Wu et al.
(m, 1H), 6.03-5.98 (m, 2H), 2.47 (td, 2H, J ) 6.8, 1.5 Hz),
1.61-1.39 (m, 4H), 0.89 (t, 3H, J ) 7.0 Hz); 13C NMR (CDCl3,
100 MHz) δ 132.7, 132.6, 132.2, 128.3, 127.1, 122.7, 117.3,
116.9, 115.0, 101.2, 93.3, 91.4, 78.1, 30.6, 21.9, 19.6, 13.6; MS
(EI) [m/z (relative intensity)] 233 (M+, 22), 218 (55), 204 (100),
190 (73), 164 (36); HRMS calcd for C17H15N 233.1205, found
233.1210.
4-(3(Z)-Decen -1,5-d iyn yl)ben zon itr ile (1h ): obtained in
46% yield as an oil according to method C; H NMR (CDCl3,
1
200 MHz) δ 7.61 (d, 2H, J ) 6.4 Hz), 7.53 (d, 2H, J ) 8.4 Hz),
5.95 (d, 2H, J ) 1.6 Hz), 2.44 (t, 2H, J ) 6.8 Hz), 1.59-1.44
(m, 4H), 0.9 (t, 3H, J ) 7.2 Hz); 13CNMR (CDCl3, 50 MHz) δ
132.0, 131.9, 128.1, 122.2, 118.4, 117.1, 111.5, 100.6, 93.9, 91.3,
78.2, 30.5, 21.8, 19.4, 13.5; MS (EI) [m/z (relative intensity)]
233 (M+, 51), 203 (51), 190 (100), 177 (35), 164 (46), 140 (28);
HRMS calcd for C17H15N, Mr ) 233.1206, found 233.1205.
4-(3(Z)-Decen -1,5-d iyn yl)ben zoch lor id e (1i): obtained in
2-(9-(Tet r a h yd r op yr a n yloxy)-3(Z)-n on en -1,5-d iyn yl)-
ben zon itr ile (1c): obtained as an oil according to method B;
1H NMR (CDCl3, 400 MHz) δ 7.67-7.63 (m, 2H), 7.58-7.50
(m, 2H), 7.43-7.35 (m, 2H), 6.03 (d, 1H, J ) 10.9 Hz), 5.96
(dt, 1H, J ) 10.9, 1.7 Hz), 4.58 (t, 1H, J ) 3.8 Hz), 3.90-3.76
(m, 2H), 3.57-3.46 (m, 2H), 2.60 (td, 2H, J ) 7.3, 1.7 Hz),
1.95-1.48 (m, 8H); 13C NMR (CDCl3, 100 MHz) δ 132.8, 132.7,
132.6, 132.4, 132.2, 128.4, 122.5, 117.1, 115.0, 100.4, 98.7, 93.2,
91.7, 78.3, 66.0, 62.1, 30.6, 28.7, 25.4, 19.5, 16.8; MS (EI) [m/z
(relative intensity)] 319 (M+, 11), 235 (68), 216 (100), 203 (38),
190 (71); HRMS calcd for C21H21NO2 319.1573, found 319.1576.
1
31% yield as an oil according to method C; H NMR (CDCl3,
200 MHz) δ 7.36 (d, 2H, J ) 8.8 Hz), 7.31 (d, 2H, J ) 8.6 Hz),
5.97-5.84 (m, 2H), 2.45 (t, 2H, J ) 6.8 Hz), 1.61-1.45 (m, 4H),
0.9 (t, 3H, J ) 7.0 Hz); 13CNMR (CDCl3, 50 MHz) δ 134.4,
132.8, 128.6, 121.7, 120.7, 117.7, 99.7, 94.7, 88.1, 78.3, 30.7,
21.8, 19.5, 13.5; MS (EI) [m/z (relative intensity)] 242 (M+,
100), 201 (16), 199 (40), 192 (78), 165 (63), 164 (45), 163 (52);
HRMS calcd for C16H15Cl, Mr ) 242.0859, found 242.0863.
(3Z)-Decen -1,5-d iyn ylben zen e (1j): obtained in 67% yield
2-(7-(Tetr a h yd r op yr a n yloxy)-3(Z)-h ep ten -1,5-d iyn yl)-
ben zon itr ile (1d ): obtained as an oil according to method
1
as an oil according to method B; HNMR(CDCl3, 200 MHz) δ
7.49-7.43 (m, 2H), 7.35-7.29 (m, 3H), 5.94 (d, 1H, J ) 10.8
Hz), 5.87 (d, 1H, J ) 10.8 Hz), 2.45 (t, 2H, J ) 6.8 Hz), 1.63-
1.43 (m, 4H), 0.9 (t, 3H, J ) 7.0 Hz); 13CNMR (CDCl3, 50 MHz)
δ 131.7 128.3, 128.2, 123.2, 120.3, 118.1, 99.4, 96.0, 87.2, 78.4,
30.7, 21.9, 19.5, 13.6; MS (EI) [m/z (relative intensity)] 208
(M+, 67), 179 (26), 178 (63), 165 (100), 163 (28), 152 (27), 139
(39), 115 (28); HRMS calcd for C16H16, Mr ) 208.1255, found
208.1252.
