The Journal of Organic Chemistry
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28.9, 28.5, 26.4, 22.56, 19.5, 14.0. Anal. Calcd for C18H24O: C, 84.32;
H, 9.44. Found: C, 84.20; H, 9.69.
(ppm) 7.29 (d, J = 6.4 Hz, 2H), 6.75 (d, J = 6.0 Hz, 2H), 5.16 (s, 1H),
2.38 (m, 2H), 1.60 (m, 2H), 1.46 (m, 2H), 1.32 (m, 8H), 0.89 (t, J =
6.0 Hz, 3H). 13C NMR (CDCl3): δ (ppm) 155.0, 133.1, 116.5, 115.3,
88.9, 80.2, 31.9, 29.2, 29.14, 29.0, 28.9, 22.7, 19.4, 14.1. Anal. Calcd for
C16H22O: C, 83.43; H, 9.63. Found: C, 83.08; H, 9.74.
(Table 5, Entry 13) 3-(Dec-1-ynyl)phenol. The general procedure
method A in Table 5 with 1.5 mol % catalyst afforded the title
compound (172 mg) in 75% isolated yield (yellowish solid). 1H NMR
(CDCl3): δ (ppm) 7.15 (t, J = 8.0 Hz, 1H), 6.97 (dd, J = 7.6, 1.2 Hz,
2H), 6.88 (dd, J = 1.2 Hz, 1H), 6.75 (dt, J = 8.0, 1.6 Hz, 1H), 5.55 (s,
1H), 2.38 (t, J = 7.2 Hz, 2H), 1.56−1.64 (m, 2H), 1.46 (m, 2H), 1.31
(m, 8H), 0.90 (t, J = 6.8 Hz, 3H). 13C NMR (CDCl3): δ (ppm) 155.2,
129.5, 125.4, 124.4, 118.4, 115.0, 90.8, 80.3, 31.9, 29.2, 29.2, 20.0, 28.8,
22.7, 19.4, 14.1. Anal. Calcd for C16H22O: C, 83.43; H, 9.63. Found: C,
83.25; H, 9.37.
(Table 5, Entry 14) 4-((Triisopropylsilyl)ethynyl)benzonitrile. The
general procedure method A in Table 5 with 0.5 mol % catalyst
afforded the title compound (229 mg) in 81% isolated yield. 1H NMR
(CDCl3): δ (ppm) 7.58 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.0 Hz, 2H),
1.11 (s, 18H), 1.09 (m, 3H). 13C NMR (CDCl3): δ (ppm) 132.5,
131.9, 128.3, 118.4, 111.6, 105.1, 96.4, 18.6, 18.5, 11.23. MS (EI) m/z:
283 (M+ − 43).
(Table 5, Entry 15) 3-(Dec-1-ynyl)aniline. The general procedure
method A in Table 5 with 1.5 mol % catalyst afforded the title
compound (180 mg) in 79% isolated yield (yellowish solid). 1H NMR
(CDCl3): δ (ppm) 7.06 (t, J = 8 Hz, 1H), 6.81 (d, J = 7.6 Hz, 1H),
6.73 (s, 1H), 6.60 (d, J = 8 Hz, 1H), 3.62 (s, 2H), 2.39 (t, J = 7.2 Hz,
2H), 1.62 (m, 2H), 1.45 (m, 2H), 1.28−1.33 (m, 8H), 0.92 (t, J = 6.8,
3H). 13C NMR (CDCl3): δ (ppm) 146.2, 129.1, 124.9, 122.0, 118.1,
114.6, 89.9, 80.7, 31.9, 29.2, 29.2, 29.0, 28.8, 22.7, 19.4, 14.1. Anal.
Calcd for C16H23N: C, 83.79; H, 10.11. Found: C, 83.67; H, 10.17.
