6
Tetrahedron
ACCEPTED MANUSCRIPT
100.7, 117.1, 118.5, 119.0, 124.5, 127.0, 132.3, 138.3, 153.7,
1H), 7.26 (ddd, J = 7.9, 7.3 and 1.2 Hz, 1H), 7.31 (dd, J = 8.3 and
160.7; HR-MS 207.044 (C12H8O2 + Na+ calcd 207.042).
1.2 Hz, 1H), 7.38-7.48 (m, 6H), 7.54 (ddd, J = 8.3, 7.3 and 1.4
Hz, 1H), 7.70 (dd, J = 7.9 and 1.4 Hz, 1H), 7.72-7.77 (m, 4H);
13C NMR (100 MHz, CDCl3) δ (ppm) 19.4, 26.9, 53.3, 79.0,
101.1, 117.1, 118.5, 119.1, 124.6, 126.9, 128.1, 130.3, 132.4,
132.9, 135.9, 137.1, 153.7, 160.3; HR-MS 461.154 (C28H26O3Si
+ Na+ calcd 461.154).
4.1.5. 4-(Cyclohexylethynyl)-2H-chromen-2-one
(14)
Following the general procedure, 2-oxo-2H-chromen-4-yl 4-
nitrobenzenesulfonate 1 (173 mg, 0.5 mmol), PdCl2(PPh3)2 (17.5
mg, 5 mol%), CuI (4.7 mg, 5 mol%), cyclohexylacetylene (79
ꢀL, 0.6 mmol) and DIPEA (109 ꢀL, 0.625 mmol) were stirred at
room temperature during 1 h and gave 14 (116 mg, 0.46 mmol,
92 %) as a brown solid. TLC Rf 0.28 (Cyclohexane/EtOAc 9/1);
mp 60-61°C; IR νmax 3064, 2933, 2924, 2845, 2221, 2209, 1718,
1603, 1555, 1484, 1460, 1448, 1369, 1323, 1302, 1273, 1251,
1238, 1174, 1152, 1139, 1105, 1030, 980, 950, 922, 887, 871,
4.1.9. 4-(3-Hydroxy-3-methylbut-1-ynyl)-2H-
chromen-2-one (19)
Following the general procedure, 2-oxo-2H-chromen-4-yl 4-
nitrobenzenesulfonate 1 (173 mg, 0.5 mmol), PdCl2(PPh3)2 (17.5
mg, 5 mol%), CuI (4.7 mg, 5 mol%), 2-methyl-3-butyn-2-ol (63
ꢀL, 0.65 mmol) and DIPEA (109 ꢀL, 0.625 mmol) %) were
stirred at room temperature during 4 h and gave 19 (102 mg, 4.45
843, 818 cm-1; H NMR (400 MHz, CDCl3) δ (ppm) 1.35-1.48
1
(m, 3H), 1.55-1.68 (m, 3H), 1.73-1.84 (m, 2H), 1.90-2.00 (m,
2H), 2.76 (m, 1H), 6.48 (s, 1H), 7.28-7.33 (m, 2H), 7.53 (ddd, J =
8.3, 7.4 and 1.6 Hz, 1H), 7.84 (dd, J = 8.3 and 1.6, 1H); 13C
NMR (100 MHz, CDCl3) δ (ppm) 25.0, 25.9, 30.3, 32.4, 75.0,
109.1, 117.1, 118.3, 119.1, 124.5, 126.9, 132.2, 138.3, 153.8,
160.7; HR-MS 253.124 (C17H16O2S calcd 253.122).
mmol, 89 %) as
(Cyclohexane/Et2O 7/3); mp 93-94°C; IR νmax 3422, 3199, 2983,
a
yellow powder. TLC Rf 0.25
1690, 1600, 1554, 1487, 1445, 1396, 1364, 1326, 1273,
1245,1210, 1169, 1128, 1029, 964, 947, 894, 858, 843 cm-1; H
1
NMR (500 MHz, CDCl3) δ (ppm) 1.70 (s, 6H), 1.94 (bs, 1H),
6.53 (s, 1H), 7.32 (ddd, J = 7.4, 7.1 and 1.6 Hz, 1H), 7.32 (dd, J
= 7.1 and 1.6 Hz, 1H), 7.55 (ddd, J = 8.1, 7.4 and 1.6 Hz, 1H),
7.80 (dd, J = 8.1 and 1.6 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ
(ppm) 31.3, 76.1, 84.2, 107.0, 117.2, 118.5, 119.1, 124.7, 126.8,
132.6, 137.0, 153.8, 160.3; HR-MS 251.067 (C14H12O2 + Na+
calcd 251.068).