1
B; H NMR (CDCl3, 400 MHz) δ 7.59-7.66 (m, 2H), 7.54 (td,
1H, J ) 7.5, 1.3 Hz), 7.41 (td, 1H, J ) 7.5, 1.3 Hz), 6.10 (d,
1H, J ) 10.8 Hz), 6.02 (td, 1H, J ) 10.8, 2.0 Hz), 4.87 (t, 1H,
J ) 3.5 Hz), 4.56 (dd, 1H, J ) 6.3, 1.9 Hz), 4.49 (dd, 1H, J )
6.3, 1.9 Hz), 3.82-3.88 (m, 1H), 3.50-3.55 (m, 1H), 1.50-1.83
(m, 6H); 13C NMR (CDCl3, 100 MHz) δ 132.8, 132.7, 132.2,
128.6, 128.5, 121.7, 121.3, 118.6, 96.8, 94.8, 92.7, 92.5, 82.9,
61.9, 55.0, 51.0, 30.2, 25.3, 18.9; MS (EI) [m/z (relative
intensity)] 291 (M+, 1.8), 190 (100), 85 (45); HRMS calcd for
2-(3(Z)-Decen -1,5-d iyn yl)p yr id in e (1k ): obtained in 84%
yield as an oil according to method B; 1HNMR(CDCl3, 200
MHz) δ 8.58 (dt, 1H, J ) 5.0, 1.0 Hz), 7.63 (td, 1H, J ) 7.6,
1.8 Hz), 7.42 (td, 1H, J ) 7.6, 1.0 Hz), 7.23-7.16 (m, 2H), 5.99-
5.93 (m, 2H), 2.43 (td, 2H, J ) 7.0, 1.6 Hz), 1.92-1.43 (m, 4H),
0.87 (t, 3H, J ) 7.0 Hz); 13CNMR (CDCl3, 50 MHz) δ 150.5,
143.3, 135.9, 127.2, 122.7, 122.1, 117.3, 100.3, 94.7, 86.8, 78.2,
30.6, 21.8, 19.5, 13.5; MS (EI) [m/z (relative intensity)] 209
(M+, 19), 180 (100), 78 (18), 51 (18); HRMS calcd for C15H15N,
Mr ) 209.1209, found 209.1205.
C
19H17NO2 291.1260, found 291.1255.
Gen er a l P r oced u r e for Cou p lin g of Ar yl Iod id es w ith
(Z)-3-Decen -1,5-d iyn e (Meth od C). A degassed solution of
(Z)-3-hexen-1,5-diyne (2.3 mmol) in dry ether (5 mL) contain-
ing Pd(PPh3)4 (0.1 mmol) and CuI (0.6 mmol) was added to a
solution of aryl iodide (4.5 mmol) containing n-butylamine (5
mmol). The resulting solution was stirred for 6 h at 25 °C,
quenched with saturated aqueous NH4Cl and Na2CO3 solu-
tions, and extracted with EtOAc. The organic layer was
separated and dried over MgSO4. After filtration, the solvent
was evaporated in vacuo. The residue was purified by flash
chromatography to give the products.
2-(3(Z)-Decen -1,5-d iyn yl)th iop h en e (1l): obtained in 53%
1
yield as an oil according to method B; H NMR (CDCl3, 200
MHz) δ 7.29 (d, 1H, J ) 5.2 Hz), 7.22 (d, 1H, J ) 2.6 Hz), 7.00
(t, 1H, J ) 5.2 Hz), 5.94 (d, 1H, J ) 10.4 Hz), 5.86 (d, 1H, J )
10.8 Hz), 2.45 (d, 2H, J ) 6.8 Hz), 1.63-1.47 (m, 4H), 0.92 (t,
3H, J ) 6.8 Hz); 13C NMR (CDCl3, 50 MHz) δ 132.1, 127.7,
127.2, 123.3, 120.1, 117.7, 99.8, 91.2, 89.1, 78.4, 30.6, 21.9, 19.5,
13.5; MS (EI) [m/z (relative intensity)] 214 (M+, 100), 184 (41),
171 (80), 165 (53); HRMS calcd for C14H14S, Mr ) 214.0811,
found 214.0817.
4-(3(Z)-Decen -1,5-diyn yl)(tr iflu or om eth yl)ben zen e (1e):
obtained in 46% yield as an oil according to method C; 1H NMR
(CDCl3, 200 MHz) δ 7.57 (s, 4H), 5.95 (d, 2H, J ) 1.6 Hz),
2.46 (t, 2H, J ) 6.8 Hz), 1.58-1.49 (m, 4H), 0.90 (t, 3H, J )
7.0 Hz); 13C NMR (CDCl3, 50 MHz) 146.9, 134.6, 131.8, 127.0,
125.3, 121.6, 117.4, 112.1, 100.2, 89.4, 78.3, 30.6, 21.9, 19.5,
13.5; MS (EI) [m/z (relative intensity)] 276 (M+, 100), 233 (59),
207 (31), 192 (24), 165 (47), 49 (43); HRMS calcd for C17H15F3,
Mr ) 276.1129, found 276.1174.
