The Journal of Organic Chemistry
Page 4 of 7
7.63 (dd, J = 8.2, 1.3 Hz, 2H), 7.56 – 7.46 (m, 3H), 7.41 (t, J = 7.6
= 6.7 Hz, 2H), 1.75 – 1.62 (m, 2H), 1.50 – 1.27 (m, 2H), 0.96 (t, J
= 7.4 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 154.1, 132.9,
130.5, 128.5, 119.6, 86.0, 80.7, 65.9, 30.4, 19.0, 13.6.
octyl 3-phenylpropiolate (3bd):27 White solid (46.0 mg, 89%
yield); Rf = 0.8 (PE/EA = 4:1); 1H NMR (400 MHz, CDCl3) δ 7.58
(d, J = 7.0 Hz, 2H), 7.44 (t, J = 7.4 Hz, 1H), 7.36 (t, J = 7.5 Hz,
2H), 4.22 (t, J = 6.8 Hz, 2H), 1.76 – 1.66 (m, 2H), 1.45 – 1.20 (m,
10H), 0.88 (t, J = 6.6 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 154.2, 132.9, 130.5, 128.5, 119.6, 86.0, 80.7, 66.2, 31.7, 29.1,
29.1, 28.4, 25.8, 22.6, 14.0.
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Hz, 2H), 7.14 – 7.02 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
151.8, 149.2, 133.2, 132.6, 131.1, 128.7, 123.2, 119.5, 119.1, 89.1,
80.0.
4-iodophenyl 3-phenylpropiolate (3ak):21,22 White solid (57.7
1
mg, 83% yield); Rf = 0.9 (PE/EA = 4:1); H NMR (400 MHz,
CDCl3) δ 7.76 – 7.69 (m, 2H), 7.65 – 7.60 (m, 2H), 7.50 (t, J = 7.4
Hz, 1H), 7.41 (t, J = 7.6 Hz, 2H), 7.02 – 6.88 (m, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ 151.8, 150.0, 138.6, 133.2, 131.1, 128.7,
123.6, 119.1, 90.5, 89.1, 80.0.
8
9
4-cyanophenyl 3-phenylpropiolate (3al):20 White solid (34.1 mg,
69% yield); Rf = 0.6 (PE/EA = 4:1); 1H NMR (400 MHz, CDCl3) δ
7.76 – 7.68 (m, 2H), 7.67– 7.61 (m, 2H), 7.55 – 7.46 (m, 1H), 7.45–
7.40 (m, 2H), 7.37 – 7.30 (m, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 153.2, 151.1, 133.8, 133.3, 131.4, 128.7, 122.6, 118.8,
118.0, 110.3, 89.8, 79.6.
4-(trifluoromethyl) phenyl 3-phenylpropiolate (3am):20 White
solid (31.9 mg, 55% yield); Rf = 0.8 (PE/EA = 4:1); 1H NMR (400
MHz, CDCl3) δ 7.70 (d, J = 8.5 Hz, 2H), 7.67– 7.63 (m, 2H), 7.55
– 7.46 (m, 1H), 7.46– 7.39 (m, 2H), 7.34 (d, J = 8.6 Hz, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ 152.5, 151.6, 133.2, 131.3, 128.7, 128.6
(q, J = 32.9 Hz), 126.9 (q, J = 3.8 Hz), 123.7 (q, J = 272.1 Hz),
122.0, 118.9, 89.4, 79.8.
2,2,2-trifluoroethyl 3-phenylpropiolate (3be):28 White solid
(36.5 mg, 80% yield); Rf = 0.9 (PE/EA = 4:1); 1H NMR (400 MHz,
CDCl3) δ 7.62 (dd, J = 8.2, 1.4 Hz, 2H), 7.53 – 7.45 (m, 1H), 7.43
– 7.37 (m, 2H), 4.60 (q, J = 8.3 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 152.1, 133.2, 131.2, 128.7, 122.6 (q, J = 275.0 Hz), 118.9,
89.2, 79.1, 61.1 (q, J = 37.0 Hz).