4.1.6. 4-(Cyclohex-1-enylethynyl)-2H-chromen-2-
one (15)
Following the general procedure, 2-oxo-2H-chromen-4-yl 4-
nitrobenzenesulfonate 1 (173 mg, 0.5 mmol), PdCl2(PPh3)2 (17.5
mg, 5 mol%), CuI (4.7 mg, 5 mol%), 1-ethynylcyclohexene (76
ꢀL, 0.65 mmol) and DIPEA (109 ꢀL, 0.625 mmol) were stirred at
room temperature during 2 h and gave 15 (109 mg, 0.43 mmol,
4.1.10. 4-(3-Hydroxy-4-methylpent-1-ynyl)-2H-
chromen-2-one (20)
1
87 %) as a brown solid. mp 92-93°C; H NMR (500 MHz,
Following the general procedure, 2-oxo-2H-chromen-4-yl 4-
nitrobenzenesulfonate 1 (173 mg, 0.5 mmol), PdCl2(PPh3)2 (17.5
mg, 5 mol%), CuI (4.7 mg, 5 mol%), 4-methylpent-1-yn-3-ol (64
ꢀL, 0.6 mmol) and DIPEA (109 ꢀL, 0.625 mmol) were stirred at
room temperature during 6h and gave 20 (94 mg, 0.39 mmol, 77
%) as a yellow powder. TLC Rf 0.23 (Cyclohexane/EtOAc 7/3);
mp 83-84°C; IR νmax 3505, 3071, 2967, 2932, 2872, 2225, 1710,
1606, 1556, 1487, 1472, 1452, 1373, 1326, 1275, 1253, 1235,
1182, 1144, 1113, 1100, 1032, 959, 940, 896, 860, 836, 808 cm-1;
1H NMR (500 MHz, CDCl3) δ (ppm) 1.11 (d, J = 6.8 Hz, 3H),
1.13 (d, J = 6.8 Hz, 3H), 2.08 (dm, J = 6.8 and 5.6 Hz, 1H), 2.17
(bs, 1H), 4.53 (d, J = 5.6 Hz, 1H), 6.55 (s, 1H), 7.31 (ddd, J =
7.6, 7.5 and 1.6 Hz, 1H), 7.32 (dd, J = 7.5 and 1.6 Hz, 1H), 7.55
(ddd, J = 8.0, 7.6 and 1.6 Hz, 1H), 7.82 (dd, J = 8.0 and 1.6 Hz,
1H); 13C NMR (125 MHz, CDCl3) δ (ppm) 17.9, 18.4, 34.8, 68.6,
79.3, 102.6, 117.3, 118.5, 119.3, 124.7, 126.8, 132.6, 137.1,
153.8, 160.3; HR-MS 265.084 (C15H14O3 calcd + Na+ 265.084).
CDCl3) δ (ppm) 1.64-1.70 (m, 2H), 1.70-1.76 (m, 2H), 2.19-2.26
(m, 2H), 2.27-2.33 (m, 2H), 6.47 (tt, J = 4.2 and 1.9 Hz, 1H),
6.50 (s, 1H), 7.31 (ddd, J = 8.4, 7.3 and 1.6 Hz, 1H), 7.32 (dd, J
= 7.7 and 1.6 Hz, 1H), 7.54 (ddd, J = 8.4, 7.3 and 1.6 Hz, 1H),
7.84 (dd, J = 7.7 and 1.6 Hz, 1H) 13C NMR (125 MHz, CDCl3) δ
(ppm) 21.5, 22.3, 26.3, 29.0, 80.9, 117.2, 118.8, 120.1, 124.5,
126.9, 132.3, 138.0, 140.3; HR-MS 273.090 (C17H14O2 + Na+
calcd 273.089).
