9236
X. Lin et al. / Tetrahedron 65 (2009) 9233–9237
(m, 12H), 6.37 (br s, 1H), 5.98 (s, 1H) ppm. 13C NMR (100 MHz,
1621,1566,1488, 1379,1269,1199,1156,1116, 965, 745, 696 cmꢁ1. 1H
NMR (400 MHz, CDCl3):
CDCl3):
d
163.2, 160.1, 152.3, 139.9, 132.1, 129.4, 128.7, 127.7, 123.9,
d
7.76 (d, J¼6.8 Hz, 1H), 7.48 (dd, J¼6.4,
123.1, 116.4, 115.9, 107.7, 47.2 ppm. MS (ESI): m/z 327 ([Mꢁ1]ꢁ).
8.8 Hz, 1H), 7.41–7.25 (m, 11H), 7.08 (br s, 1H), 6.73 (dd, J¼6.4,
16.4 Hz, 1H), 6.51 (d, J¼16.4 Hz, 1H), 5.44 (d, 6.4 Hz, 1H) ppm. 13C
4.4.5. 4-Hydroxy-3-((4-methoxyphenyl) (phenyl) methyl)-2H-chro-
NMR (100 MHz, CDCl3): d 162.7, 159.8, 151.0, 139.2, 135.9, 134.1,
men-2-one (3e)8. Yellow solid; mp: 164–166 ꢀC. IR (KBr): 3398,
132.1, 129.5, 129.4, 128.7, 128.1, 128.0, 127.8, 127.7, 126.5, 122.8, 117.9,
117.0, 107.3, 44.0 ppm. MS (ESI): m/z 388 ([Mꢁ1]ꢁ). Anal. Calcd for
C24H17ClO3: C, 74.13; H, 4.41. Found: C, 74.43; H, 4.30.
1666, 1609, 1509, 1250, 1178, 1036, 756 cmꢁ1 1H NMR (400 MHz,
.
CDCl3):
7.18 (d, J¼8.4 Hz, 2H), 6.91 (d, J¼8.8 Hz, 2H), 6.34 (s,1H), 5.91 (s,1H),
3.81 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3):
163.2, 160.1, 159.0,
d
7.73 (dd, J¼6.0, 7.6 Hz,1H), 7.54 (m,1H), 7.38–7.26 (m, 7H),
d
4.4.12. 6-Chloro-4-hydroxy-3-(1-(3-methoxyphenyl)-3-phenylprop-
2-ynyl)-2H-chromen-2-one (3l). Brown solid; mp: 126–128 ꢀC. IR
(KBr): 3333, 1683, 1627, 1609, 1571, 1491, 1394, 1260, 1199, 1050,
152.6,140.2,132.0,131.6,129.8,129.3,128.6,127.6,123.9,123.1,116.4,
115.9,114.8,107.8, 55.3, 46.5 ppm. MS (ESI): m/z 357 ([Mꢁ1]ꢁ). Anal.
Calcd for C23H18O4: C, 77.08; H, 5.06. Found: C, 77.12; H, 5.02.
759, 691 cmꢁ1. 1H NMR (400 MHz, CDCl3):
d 8.27 (br s, 1H), 7.86 (d,
J¼8.4 Hz, 1H), 7.57–7.50 (m, 3H), 7.39–7.26 (m, 6H), 7.22–7.17 (m,
4.4.6. (E)-3-(1,3-Diphenylallyl)-4-hydroxy-2H-chromen-2-one
2H), 6.84 (d, J¼8.4 Hz, 1H), 5.77 (s, 1H), 3.81 (s, 3H) ppm. 13C NMR
(3f)8. White solid; mp: 155–157 ꢀC. IR (KBr): 3327, 1671, 1624, 1610,
(100 MHz, CDCl3): d 162.6, 161.2, 160.0, 152.6, 140.0, 132.4, 131.8,
1494, 1392, 1201, 754 cmꢁ1. 1H NMR (400 MHz, CDCl3):
d
7.81 (dd,
130.0, 129.1, 128.5, 124.0, 123.4, 121.4, 119.3, 116.5, 115.9, 113.1, 112.9,
104.8, 87.8, 86.2, 55.3, 33.3 ppm. MS (ESI): m/z 381 ([Mꢁ1]ꢁ). Anal.
Calcd for C25H18O4: C, 78.52; H, 4.74. Found: C, 78.50; H, 4.75.
J¼6.8, 8.0 Hz, 1H), 7.54–7.50 (m, 1H), 7.42–7.24 (m, 13H), 6.79 (dd,
J¼6.0, 16.0 Hz, 1H), 6.52 (d, J¼16.0 Hz, 1H), 5.47 (d, J¼6.0 Hz,
1H) ppm. 13C NMR (100 MHz, CDCl3):
d 163.2, 160.9, 152.6, 139.6,
136.1,133.8, 132.1,129.2,128.6,128.1,128.0, 127.6,126.5, 124.0, 123.1,
4.4.13. 6-Chloro-3-(1-(4-chlorophenyl)-3-phenylprop-2-ynyl)-4-hy-
116.5, 115.8, 106.4, 43.9 ppm. MS (ESI): m/z 353 ([Mꢁ1]ꢁ).
droxy-2H-chromen-2-one (3m). Yellow solid; mp: 174–175 ꢀC. IR
(KBr): 3311, 1679, 1614, 1570, 1210, 1164, 1109, 1071, 759, 692 cmꢁ1
.
