,
2H), 6.90 (dd, J = 7.5, 1.0 Hz, 1H), 5.85 (s, 1H), 4.16
(t, J = 4.5 Hz, 2H), 3.75–3.65 (m, 3H), 3.51 (dd,
J = 11.0, 6.0 Hz, 1H), 3.23 (ddd, J = 17.0, 11.5,