4.1.7. 4-(3-Hydroxyprop-1-ynyl)-2H-chromen-2-one
(17)
Following the general procedure, 2-oxo-2H-chromen-4-yl 4-
nitrobenzenesulfonate 1 (173 mg, 0.5 mmol), PdCl2(PPh3)2 (17.5
mg, 5 mol%), CuI (4.7 mg, 5 mol%), propargyl alcohol (38 ꢀL,
0.65 mmol) and DIPEA (109 ꢀL, 0.625 mmol) were stirred at
room temperature during 14 h and gave 17 (10 mg, 0.05 mmol,
10 %) as a yellow powder. TLC Rf 0.23 (Cyclohexane/Et2O 7/3);
mp 89-91°C; IR νmax 3265, 2924, 2851, 1671, 1604, 1557, 1530,
1442, 1372, 1349, 1278, 1260, 1229, 1191, 1138, 1100, 1016,
970, 950, 914, 877, 856, 811 cm-1; 1H NMR (500 MHz, CDCl3) δ
(ppm) 4.64 (s, 2H), 6.56 (s, 1H), 7.32 (ddd, J = 8.3, 7.7 and 1.3
Hz, 1H), 7.33 (dd, J = 7.2 and 1.3 Hz, 1H), 7.56 (ddd, J = 8.3, 7.2
and 1.3 Hz, 1H), 7.85(dd, J = 7.7 and 1.3 Hz, 1H); HR-MS
223.036 (C12H8O3 + Na+ calcd 223.037).
4.1.11. 4-(6-Hydroxyhex-1-ynyl)-2H-chromen-2-one
(21)
Following the general procedure, 2-oxo-2H-chromen-4-yl 4-
nitrobenzenesulfonate 1 (173 mg, 0.5 mmol), PdCl2(PPh3)2 (17.5
mg, 5 mol%), CuI (4.7 mg, 5 mol%), 5-hexyn-1-ol (72 ꢀL, 0.65
mmol) and DIPEA (109 ꢀL, 0.625 mmol) were stirred at room
temperature during 6 h and gave 21 (86 mg, 0.36 mmol, 71 %) as
a white solid. TLC Rf 0.13 (Cyclohexane/EtOAc 7/3); mp 50-
51°C; IR νmax 3321, 3068, 2940, 2223, 1711, 1682, 1603, 1555,
1485, 1449, 1420, 1373, 1329, 1273, 1256, 1179, 1136, 1103,
1049, 1031, 984, 936, 858, 813 cm-1; 1H NMR (400 MHz,
CDCl3) δ (ppm) 1.74- 1.84 (m, 4H), 2.62 (t, J = 6.8 Hz, 2H), 3.74
(t, J = 5.7 Hz, 2H), 6.48 (s, 1H), 7.27-7.33 (m, 2H), 7.53 (ddd, J
4.1.8. 4-(3-(tert-Butyldiphenylsilyloxy)prop-1-
ynyl)-2H-chromen-2-one (18)
Following the general procedure, 2-oxo-2H-chromen-4-yl 4-
nitrobenzenesulfonate 1 (173 mg, 0.5 mmol), PdCl2(PPh3)2 (17.5
mg, 5 mol%), CuI (4.7 mg, 5 mol%), tert-butyldiphenyl(prop-2-
yn-1-yloxy)silane (191 mg, 0.65 mmol) and DIPEA (109 ꢀL,
0.625 mmol) were stirred at room temperature during 14 h and
gave 18 (147 mg, 3.3 mmol, 67 %) as a brown oil. TLC Rf 0.20
(Cyclohexane/Et2O 8/2); IR νmax 3070, 2929, 2856, 1721, 1605,
1557, 1488, 1471, 1450, 1427, 1369, 1323, 1274, 1253, 1230,
1178, 1137, 1105, 1075, 1031, 997, 932, 860, 822 cm-1; 1H NMR
(400 MHz, CDCl3) δ (ppm) 1.10 (s, 9H), 4.67 (s, 2H), 6.40 (s,
= 8.3, 7.4 and 2.0 Hz, 1H), 7.83 (dd, J = 8.1 and 2.0 Hz, 1H); 13
NMR (100 MHz, CDCl3) δ (ppm) 19.9, 24.9, 32.1, 62.4, 75.3,
104.7, 117.1, 118.5, 118.9, 124.6, 126.9, 132.3, 138.2, 153.7,
160.6; HR-MS 265.084 (C15H14O3 + Na+ calcd 265.084).
C
4.1.12. 2-(4-(2-Oxo-2H-chromen-4-yl)but-3-
ynyl)isoindoline-1,3-dione (22)