5
3.24 (br s, 4H), 4.43 (d, J = 13.0 Hz, 1H), 7.60 (d, J = 13.0 Hz,
1H) ppm; 13C NMR (125 MHz, CDCl3) δ 25.3, 28.6, 46.3 (br w),
51.6 (br w), 78.0, 86.4, 148.1, 169.4 ppm; IR (film) ν: 2973,
2927, 1684, 1611, 1456, 1388, 1132, 787 cm-1; HRMS calcd for
[C18H25NO2Na]+ (M+Na)+: 198.1489; found: 198.1489.
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
ACCEPTED MANUSCRIPT
1:3) to give the known compound 12i[18a] as a yellow oil (58 mg,
yield: 58%); H NMR (500 MHz, CDCl3) δ 1.18 (d, J = 6.8 Hz,
12H ), 1.24 (t, J = 7.1 Hz, 3H), 3.62 (br s, 2H), 4.10 (q, J = 7.1
Hz, 2H), 4.64 (d, J = 13.2 Hz, 1H), 7.54 (d, J = 13.2 Hz, 1H)
ppm; 13C NMR (125 MHz, CDCl3) δ 14.7, 20.9 (br w), 47.9 (br),
58.6, 83.3 147.1, 170.1 ppm; IR (film) ν: 2976, 2933, 1688, 1603,
1462, 1369, 1273, 1186, 1132, 1050 cm-1; HRMS calcd for
[C11H21NO2Na]+ (M+Na)+: 222.1465; found: 222.1473.
1
4.2.4. Ethyl (E)-3-(piperidin-1-yl)acrylate (12d)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:3) to give the known compound 12d[18a] as a yellow oil (82 mg,
1
yield: 89%); H NMR (400 MHz, CDCl3) δ 1.25 (t, J = 7.1 Hz,
3H), 1.60 (m, 6H), 3.19 (m, 4H), 4.13 (q, J = 7.1 Hz, 2H), 4.60
(d, J = 13.0 Hz, 1H), 7.39 (d, J = 13.0 Hz, 1H) ppm; 13C NMR
(100 MHz, CDCl3) δ 14.6, 24.1, 25.4, 50.2 (br w), 58.8, 83.8,
152.0, 170.1 ppm; IR (film) ν: 2937, 2855, 1688, 1611, 1451,
1384, 1369, 1237, 1153, 1115, 1047, 788 cm-1; HRMS calcd
for [C9H15NO2Na]+ (M+Na)+: 206.1151; found: 206.1152.
4.2.10. Ethyl (E)-3-morpholinoacrylate (12j)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:5) to give the known compound 12j[18d] as a yellow oil (84 mg,
1
yield: 91%); H NMR (400 MHz, CDCl3) δ 1.22 (t, J = 7.1 Hz,
3H), 3.17 (t, J = 5.1 Hz, 4H), 3.67 (t, J = 5.1 Hz, 4H), 4.10 (q, J
= 7.1 Hz. 2H), 4.65 (d, J = 13.2 Hz, 1H), 7.32 (d, J = 13.2 Hz,
1H) ppm; 13C NMR (125 MHz, CDCl3) δ 14.5, 48.6 (br), 59.0,
66.1, 86.1, 151.7, 169.4 ppm; IR (film) ν: 2975, 2853, 1688,
1616, 1045, 974, 792 cm-1; HRMS calcd for [C9H15NO3Na]+
(M+Na)+: 208.0944; found: 208.0937.
4.2.5. Ethyl (E)-3-(indolin-1-yl)acrylate (12e).
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:5) to give the compound 12e as a yellow oil (92 mg, yield:
1
85%); H NMR (400 MHz, CDCl3) δ 1.32 (t, J = 7.1 Hz, 3H),
3.22 (t, J = 8.7 Hz, 2H), 3.78 (t, J = 8.7 Hz, 2H), 4.22 (q, J = 7.1
Hz, 2H), 4.89 (d, J = 13.1 Hz, 1H), 6.90-6.98 (m, 2H), 7.17-7.21
(m, 2H), 8.09 (d, J = 13.1 Hz, 1H) ppm; 13C NMR (125 MHz,
CDCl3) δ 14.6, 27.5, 47.8, 59.4, 90.1, 108.3, 122.2, 125.5, 127.8,
130.5, 140.4, 144.1, 168.9 ppm; IR (film) ν: 3052, 2969, 1686,
1672, 1595, 1495, 1461, 1163, 1030, 972, 788, 732 cm-1; HRMS
calcd for [C13H15NO2Na]+ (M+Na)+: 240.0995; found: 240.0993.
