The Journal of Organic Chemistry
Note
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(924 mg, 87%); H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 7.2 Hz,
13.9; IR (KBr) ν 2978, 2932, 1735, 1717, 1676, 1599, 1575, 1366,
1284, 1252, 1169, 1133, 1031, 832, 758 cm−1; MS (m/z, ESI) 523 [M
+ H]+; HRMS (ESI) calcd for C30H35O8 [M + H]+ 523.2326, found
523.2323.
2H), 7.56 (t, J = 7.4 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 7.26 (s, 1H),
6.78 (s, 1H), 6.00 (s, 2H), 4.24 (q, J = 7.2 Hz, 4H), 4.09 (s, 2H), 3.38
(s, 2H), 1.49 (s, 9H), 1.24 (t, J = 7.0 Hz, 6H); 13C NMR (100 M,
CDCl3) δ 197.2, 169.4, 164.2, 149.7, 147.2, 136.5, 133.2, 128.5, 128.2,
128.1, 118.5, 113.4, 109.9, 102.0, 88.6, 82.5, 81.0, 61.9, 55.1, 41.1, 28.0,
24.6, 13.9; IR (KBr) ν 2979, 2931, 1736, 1719, 1687, 1600, 1504,
1370, 1249, 1183, 1124, 1034, 1002, 932, 857, 749, 689 cm−1; MS (m/
z, ESI) 554 [M + NH4]+; HRMS (ESI) calcd for C30H36NO9 [M +
NH4]+ 554.2385, found 554.2382.
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)-4-methoxyphenyl)prop-2-
yn-1-yl)-2-(2-oxo-2-phenylethyl)malonate (1d). Yellow oil (758
mg, 73%); 1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 7.2 Hz,
2H), 7.56 (t, J = 7.2 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 7.32−7.28 (m,
2H), 6.90 (dd, J = 2.8, 8.4 Hz, 1H), 4.25 (q, J = 7.1 Hz, 4H), 4.09 (s,
2H), 3.80 (s, 3H), 3.39 (s, 2H), 1.50 (s, 9H), 1.25 (t, J = 7.0 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ 197.1, 169.4, 165.0, 158.6, 136.4,
135.5, 134.9, 133.2, 128.4, 128.1, 117.1, 115.3, 114.7, 87.6, 82.3, 81.3,
61.8, 55.3, 55.0, 41.1, 27.9, 24.5, 13.9; IR (KBr) ν 2979, 2934, 2255,
1735, 1721, 1687, 1603, 1563, 1496, 1448, 1366, 1291, 1250, 1183,
1165, 1075, 1039, 1002, 911, 849, 730, 689 cm−1; MS (m/z, ESI) 540
[M + NH4]+; HRMS (ESI) calcd for C30H38NO8 [M + NH4]+
540.2592, found 540.2592.
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)-4-fluorophenyl)prop-2-yn-
1-yl)-2-(2-oxo-2-phenylethyl)malonate (1e). Yellow oil (608 mg,
60%); H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 7.6 Hz, 2H), 7.57
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)phenyl)prop-2-yn-1-yl)-2-(2-
(4-chlorophenyl)-2-oxoethyl)malonate (1i). Yellow oil (520 mg,
1
45%); H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.4 Hz, 2H), 7.80
(d, J = 8.0 Hz, 1H), 7.43−7.27 (m, 5H), 4.24 (q, J = 6.9 Hz, 4H), 4.08
(s, 2H), 3.39 (s, 2H), 1.51 (s, 9H), 1.25 (t, J = 7.0, 6H); 13C NMR
(100 MHz, CDCl3) δ 196.1, 169.3, 165.1, 139.7, 134.9, 134.2, 133.6,
131.0, 130.0, 129.7, 128.8, 127.5, 123.2, 89.7, 82.6, 81.2, 62.0, 55.1,
41.1, 28.0, 24.6, 14.0; IR (KBr) ν 3475, 3377, 2978, 2925, 2221, 1732,
1686, 1591, 1448, 1365, 1286, 1249, 1183, 1136, 1085, 1067, 1047,
999, 861, 758, 692 cm−1; MS (m/z, ESI) 544 [M + NH4]+; HRMS
(ESI) calcd for C29H35ClNO7 [M + NH4]+ 544.2097, found 544.2094.