(Table 5, Entry 16) 4-(Dec-1-ynyl)benzamide. The general
procedure method A in Table 5 with 1.5 mol % catalyst afforded
the title compound (224 mg) in 87% isolated yield (yellowish solid).
1H NMR (CDCl3): δ (ppm) 7.70 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4
Hz, 2H), 6.41 (s, 2H), 2.38 (t, J = 7.2 Hz, 2H), 1.57 (m, 2H), 1.40 (m,
2H), 1.22−1.28 (m, 8H), 0.86 (t, J = 6.0 Hz, 3H). 13C NMR (CDCl3):
δ (ppm) 169.3, 131.7, 128.9, 128.1, 127.3, 93.6, 80.0, 31.8, 29.2, 29.1,
28.9, 28.6, 22.6, 19.5, 14.1. Anal. Calcd for C17H23NO: C, 79.33; H,
9.01. Found: C, 78.96; H, 8.85.
(Table 5, Entry 4) 2-(Dec-1-ynyl)-1,3,5-trimethylbenzene. The
general procedure method A in Table 5 with 0.5 mol % catalyst
afforded the title compound (215 mg) in 84% isolated yield (yellowish
1
solid). H NMR (CDCl3): δ (ppm) 6.88 (s, 2H), 2.54 (t, J = 6.8 Hz,
2H), 2.44 (s, 6H), 2.31 (s, 3H), 1.69 (m, 2H), 1.55 (m, 2H), 1.21−
1.37 (m, 8H), 0.95 (t, J = 6.7 Hz, 3H). 13C NMR (CDCl3): δ (ppm)
139.8, 136.5, 127.4, 120.9, 98.0, 78.2, 31.9, 29.3, 29.1, 28.9, 22.66, 21.2,
21.0, 19.7, 14.1. Anal. Calcd for C19H28: C, 88.99; H, 11.01. Found: C,
88.96; H, 10.99.
(Table 5, Entry 5) 2-(Dec-1-ynyl)-4-fluoro-1-methoxybenzene.
The general procedure method A in Table 5 with 1 mol % catalyst
afforded the title compound (236 mg) in 90% isolated yield. 1H NMR
(CDCl3): δ (ppm) 7.06 (dd, J = 3.2 8.8 Hz, 1H), 6.89 (td, J = 3.2, 8.4
Hz, 1H), 6.74 (dd, J = 4.4, 8.8 Hz, 1H), 3.82 (s, 3H), 2.44 (t, J = 6.8
Hz, 2H), 1.61 (m, 2H), 1.44 (m, 2H), 1.29 (m, 8H), 0.88 (t, J = 6.8
Hz, 3H). 13C NMR (CDCl3): δ (ppm) 157.6, 156.2, 156. 2, 155.2,
119.9, 119.7, 115.1, 114.9, 114.5, 114.4, 111.53, 111.4, 95.7, 75.8, 75.7,
56.3, 31.8, 29.1, 29.1, 28.8, 28.6, 22.6, 19.6, 14.1. Anal. Calcd for
C17H23FO: C, 77.82; H, 8.84; Found: C, 77.90; H, 9.22.
(Table 5, Entry 6) 2-(Cyclohexenylethynyl)benzonitrile. The
general procedure method A in Table 5 with 1 mol % catalyst
afforded the title compound (201 mg) in 97% isolated yield. 1H NMR
(CDCl3): δ (ppm) 7.58 (d, J = 7.6 Hz, 1H), 7.47 (d, J = 4.4 Hz, 2H),
7.31 (m, 1H), 6.33 (m, 1H), 2.33 (m, 2H), 2.63 (m, 2H), 1.65−1.68
(m, 2H), 1.58−1.64 (m, 2H). 13C NMR (CDCl3): δ (ppm) 137.7,
132.5, 132.2, 131.9, 127.9, 127.6, 120.2, 117.6, 115.1, 98.1, 83.2, 28.8,
25.9, 22.2, 21.4. MS(EI) m/z: 207 (M+).