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benzyl 3-phenylpropiolate (3bf):26,32 White solid (45.3 mg, 96%
yield); Rf = 0.9 (PE/EA = 4:1); 1H NMR (400 MHz, CDCl3) δ 7.62
– 7.54 (m, 2H), 7.49 – 7.30 (m, 8H), 5.28 (s, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ 153.8, 134.9, 133.0, 130.6, 128.6, 128.6,
128.6, 128.5, 119.5, 86.7, 80.5, 67.7.
naphthalen-2- ylmethyl 3-phenylpropiolate (3bg):29 White solid
(53.2 mg, 93% yield); Rf = 0.9 (PE/EA = 4:1); 1H NMR (400 MHz,
CDCl3) δ 7.92 – 7.81 (m, 4H), 7.62 – 7.57 (m, 2H), 7.56 – 7.49 (m,
4-nitrophenyl 3-phenylpropiolate (3an):22 White solid (37.4 mg,
70% yield); Rf = 0.8 (PE/EA = 4:1); 1H NMR (400 MHz, CDCl3) δ
8.34 – 8.25 (m, 2H), 7.69 – 7.61 (m, 2H), 7.56 – 7.48 (m, 1H), 7.46
– 7.32 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3) δ 154.7, 151.0,
145.7, 133.3, 131.4, 128.8, 125.3, 122.3, 118.8, 90.0, 79.6.
naphthalen-2-yl 3-phenylpropiolate (3ao):23 White solid (50.1
3H), 7.48 – 7.42 (m, 1H), 7.40 – 7.33 (m, 2H), 5.44 (s, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ 153.9, 133.2, 133.1, 133.0, 132.3, 130.7,
128.5, 128.5, 128.0, 127.9, 127.7, 126.4, 126.3, 126.0, 119.5, 86.8,
80.5, 67.8.
cinnamyl 3-phenylpropiolate (3bh):30 White solid (51.4 mg, 98%
yield); Rf = 0.8 (PE/EA = 4:1);1H NMR (400 MHz, CDCl3) δ 7.62–
7.58 (m, 2H), 7.48 – 7.18 (m, 8H), 6.73 (d, J = 15.9 Hz, 1H), 6.33
(dt, J = 15.8, 6.6 Hz, 1H), 4.89 (dd, J = 6.6, 1.3 Hz, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ 153.8, 135.9, 135.3, 133.0, 130.7, 128.6,
128.5, 128.2, 126.7, 122.0, 119.5, 86.6, 80.5, 66.5.
1
mg, 92% yield); Rf = 0.8 (PE/EA = 4:1); H NMR (400 MHz,
CDCl3) δ 7.95 – 7.76 (m, 3H), 7.73 – 7.60 (m, 3H), 7.57 – 7.46 (m,
3H), 7.42 (t, J = 7.5 Hz, 2H), 7.34 (dd, J = 8.9, 2.2 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ 152.4, 147.8, 133.7, 133.2, 131.7, 131.0,
129.6, 128.7, 127.8, 127.8, 126.7, 126.0, 120.7, 119.3, 118.6, 88.8,
80.3.
thiophen-2-ylmethyl 3-phenylpropiolate (3bi):31 White solid
(40.2 mg, 83% yield); Rf = 0.8 (PE/EA = 4:1); 1H NMR (400 MHz,
CDCl3) δ 7.57 (dd, J = 8.2, 1.3 Hz, 2H), 7.50 – 7.40 (m, 1H), 7.41
– 7.32 (m, 3H), 7.18 (d, J = 3.4 Hz, 1H), 7.02 (dd, J = 5.1, 3.5 Hz,
1H), 5.42 (s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 153.7, 136.6,
133.0, 130.7, 129.1, 128.5, 127.4, 126.9, 119.4, 87.0, 80.3, 61.6.
Furan-2- ylmethyl 3-phenylpropiolate (3bj):31 White solid (38.0
naphthalen-1-yl 3-phenylpropiolate (3ap):24 White solid (48.4
1
mg, 89% yield); Rf = 0.8 (PE/EA = 4:1); H NMR (400 MHz,
CDCl3) δ 8.02 (dd, J = 7.0, 1.9 Hz, 1H), 7.91 (dd, J = 6.9, 2.5 Hz,
1H), 7.80 (d, J = 8.3 Hz, 1H), 7.69 – 7.63 (m, 2H), 7.61 – 7.46 (m,
4H), 7.46 – 7.31 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
152.4, 146.1, 134.7, 133.2, 131.1, 128.7, 128.0, 126.7, 126.6, 126.6,
126.5, 125.3, 121.2, 119.3, 118.1, 89.1, 80.2.