4.4.7. 3-(1,3-Diphenylprop-2-ynyl)-4-hydroxy-2H-chromen-2-one
1H NMR (400 MHz, CDCl3):
1H), 7.58–7.50 (m, 5H), 7.40–7.30 (m, 7H), 5.73 (s,1H) ppm. 13C NMR
(100 MHz, CDCl3): 162.5, 161.3, 152.6, 137.1, 133.5, 132.5, 131.8,
d
8.51 (s, 1H), 7.87 (dd, J¼6.4, 8.0 Hz,
(3g)8. White solid; mp: 157–158 ꢀC. IR (KBr): 3337, 3058, 1668,
1613, 1567, 1492, 1209, 756, 717, 693 cmꢁ1
.
1H NMR (400 MHz,
d
CDCl3):
J¼7.6 Hz, 2H), 7.56–7.50 (m, 3H), 7.38–7.25 (m, 8H), 5.79 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3):
162.6, 161.1, 152.6, 138.5,
d
8.40 (br s, 1H), 7.86 (dd, J¼6.8, 8.4 Hz, 1H), 7.61 (d,
129.4, 129.0, 128.6, 128.5, 124.2, 123.4, 121.0, 116.5, 115.8,104.4, 88.2,
85.9, 32.9 ppm. MS (ESI): m/z 386 ([Mꢁ1]ꢁ). Anal. Calcd for
C24H15ClO3: C, 74.52; H, 3.91. Found: C, 74.45; H, 3.86.
d
132.3, 131.8, 129.1, 129.0, 128.5, 127.7, 127.1, 124.0, 123.4, 121.3, 116.4,
115.9, 104.9, 87.8, 86.4, 33.3 ppm. MS (ESI): m/z 351 ([Mꢁ1]ꢁ).
4.4.14. 3-(1-(4-Bromophenyl)-3-phenylprop-2-ynyl)-6-chloro-4-hy-
droxy-2H-chromen-2-one (3n). Yellow solid; mp: 179–180 ꢀC. IR
(KBr): 3422, 1677, 1625, 1611, 1570, 1490, 1202, 757 cmꢁ1. 1H NMR
4.4.8. (E)-3-(1,3-Diphenylallyl)-6-ethoxy-4-hydroxy-2H-chromen-2-
one (3h). White solid; mp: 154–155 ꢀC. IR (KBr): 3401, 1668, 1572,
(400 MHz, CDCl3):
7.47 (m, 7H), 7.38–7.30 (m, 5H), 5.71 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3): 162.5, 161.3, 152.6, 137.7, 132.5, 132.0, 131.8,
d
8.50 (s, 1H), 7.87 (dd, J¼6.8, 8.0 Hz, 1H), 7.55–
1497, 1448, 1213, 1184, 746, 696 cmꢁ1 1H NMR (400 MHz, CDCl3):
.
d
7.43–7.24 (m,11H), 7.19 (d, J¼2.8 Hz,1H), 7.12 (dd, J¼6.0, 9.2 Hz,1H),
d
6.99 (s,1H), 6.75 (dd, J¼6.0,16.0 Hz,1H), 6.52 (d, J¼16.0 Hz,1H), 5.48
129.4, 128.9, 128.6, 124.1, 123.4, 121.7, 121.0, 116.5, 115.8, 104.3, 88.3,
85.9, 33.0 ppm. MS (ESI): m/z 431 ([Mꢁ1]ꢁ). Anal. Calcd for
C24H15BrO3: C, 66.84; H, 3.51. Found: C, 66.74; H, 3.48.
(d, J¼6.0 Hz,1H), 4.03 (q, J¼6.8 Hz, 2H),1.14 (t, J¼6.8 Hz, 3H) ppm.13C
NMR (100 MHz, CDCl3): d 163.4,160.8,155.2,147.1,139.6,136.1,133.8,
129.2, 128.6, 128.2, 128.0, 128.0, 127.6, 126.5, 120.9, 117.6, 116.1, 106.5,
105.4, 64.1, 44.0, 14.7 ppm. MS (ESI): m/z 397 ([Mꢁ1]ꢁ). Anal. Calcd
for C26H22O4: C, 78.37; H, 5.57. Found: C, 78.31; H, 5.52.
4.4.15. 4-Hydroxy-3-(1-(naphthalen-2-yl)-3-phenylprop-2-ynyl)-
2H-chromen-2-one (3o). Yellow solid; mp: 188–190 ꢀC. 7% ee, de-
termined by HPLC analysis (Chiralcel AD-H column, IPA/
hexane¼30:70, 254 nm); retention time: t1¼10.703 (53%) and
t2¼12.895 (46%) min. IR (KBr): 3385, 1679, 1614, 1570, 1491, 1198,
4.4.9. 3-Benzhydryl-6-ethoxy-4-hydroxy-2H-chromen-2-one
(3i). White solid; mp: 222–223 ꢀC. IR (KBr): 3384, 1697, 1628, 1585,
1495, 1443, 1396, 1272, 1251, 1228, 1180, 1043, 703 cmꢁ1
.