(Table 5, Entry 7) 4-(Cyclohexenylethynyl)benzonitrile. The
general procedure method A in Table 5 with 1 mol % catalyst
afforded the title compound (195 mg) in 94% isolated yield (yellowish
solid). 1H NMR (CDCl3): δ (ppm) 7.54 (d, J = 8.0 Hz, 2H), 7.44 (d, J
= 8.0 Hz, 2H), 6.25 (m, 1H), 2.13−2.21 (m, 4H), 1.59−1.68 (m, 4H).
13C NMR (CDCl3): δ (ppm) 137.2, 132.0, 131.9, 129.0, 120.3, 118.6,
110.9, 95.9, 85.4, 29.1, 25.9, 22.2, 21.4. MS (EI) m/z: 207 (M+).
(Table 5, Entry 8) 9-(Cyclohexenylethynyl)anthracene. The
general procedure method A in Table 5 with 1 mol % catalyst
afforded the title compound (237 mg) in 84% isolated yield (yellowish
solid). 1H NMR (CDCl3): δ (ppm) 8.58 (d, J = 8.4 Hz, 2H), 8.40 (s,
1H), 8.01 (d, J = 8.4 Hz, 2H), 7.58 (t, J = 6.4 Hz, 2H), 7.52 (t, J = 6.8
Hz, 2H), 6.50 (s, 1H), 2.52 (m, 2H), 2.29 (m, 2H), 1.84 (m, 2H), 1.76
(m, 2H). 13C NMR (CDCl3): δ (ppm) 135.4, 132.4, 131.2, 128.6,
127.0, 126. 9, 126.3, 125.6, 121.3, 118.0, 103.1, 83.8, 29.6, 26.0, 22.5,
21.6. Anal. Calcd for C22H18: C, 93.57; H, 6.43. Found: C, 93.35; H,
6.26.
(Table 5, Entry 9) 2-(Phenylethynyl)benzonitrile. The general
procedure method C in Table 5 with 1 mol % catalyst afforded the title
compound (187 mg) in 92% isolated yield (yellowish solid). 1H NMR
(CDCl3): δ (ppm) 7.59 (m, 1H), 7.56 (m, 3H), 7.52 (m, 1H), 7.36
(m, 4H). 13C NMR (CDCl3): δ (ppm) 132.7, 132.4, 132.1, 132.0,
129.2, 128.5, 128.2, 127.3, 122.1, 117.5, 115.4, 96.0, 85.6. MS(EI) m/z:
203 (M+).
(Table 5, Entry 10) 4-(Phenylethynyl)benzonitrile. The general
procedure method C in Table 5 with 1 mol % catalyst afforded the title
compound (177 mg) in 87% isolated yield (yellowish solid). 1H NMR
(CDCl3): δ (ppm) 7.61 (d, J = 5.6 Hz, 2H), 7.59 (d, J = 6.4 Hz, 2H),
7.54 (dd, J = 2.4, 6.4 Hz, 2H), 7.36 (m, 3H). 13C NMR (CDCl3): δ
(ppm) 132.0, 132.0, 131.7, 129.0, 128.4, 128.2, 122.19, 118.4, 111.5,
93.7, 87.6. MS(EI) m/z: 203 (M+).
(Table 5, Entry 11) 1-Methoxy-4-(phenylethynyl)benzene. The
general procedure method C in Table 5 with 1 mol % catalyst afforded
the title compound (187 mg) in 91% isolated yield (yellowish solid).
1H NMR (CDCl3): δ (ppm) 7.50 (d, J = 6.0 Hz, 2H), 7.47 (d, J = 6.8
Hz, 2H), 7.33 (m, 3H), 6.85 (d, J = 8.8 Hz, 2H), 3.82 (s, 3H). 13C
NMR (CDCl3): δ (ppm) 159.6, 133.0, 131.4, 128.2, 127.9, 123.6,
115.4, 114.0, 89.3, 88.0, 55.2. MS(EI) m/z: 208 (M+).