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)phenyl)prop-2-yn-1-yl)-2-(2-
(4-nitrophenyl)-2-oxoethyl)malonate (1j). Yellow solid (512 mg,
1
48%); mp 101−102 °C; H NMR (400 MHz, CDCl3) δ 8.31−8.25
(m, 4H), 7.81 (dd, J = 8.2, 1.0 Hz, 1H), 7.42−7.35 (m, 2H), 7.30 (td, J
= 7.5, 1.7 Hz, 1H), 4.29−4.23 (m, 4H), 4.18 (s, 2H), 3.40 (s, 2H),
1.52 (s, 9H), 1.26 (t, J = 7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ
196.1, 169.2, 165.0, 150.4, 141.0, 134.2, 133.6, 131.1, 130.0, 129.4,
127.6, 123.7, 123.1, 89.5, 82.8, 81.2, 62.1, 55.2, 41.7, 28.0, 24.7, 14.0;
IR (KBr) ν 2977, 2914, 1733, 1709, 1691, 1602, 1529, 1446, 1345,
1285, 1250, 1184, 1138, 1085, 1069, 1004, 892, 781, 700 cm−1; MS
(m/z, ESI) 555 [M + NH4]+; HRMS (ESI) calcd for C29H35N2O9 [M
+ NH4)+ 555.2337, found 555.2334.
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(t, J = 7.4, 1H), 7.51−7.43 (m, 3H), 7.36 (dd, J = 4.8, 9.2 Hz, 1H),
7.06 (td, J = 8.2, 2.4 Hz, 1H), 4.25 (q, J = 7.1 Hz, 4H), 4.09 (s, 2H),
3.40 (s, 2H), 1.50 (s, 9H), 1.25 (t, J = 7.0 Hz, 6H); 13C NMR (100
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)phenyl)prop-2-yn-1-yl)-2-(2-
(naphthalen-2-yl)-2-oxoethyl)malonate (1k). Yellow oil (659 mg,
62%); 1H NMR (400 MHz, CDCl3) δ 8.63 (s, 1H), 8.08 (dd, J = 8.8,
1.6 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.89−7.84 (m, 2H), 7.78 (dd, J
= 7.8, 1.4 Hz, 1H), 7.61−7.50 (m, 2H), 7.38 (dd, J = 7.8, 1.0 Hz, 1H),
7.34−7.24 (m, 2H), 4.28 (q, J = 7.1 Hz, 4H), 4.23 (s, 2H), 3.46 (s,
2H), 1.45 (s, 9H), 1.26 (t, J = 7.0 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ 197.1, 169.5, 165.2, 135.7, 134.2, 133.9, 133.7, 132.4, 130.9,
130.2, 129.9, 129.6, 128.5, 128.3, 127.7, 127.5, 126.6, 123.7, 123.1,
89.8, 82.6, 81.2, 62.0, 55.2, 41.1, 28.0, 24.6, 14.0; IR (KBr) ν 3061,
2978, 2931, 2238, 1735, 1718, 1680, 1469, 1366, 1281, 1255, 1180,
1132, 1083, 856, 818, 756 cm−1; MS (m/z, ESI) 560 [M + NH4]+;
HRMS (ESI) calcd for C33H38NO7 [M + NH4]+ 560.2643, found
560.2641.