1H NMR
758 cmꢁ1. 1H NMR (400 MHz, CDCl3):
d 8.38 (br s, 1H), 8.08 (s, 1H),
(400 MHz, CDCl3):
1H), 5.99 (s, 1H), 4.01 (q, J¼6.8 Hz, 2H), 1.41 (t, J¼6.8 Hz, 3H) ppm.
13C NMR (100 MHz, CDCl3):
163.4, 160.5, 155.2, 147.1, 140.0, 129.4,
128.7, 127.7, 120.9, 117.5, 116.1, 107.8, 105.4, 64.0, 47.3, 14.7 ppm. MS
(ESI): m/z 371 ([Mꢁ1]ꢁ). Anal. Calcd for C24H20O4: C, 77.40; H, 5.41.
Found: C, 77.31; H, 5.40.
d
7.40–7.23 (m, 11H), 7.14–7.09 (m, 2H), 6.25 (s,
7.87–7.80 (m, 4H), 7.68–7.66 (m, 1H), 7.56–7.46 (m, 5H), 7.40–7.25
(m, 5H), 5.95 (s, 1H) ppm. 13C NMR (100 MHz, DMSO):
d
161.6, 161.4,
d
152.8, 137.4, 133.3, 133.0, 132.5, 132.1, 129.2, 128.8, 128.3, 127.9,
126.7, 126.2, 126.0, 124.5, 124.3, 123.5, 116.9, 116.6, 105.9, 89.3, 83.0,
33.0 ppm. MS (ESI): m/z 401 ([Mꢁ1]ꢁ). Anal. Calcd for C28H18ClO3:
C, 83.57; H, 4.51. Found: C, 83.60; H, 4.51.
4.4.10. 3-(1,3-Diphenylprop-2-ynyl)-6-ethoxy-4-hydroxy-2H-chro-
4.4.16. 2,4-Diphenylpyrano[3,2-c]chromen-5(4H)-one (4a)12a. White
men-2-one (3j). White solid; mp: 165–167 ꢀC. IR (KBr): 3333, 3601,
solid; mp: 173–175 ꢀC. IR (KBr): 1716, 1631, 1610, 1493, 1454, 1387,
2979, 1673, 1624, 4575, 1493, 1275, 1187, 1047, 756, 692 cmꢁ1
.
1H
1271, 1205, 1169, 1112, 1013, 765, 698 cmꢁ1 1H NMR (400 MHz,
.
NMR (400 MHz, CDCl3):
d
8.39 (s, 1H), 7.61 (d, J¼7.6 Hz, 2H), 7.52–
CDCl3):
d
8.02 (dd, J¼6.4, 8.0 Hz, 1H), 7.75–7.72 (m, 2H), 7.59–7.55
7.50 (m, 2H), 7.38–7.21 (m, 8H), 7.10 (dd, J¼6.0, 8.8 Hz, 1H), 5.79 (s,
(m, 1H), 7.48–7.38 (m, 6H), 7.36–7.30 (m, 3H), 7.25–7.21 (m, 1H),
1H), 4.04 (q, J¼7.2 Hz, 2H), 1.42 (t, J¼7.23 Hz, 3H) ppm. 13C NMR
5.85 (d, J¼4.8 Hz, 1H), 4.72 (d, J¼4.8 Hz, 1H) ppm. 13C NMR
(100 MHz, CDCl3):
d
162.7, 160.9, 155.2, 147.0, 138.5, 131.8, 129.1,
(100 MHz, CDCl3): d 161.4, 155.6, 152.7, 146.8, 143.5, 132.5, 131.9,
128.9, 128.5, 127.7, 127.0, 121.3, 121.1, 117.6, 116.1, 105.5, 105.0, 87.8,
86.5, 64.1, 33.3, 14.7 ppm. MS (ESI): m/z 395 ([Mꢁ1]ꢁ). Anal. Calcd
for C26H20O4: C, 78.77; H, 5.09. Found: C, 78.77; H, 5.06.
129.2, 128.6, 128.6, 128.4, 127.2, 124.6, 124.1, 122.6, 116.7, 114.5,
103.7, 103.6, 36.5 ppm. MS (ESI): m/z 375 ([MþNa]þ).
4.4.17. 4-(3-Methoxyphenyl)-2-phenylpyrano[3,2-c]chromen-5(4H)-
one (4b)12b. White solid; mp: 144–146 ꢀC. IR (KBr): 1718, 1628,
1609, 1491, 1389, 1262, 1019, 766 cmꢁ1. 1H NMR (400 MHz, CDCl3):
4.4.11. (E)-6-Chloro-3-(1,3-diphenylallyl)-4-hydroxy-2H-chromen-2-
one (3k). White solid; mp:159–161 ꢀC. IR (KBr): 3326, 3026, 1673,