(Table 5, Entry 17) 5-(Pyridin-2-yl)pent-4-yn-1-ol. The general
procedure method B in Table 5 with 1 mol % catalyst afforded the title
1
compound (129 mg) in 80% isolated yield. H NMR (CDCl3): δ
(ppm) 8.24 (d, J = 1.6 Hz, 1H), 7.52 (td, J = 8.0, 1.2 Hz, 1H), 7.27
(dd, J = 8.0, 1.2 Hz, 1H), 7.09 (td, J = 8.0, 1.2 Hz, 1H), 4.0 (s, 1H),
3.73 (t, J = 6.0 Hz, 2H), 2.50 (t, J = 8.8 Hz, 2H), 1.82 (q, J = 6.4 Hz,
2H). 13C NMR (CDCl3): δ (ppm) 149.5, 143.6, 136.2, 126.9, 122.4,
90.8, 80.4, 60.9, 31.2, 15.9. Anal. Calcd for C10H11NO: C, 74.51; H,
6.88. Found: C, 74.43; H, 6.92.
(Table 5, Entry 18) 2-((3-Aminophenyl)ethynyl)benzonitrile. The
general procedure method C in Table 5 with 1 mol % catalyst afforded
the title compound (157 mg) in 72% isolated yield. 1H NMR
(CDCl3): δ (ppm) 7.65 (d, J = 7.6 Hz, 1H), 7.60 (d, J = 8 Hz, 1H),
7.56 (m, 1H), 7.39 (m, 1H), 7.15 (t, J = 7.6 Hz, 1H), 7.02 (m, 1H),
6.72 (m, 1H), 6.70 (d, J = 8.0 Hz, 1H), 3.78 (s, 2H). 13C NMR
(CDCl3): δ (ppm) 146.6, 132.6, 132.4, 132.1, 129.4, 128.2, 127.4,
122.7, 122.2, 118.1, 117.7, 116.3, 115.2, 96.5, 85.1. Anal. Calcd for
C15H10N2: C, 82.55; H, 4.62. Found: C, 82.29; H, 4.73.
(Table 5, Entry 19) 4-(5-Chloropent-1-ynyl)benzonitrile. The
general procedure method A in Table 5 with 1 mol % catalyst
afforded the title compound (183 mg) in 90% isolated yield. 1H NMR
(CDCl3): δ (ppm) 7.55 (d, J = 6.8 Hz, 2H), 7.45 (d, J = 6.8 Hz, 2H),
3.69 (t, J = 6.4 Hz, 2H), 2.60 (t, J = 6.8 Hz, 2H), 2.05 (q, J = 6.4 Hz,
2H). 13C NMR (CDCl3): δ (ppm) 132.2, 131.95, 128.6, 118.5, 111.1,
93.25, 80.3, 43.6, 31.1, 17.0. MS (EI) m/z: 203 (M+).
(Table 5, Entry 20) 4-(Cyclohexenylethynyl)-2-(methylthio)-
pyrimidine. The general procedure method B in Table 5 with 1 mol
% catalyst afforded the title compound (238 mg) in 91% isolated yield.
1H NMR (CDCl3): δ (ppm) 8.42 (d, J = 5.21 Hz, 1H), 6.96 (d, J = 5.2
(Table 5, Entry 12) 4-(Dec-1-ynyl)phenol. The general procedure
method A in Table 5 with 1.5 mol % catalyst afforded the title
1
compound (145 mg) in 67% isolated yield. H NMR (CDCl3): δ
Hz, 1H), 6.41 (m, 1H), 2.56 (s, 3H), 2.23 (m, 2H), 2.17 (m, 2H),
K
dx.doi.org/10.1021/jo302195y | J. Org. Chem. XXXX, XXX, XXX−XXX