4.2.11.Ethyl (E)-3-(2,6-dimethylmorpholino)
acrylate (12k)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:3) to give the compound 12k as a yellow oil (96 mg, yield:
1
90%); H NMR (500 MHz, CDCl3) δ 1.14 (d, J = 6.3 Hz, 6H),
1.14 (t, J = 7.2 Hz, 3H), 2.65 (t, J = 11.3 Hz, 2H), 3.19 (dd, J =
1.5, 13.1 Hz, 2H), 3.52-3.62 (m, 2H), 4.08 (q, J = 7.2 Hz, 2H),
4.62 (d, J = 13.3 Hz, 1H), 7.32 (d, J = 13.3 Hz, 1H) ppm; 13C
NMR (125 MHz, CDCl3) δ 14.5, 18.5, 33.8 (br, w), 53.8, 58.9,
71.2, 85.4, 151.1, 169.5 ppm; IR (film) ν: 2976, 2929, 2875,
1690, 1614, 1450, 1372, 1340, 1253, 1183, 1150, 1086, 1047,
790 cm-1; HRMS calcd for [C11H19NO3Na]+ (M+Na)+: 236.1257;
found: 236.1264.
4.2.6. Ethyl (E)-3-(3,4-dihydroquinolin-1(2H)-
yl)acrylate (12f)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:5) to give the compound 12f as a yellow oil (103mg, yield:
1
89%); H NMR (400 MHz, CDCl3) δ 1.31 (t, J = 7.1 Hz, 3H),
2.03 (m, 2H), 2.72 (t, J = 6.4 Hz, 2H), 3.47 (t, J = 6.4 Hz, 2H),
4.21 (q, J = 7.1 Hz, 2H), 5.04 (d, J = 13.2 Hz, 1H), 6.97 (td, J =
7.3, 1.1 Hz, 1H), 7.10 (d, J = 7.1 Hz, 1H), 7.16 (d, J = 7.7 Hz,
1H), 7.20-7.25 (m, 1H), 8.19 (d, J = 13.2 Hz, 1H) ppm; 13C NMR
(125 MHz, CDCl3) δ 14.6, 22.4, 27.4, 45.9, 59.4, 90.7, 115.9,
122.3, 127.6, 128.1, 128.8, 140.2, 145.6, 169.2 ppm; IR (film) ν:
2976, 2946, 2868, 1693, 1615, 599, 1496, 1047, 968, 799, 751
cm-1; HRMS calcd for [C14H17NO2Na]+ (M+Na)+: 254.1151;
found: 254.1154.
4.2.12. Ethyl (E)-3-(4-cyanopiperidin-1-yl)acrylate
(12l)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:3) to give the compound 12l as a yellow oil (85 mg, yield:
1
82%); H NMR (500 MHz, CDCl3) δ 1.22 (t, J = 7.2 Hz, 3H),
1.80-1.87 (m, 2H), 1.88-1.94 (m, 2H), 2.81-2.89 (m, 1H), 3.10-
3.21 (m, 2H), 3.32-3.43 (m, 2H), 4.08 (q, J = 7.2 Hz, 2H), 4.66
(d, J = 13.3 Hz, 1H), 7.29 (d, J = 13.3 Hz, 1H) ppm; 13C NMR
(125 MHz, CDCl3) δ 14.4, 25.9, 27.8, 46.5 (br, w), 59.0, 86.3,
120.3, 151.1, 169.3 ppm; IR (film) ν: 2971, 2930, 2851, 2244,
1690, 1678, 1611, 1383, 1140, 1092, 1047, 790 cm-1; HRMS
calcd for [C11H16N2O2Na]+ (M+Na)+: 231.1104; found: 231.1113.