MHz, CDCl3) δ 197.1, 169.4, 163.8 (d, JCF = 2.6 Hz), 161.3 (d, JCF
=
248.8 Hz), 136.5, 136.0 (d, JCF = 7.8 Hz), 135.5 (d, JCF = 7.4 Hz),
133.3, 128.5, 128.2, 119.4 (d, JCF = 3.8 Hz), 118.4 (d, JCF = 21.9 Hz),
117.0 (d, JCF = 23.8 Hz), 89.6 (d, JCF = 1.8 Hz), 81.8, 81.5, 61.9, 55.0,
41.1, 27.9, 24.5, 13.9; IR (KBr) ν 2980, 2933, 2226, 1724, 1686, 1600,
1491, 1449, 1367, 1304, 1249, 1184, 1159, 1067, 1002, 942, 831, 749,
689 cm−1; MS (m/z, ESI) 528 [M + NH4]+; HRMS (ESI) calcd for
C29H35FNO7 [M + NH4]+ 528.2392, found 528.2388.
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)-4-chlorophenyl)prop-2-yn-
1-yl)-2-(2-oxo-2-phenylethyl)malonate (1f). Yellow solid (281 mg,
27%); mp 59−60 °C; 1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 7.6
Hz, 2H), 7.76 (s, 1H), 7.57 (t, J = 7.4 Hz, 1H), 7.45 (t, J = 7.6 Hz,
2H), 7.31 (s, 2H), 4.25 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 3.41 (s, 2H),
1.50 (s, 9H), 1.24 (t, J = 7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ
197.1, 169.3, 163.8, 136.5, 135.4, 135.0, 133.4, 133.3, 131.1, 130.0,
128.5, 128.2, 121.8, 91.1, 81.9, 81.6, 61.9, 55.0, 41.1, 28.0, 24.6, 14.0;
IR (KBr) ν 2970, 2928, 1731, 1715, 1686, 1596, 1476, 1356, 1295,
1250, 1185, 1166, 1142, 1094, 1047, 999, 836, 746, 687 cm−1; MS (m/
z, ESI) 544 [M + NH4]+; HRMS (ESI) calcd for C29H35ClNO7 [M +
NH4]+ 544.2097, found 544.2095.
tert-Butyl 2-(6-Oxohept-1-yn-1-yl)benzoate (1l). Yellow oil (378
1
mg, 66%); H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 7.2 Hz, 1H),
7.48−7.45 (m, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.32−7.27 (m, 1H), 2.72
(t, J = 7.4 Hz, 2H), 2.52 (t, J = 6.8 Hz, 2H), 2.18 (s, 3H), 1.93−1.85
(m, 2H), 1.60 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 208.6, 165.8,
134.0, 133.9, 130.8, 129.8, 127.2, 123.5, 94.0, 81.3, 80.2, 42.1, 30.0,
28.1, 22.4, 19.0; IR (KBr) ν 3413, 3065, 2977, 2932, 2234, 1710, 1596,
1567, 1445, 1367, 1252, 1183, 1171, 1131, 1082, 1038, 954, 847, 757,
699 cm−1; MS (m/z, ESI) 304 [M + NH4)+; HRMS (ESI) calcd for
C18H26NO3 [M + NH4]+ 304.1907, found 304.1909.