2-(3(Z)-Decen -1,5-diyn yl)(tr iflu or om eth yl)ben zen e (1f):
obtained in 33% yield as an oil according to method C; 1H NMR
(CDCl3, 200 MHz) δ 7.64 (td, 2H, J ) 7.8, 1.8 Hz), 7.39-7.37
(m, 2H), 6.02-5.87 (m, 2H), 2.45 (t, 2H, J ) 7.0 Hz), 1.60-
1.51 (m, 4H), 0.90 (t, 3H, J ) 7.0 Hz); 13CNMR (CDCl3, 50
MHz) δ 146.3, 134.2, 131.2, 128.0, 125.8, 125.7, 121.6, 117.5,
112.1, 100.3, 92.5, 91.5, 78.0, 30.6, 21.9, 19.5, 13.5; MS (EI)
[m/z (relative intensity)] 276 (M+, 100), 233 (34), 232 (29), 221
(48), 214 (22), 183 (29), 165 (14); HRMS calcd for C17H15F3,
Mr ) 276.1174, found 276.1174.
3-(3(Z)-Decen -1,5-diyn yl)(tr iflu or om eth yl)ben zen e (1g):
obtained in 46% yield as an oil according to method C; 1H NMR
(CDCl3, 200 MHz) δ 7.72 (s, 1H), 7.61 (d, 1H, J ) 7.6 Hz),
7.55 (d, 1H, J ) 8.0 Hz), 7.45 (t, 1H, J ) 7.6 Hz), 5.97 (d, 1H,
J ) 10.8 Hz), 5.92 (d, 1H, J ) 10.8 Hz), 2.46 (t, 2H, J ) 6.8
Hz), 1.62-1.45 (m, 4H), 0.90 (t, 3H, J ) 7.2 Hz); 13CNMR
(CDCl3 50 MHz) δ 146.9, 134.6, 128.8, 128.5, 124.8, 124.8,
124.2, 121.5, 117.4, 100.1, 94.2, 88.6, 78.3, 30.6, 21.8, 19.5, 13.4;
MS (EI) [m/z (relative intensity)] 276 (M+, 100), 261 (30), 246
(34), 233 (84), 207 (47), 183 (62), 178 (37), 165 (68); HRMS
calcd for C17H15F3, Mr ) 276.1125, found 276.1174.
2-(3(Z)-Decen -1,5-d iyn yl)p yr a zin e (1m ): obtained in 99%
1
yield as an oil according to method B; H NMR (CDCl3, 200
MHz) δ 8.66 (d, 1H, J ) 1.6 Hz), 8.55 (s, 1H), 8.45 (d, 1H, J )
2.4 Hz), 5.98 (m, 2H), 2.44 (t, 2H, J ) 6.8 Hz), 1.58-1.43 (m,
4H), 0.88 (t, 3H, J ) 7.0 Hz); 13C NMR (CDCl3, 50 MHz) δ
147.8, 144.4, 142.6, 140.3, 123.5, 116.5, 101.3, 91.7, 90.8, 78.1,
30.5, 21.8, 19.5, 13.5; MS (EI) [m/z (relative intensity)] 210
(M+, 39), 181 (100), 168 (14), 127 (17); HRMS calcd for
C
14H14N2, Mr ) 210.1154, found 210.1158.
4-(3(Z)-Decen -1,5-d iyn yl)ben zon itr id e (1n ): obtained in
1
59% yield as an oil according to method B; H NMR (CDCl3,
200 MHz) δ 8.16 (d, 2H, J ) 9.0 Hz), 7.60 (d, 2H, J ) 9.0 Hz),
5.97 (s, 2H), 2.45 (t, 2H, J ) 6.4 Hz), 1.61-1.45 (m, 4H), 0.9
(t, 3H, J ) 7.0 Hz); 13CNMR (CDCl3, 50 MHz) δ 147.0, 132.1,
123.5, 122.6, 118.3, 117.0, 100.9, 93.6, 92.2, 78.2, 30.6, 21.8,
19.5, 13.5; MS (EI) [m/z (relative intensity)] 253 (M+, 100), 238
(16), 210 (16), 192 (14), 165 (13), 163 (21); HRMS calcd for
C
16H15NO2, Mr ) 253.1105, found 253.1103.
2-(3(Z)-Decen -1,5-d iyn yl)ben zoa te (1o): obtained in 31%
yield as an oil according to method B; 1HNMR (CDCl3, 200
MHz) δ 7.95 (d, 1H, J ) 7.8 Hz), 7.57 (d, 1H, J ) 7.4 Hz),
7.46-7.31 (m, 2H), 6.00 (d, 1H, J ) 10.8 Hz), 5.91 (d, 1H, J )
10.8 Hz, 3.91 (s, 2H), 2.45 (t, 2H, J ) 6.8 Hz), 1.62-1.42 (m,
4H), 0.87 (t, 3H, J ) 7.0 Hz); 13CNMR (CDCl3, 50 MHz) δ 166.5,
5910 J . Org. Chem., Vol. 67, No. 17, 2002