4.2.7. Ethyl (E)-3-(diethylamino)acrylate (12g)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:3) to give the known compound 12g[18e] as a yellow oil (79 mg,
1
yield: 92%); H NMR (500 MHz, CDCl3) δ 1.14 (t, J = 7.2 Hz,
6H ), 1.25 (t, J = 7.1 Hz, 3H), 3.17 (q, J = 7.2 Hz, 4H), 4.11 (q, J
= 7.1 Hz, 2H), 4.55 (d, J = 13.1 Hz, 1H), 7.23 (d, J = 13.1 Hz,
1H) ppm; 13C NMR (125 MHz, CDCl3) δ 12.0 (br w), 13.7 (br w),
14.6, 42.4 (br w), 49.7 (br w), 58.8, 83.4, 150.1, 170.2 ppm; IR
(film) ν: 2974, 2931, 1687, 1611, 1365, 1242, 1195, 1154, 1111,
1049, 788 cm-1; HRMS calcd for [C9H17NO2Na]+ (M+Na)+:
194.1151; found: 194.1155.
4.2.13. Ethyl (E)-1-(3-ethoxy-3-oxoprop-1-en-1-
yl)piperidine-4-carboxylate (12m)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:1) to give the compound 12m as a yellow oil. (74 mg, yield:
1
58%); H NMR (400 MHz, CDCl3) δ 1.21-1.27 (m, 6H), 1.65-
1.75 (m 2H), 1.89-1.96 (m, 2H), 2.43-2.52 (m, 1H), 3.07 (t, J =
11.2 Hz, 2H), 3.45 (t, J = 4.0 Hz, 1H), 3.49 (t, J = 4.0 Hz, 1H),
4.13 (m, 4H), 4.65 (d, J = 13.3 Hz, 1H), 7.36 (d, J = 13.3 Hz, 1H)
ppm; 13C NMR (125 MHz, CDCl3) δ 14.2, 14.6, 27.5, 40.6, 47.8
(br, w), 58.9, 60.7, 85.1, 151.6, 169.8, 173.9 ppm; IR (film) ν:
2978, 1730, 1688, 1611, 1449, 1371, 1338, 1145., 1097, 1042,
789 cm-1; HRMS calcd for [C13H21NO4Na]+ (M+Na)+: 278.1363;
found: 278.1360.
4.2.8. Ethyl (E)-3-(dibenzylamino)acrylate (12h)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:5) to give the compound 12h as a yellow oil (118 mg, yield:
1
80%); H NMR (500 MHz, CDCl3): δ 1.35 (t, J = 7.1 Hz, 3H),
4.24 (q, J = 7.1 Hz, 2H), 4.39 (s, 4H), 4.90 (d, J = 13.1 Hz, 1H),
7.24-7.28 (m, 4H), 7.37-7.45 (m, 6H), 7.90 (d, J = 13.1 Hz, 1H);
13C NMR (125 MHz, CDCl3): δ 14.6, 50.7 (br w), 59.1, 85.8,
127.5, 127.8, 128.8, 136.0, 152.7, 169.9 ppm; IR (film) ν: 3062,
3028, 2977, 2856, 1682, 1613, 1495, 1453, 1366, 1253, 1141,
1046, 974, 791, 732, 698 cm-1; HRMS calcd for [C19H21NO2Na]+
(M+Na)+: 318.1465; found: 318.1463.
4.2.14. tert-Butyl (E)-4-(3-ethoxy-3-oxoprop-1-en-
1-yl)piperazine-1-carboxylate (12n)
Flash chromatography on silica gel (eluent: EtOAc/n-Hexane =
1:3) to give the compound 12n as a yellow oil (90 mg, yield:
1
63%); H NMR (500 MHz, CDCl3) δ 1.21 (t, J = 7.1 Hz, 3H),
1.43 (s, 9H), 3.14 (br t, J = 5.0 Hz, 4H), 3.42 (br t, J = 5.0 Hz,
4H), 4.08 (q, J = 7.1 Hz, 2H), 4.65 (d, J = 13.2 Hz, 1H), 7.34 (d,
4.2.9. Ethyl (E)-3-(diisopropylamino)acrylate (12i)