Diethyl 2-(3-(4-Bromo-2-(tert-butoxycarbonyl)phenyl)prop-2-yn-
1-yl)-2-(2-oxo-2-phenylethyl)malonate (1g). Yellow solid (910 mg,
82%); mp 62−63 °C; H NMR(400 MHz, CDCl3) δ 8.06 (d, J = 7.6
1
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)phenyl)prop-2-yn-1-yl)-2-(3-
1
oxo-3-phenylpropyl)malonate (1o). Yellow oil (617 mg, 52%); H
Hz, 2H), 7.92 (d, J = 2.0 Hz, 1H), 7.57 (t, J = 7.4 Hz, 1H), 7.48−7.43
(m, 3H), 7.24 (d, J = 8.4 Hz, 1H), 4.24 (q, J = 7.2 Hz, 4H), 4.09 (s,
2H), 3.40 (s, 2H), 1.50 (s, 9H), 1.24 (t, J = 7.2 Hz, 6H); 13C NMR
(100 MHz, CDCl3) δ 197.1, 169.3, 163.7, 136.4, 135.5, 135.1, 134.0,
133.3, 132.9, 128.5, 128.2, 122.2, 121.4, 91.3, 81.9, 81.7, 61.9, 55.0,
41.1, 28.0, 24.6, 13.9; IR (KBr) ν 2972, 2927, 2236, 1730, 1684, 1597,
1580, 1472, 1448, 1367, 1293, 1249, 1184, 1164, 1143, 1092, 1046,
999, 833, 760, 747, 688 cm−1; MS (m/z, ESI) 588 [M + NH4]+;
HRMS (ESI) calcd for C29H35BrNO7 [M + NH4]+ 588.1591, found
588.1588.
NMR (400 MHz, CDCl3) δ 7.98−7.96 (m, 2H), 7.82 (dd, J = 7.8, 1.0
Hz, 1H), 7.54−7.50 (m, 1H), 7.45−7.34 (m, 4H), 7.31 (dd, J = 7.4,
1.4 Hz, 1H), 4.28−4.19 (m, 4H), 3.19 (s, 2H), 3.14 (t, J = 8.0 Hz,
2H), 2.61 (t, J = 8.0 Hz, 2H), 1.54 (s, 9H), 1.25 (t, J = 7.2 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ 198.7, 170.1, 165.2, 136.6, 134.5,
133.6, 132.9, 131.0, 129.9, 128.5, 128.0, 127.5, 123.1, 89.0, 82.7, 81.3,
61.7, 56.5, 33.8, 28.1, 27.2, 24.9, 14.0; IR (KBr) ν 3064, 2980, 2934,
2230, 1727, 1687, 1597, 1481, 1447, 1368, 1299, 1253, 1132, 1080,
1039, 849, 758, 692 cm−1; MS (m/z, ESI) 524 [M + NH4]+; HRMS
(ESI) calcd for C30H38NO7 [M + NH4]+ 524.2643, found 524.2641.
tert-Butyl 2-((2-Formylphenyl)ethynyl)benzoate (1p). Yellow solid
(581 mg, 95%); mp 66−67 °C; 1H NMR (400 MHz, CDCl3) δ 10.75
(s, 1H), 7.96 (d, J = 7.6 Hz, 1H), 7.92 (d, J = 7.6 Hz, 1H), 7.67 (t, J =
8.0 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.51−7.39 (m, 3H), 1.60 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 192.4, 165.1, 136.1, 134.0,
133.8, 133.6, 133.1, 131.2, 130.2, 128.6, 128.5, 127.0, 126.9, 122.3,
95.0, 89.3, 81.7, 28.1; IR (KBr) ν 3066, 2979, 2930, 1712, 1688, 1590,
Diethyl 2-(3-(2-(tert-Butoxycarbonyl)phenyl)prop-2-yn-1-yl)-2-(2-
(4-methoxyphenyl)-2-oxoethyl)malonate (1h). Yellow oil (810 mg,
78%); H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 9.2 Hz, 2H), 7.80
(dd, J = 7.8, 0.6 Hz, 1H), 7.40−7.28 (m, 3H), 6.92 (d, J = 8.8 Hz, 2H),
4.24 (q, J = 6.8 Hz, 4H), 4.03 (s, 2H), 3.86 (s, 3H), 3.39 (s, 2H), 1.52
(s, 9H), 1.25 (t, J = 7.0 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ
195.6, 169.5, 165.2, 163.6, 134.3, 133.6, 130.9, 130.5, 129.9, 129.6,
127.5, 123.2, 113.6, 89.9, 82.5, 81.3, 61.9, 55.4, 55.1, 40.7, 28.0, 24.6,
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J. Org. Chem. XXXX, XXX, XXX−XXX