4-(1H-pyrrol-1-yl)phenyl 3-phenylpropiolate (3aq): White solid
(48.8 mg, 85% yield); mp = 104−105 °C; Rf = 0.8 (PE/EA = 4:1);
1H NMR (400 MHz, CDCl3) δ 7.63 (dd, J = 8.3, 1.3 Hz, 2H), 7.51
– 7.44 (m, 1H), 7.43 – 7.32 (m, 4H), 7.27 – 7.21 (m, 2H), 7.04 (t, J
= 2.1 Hz, 2H), 6.35 (t, J = 2.0 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 152.2, 147.6, 138.9, 133.2, 131.1, 128.7, 122.5, 121.5,
119.4, 119.1, 110.7, 89.0, 80.1; IR (KBr) ṽ 3135, 2238, 1723, 1517,
1437, 1334, 1287, 1215, 1152, 1072, 922, 851, 763, 723, 675, 612,
526 cm−1; HRMS (ESI-TOF) m/z: calcd. for C19H13NNaO2
[M+Na]+: 310.0838, found 310.0838.
methyl 3-phenylpropiolate (3ba):25 White solid (24.9 mg, 78%
yield); Rf = 0.8 (PE/EA = 4:1); 1H NMR (400 MHz, CDCl3) δ 7.58
(d, J = 7.4 Hz, 2H), 7.45 (t, J = 7.4 Hz, 1H), 7.37 (t, J = 7.5 Hz,
2H), 3.84 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 154.4, 133.0,
130.7, 128.5, 119.5, 86.5, 80.3, 52.8.
ethyl 3-phenylpropiolate (3bb):25 White solid (34.5 mg, 99%
yield); Rf = 0.8 (PE/EA = 4:1); 1H NMR (400 MHz, CDCl3) δ 7.58
(d, J = 7.5 Hz, 2H), 7.44 (t, J = 7.2 Hz, 1H), 7.36 (t, J = 7.6 Hz,
2H), 4.29 (q, J = 7.1 Hz, 2H), 1.35 (t, J = 7.1 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 154.0, 132.9, 130.5, 128.5, 119.6, 86.0,
80.7, 62.0, 14.0.
butyl 3-phenylpropiolate (3bc):26 White solid (37.2 mg, 92%
yield); Rf = 0.8 (PE/EA = 4:1); 1H NMR (400 MHz, CDCl3) δ 7.60
– 7.55 (m, 2H), 7.47 – 7.40 (m, 1H), 7.40 – 7.32 (m, 2H), 4.23 (t, J
1
mg, 84% yield); Rf = 0.8 (PE/EA = 4:1); H NMR (400 MHz,
CDCl3) δ 7.59 – 7.54 (m, 2H), 7.48 – 7.41 (m, 2H), 7.39 – 7.32 (m,
2H), 6.49 (d, J = 3.2 Hz, 1H), 6.39 (dd, J = 3.3, 1.8 Hz, 1H), 5.22
(s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 153.6, 148.4, 143.6,
133.0, 130.7, 128.5, 119.4, 111.5, 110.7, 87.0, 80.2, 59.2.
2-(pyridin-2-yl)ethyl 3-phenylpropiolate (3bk): Colorless oil
(37.7 mg, 75% yield); Rf = 0.3 (PE/EA = 4:1); 1H NMR (400 MHz,
CDCl3) δ 8.56 (d, J = 4.2 Hz, 1H), 7.63 (td, J = 7.7, 1.8 Hz, 1H),
7.59 – 7.54 (m, 2H), 7.47 – 7.40 (m, 1H), 7.39 – 7.30 (m, 2H), 7.23
(d, J = 7.8 Hz, 1H), 7.19 – 7.14 (m, 1H), 4.64 (t, J = 6.8 Hz, 2H),
3.20 (t, J = 6.8 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 157.4,
154.0, 149.5, 136.5, 133.0, 130.6, 128.5, 123.5, 121.8, 119.5, 86.4,
80.5, 65.1, 37.1; IR (KBr) ṽ 3388, 3063, 3016, 2960, 2928, 2857,
2222, 1706, 1588, 1493, 1437, 1390, 1287, 1176, 1040, 993, 755,
692, 596, 525, 501 cm−1; HRMS (ESI-TOF) m/z: calcd. for
C16H14NO2 [M+H]+: 252.1019, found 252.1015.
3-phenylprop-2-yn-1-yl 3-phenylpropiolate (3bl):30 White solid
(46.8 mg, 90% yield; 221.2 mg, 85% yield for 1 mmol scale
reaction), Rf = 0.6 (PE/EA = 10:1); 1H NMR (400 MHz, CDCl3) δ
7.60 (d, J = 7.1 Hz, 2H), 7.51 – 7.43 (m, 3H), 7.42 – 7.27 (m, 5H),
5.07 (s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 153.2, 133.0,
131.9, 130.8, 128.9, 128.6, 128.3, 121.9, 119.3, 87.4, 87.3, 81.9,
80.0, 54.1.
cyclopentyl -3- phenylpropiolate (3bm):32 White solid (25.7 mg,
60% yield); Rf = 0.8 (PE/EA = 6:1); 1H NMR (400 MHz, CDCl3) δ
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