(2H, t, J = 8.1 Hz), 2.11 (2H, qn, J = 7.5 Hz). 13C NMR (100 MHz,
CDCl3) d: 174.8, 167.7, 138.9, 128.0, 119.8, 107.5, 51.6, 48.8, 29.8,
18.2. umax (neat)/cm-1; 1749, 1699, 1614 cm-1. HRMS(EI) found
[M]+ 195.0898, C10H13O3N requires 195.0895.
26Z,E 1H NMR (400 MHz, CDCl3) d: 8.33 (1H, bd, J =
8.6 Hz), 7.89–7.90 (2H, m), 7.61–7.67 (4H, m), 7.30 (1H, dd,
J = 10.9, 9.6 Hz), 5.97 (1H, d, J = 14.9 Hz), 5.66 (1H, dd,
J = 12.3, 9.0 Hz), 3.73 (3H, s). 13C NMR (100 MHz, CDCl3) d:
167.7, 164.4, 136.6, 132.9, 132.7, 128.9, 128.6, 127.4, 119.4, 107.6,
51.7. umax (neat)/cm-1; 3308.0, 1683.9, 1666.5, 1626.0, 1602.9 cm-1.
HRMS(EI) found [M]+ 231.0899, C13H13O3N requires 231.0895.
26E,E 1H NMR (400 MHz, CDCl3) d: 7.99 (1H, bd, J =
12.3 Hz), 7.85–7.87 (2H, m), 7.51–7.64 (4H, m), 7.41 (1H, dd,
J = 15.2, 11.4 Hz), 6.12 (1H, dd, J = 14.1, 11.9 Hz), 5.86 (1H,
d, J = 15.2 Hz), 3.78 (3H, s, CH3). 13C NMR (100 MHz, CDCl3)
d: 166.6, 163.5, 142.5, 132.1, 131.6, 127.8, 126.3, 116.9, 110.2,
50.5. umax (neat)/cm-1; 3304.1, 1670.4, 1622.2, 1608.7, 1583.6 cm-1.
HRMS(EI) found [M]+ 231.0897, C13H13O3N requires 231.0895.
(2E,4Z)-Methyl 5-(2-oxopiperidin-1-yl)penta-2,4-dienoate, 24Z,
E, and (2E,4E)-Methyl 5-(2-oxopiperidin-1-yl)penta-2,4-dienoate,
24E,E.. Dienamides 24Z,E and 24E,E. were prepared using the
general procedure, starting from a solution of imide 17 (200 mg,
1.57 mmol) in dichloromethane (15 mL) and using ylide 11 (1.70 g,
4.72 mmol). Purification by flash column chromatography (silica
gel, 10% ethyl acetate, 1% triethylamine/petroleum ether) afforded
114 mg of dienamides 24Z,E and 24E,E. (35%) as a 10:1 mixture
of inseparable isomers.
1
24Z,E H NMR (400 MHz, CDCl3) d = 7.56 (1H, appt, J =
(2E,4Z)-Methyl 5-(picolinamido)penta-2,4-dienoate, 27Z,E, and
(2E,4E)-Methyl 5-(picolinamido)penta-2,4-dienoate, 27E,E. Di-
enamides 27Z,E and 27E,E were prepared using the general pro-
cedure, starting from a solution of imide 20 (100 mg, 0.66 mmol) in
dichloromethane (10 mL) and using ylide 11 (720 mg, 1.99 mmol).
Purification by flash column chromatography (silica gel, 10% ethyl
acetate, 1% triethylamine/petroleum ether) afforded 132 mg (87%)
of the Z,E-dienamide 27Z,E and E,E-dienamide 27E,E as an
inseparable (3:2) mixture of isomers, and as a clear oil.
27Z,E 1H NMR (400 MHz, CDCl3) d: 10.27 (1H, bd, J =
11.5 Hz), 7.82–7.86 (2H, m), 7.65 (1H, dd, J = 12.2, 14.9 Hz),
7.39–7.47 (2H, m), 7.14 (1H, dd, J = 11.7, 9.1 Hz), 5.88 (1H, d,
J = 14.9 Hz), 5.59 (1H, dd, J = 8.9, 12.2 Hz), 3.73 (3H, s). 13C
NMR (100 MHz, CDCl3) d = 167.6, 161.3, 148.4, 148.3, 137.7,
136.7, 127.6, 127.1, 122.8, 119.5, 108.3, 51.6.
27E,E 1H NMR (400 MHz, CDCl3) d: 9.88 (1H, bd, J =
10.4 Hz), 8.52–8.60 (2H, m), 8.15 (2H, m), 7.39–7.47 (1H, dd,
J = 15.2, 11.3 Hz), 7.33 (1H, dd, J = 13.2, 11.0, Hz), 6.11 (1H,
dd, J = 13.3, 11.3 Hz), 5.78 (1H, d, J = 15.2 Hz), 3.68 (3H, s).
umax (neat)/cm-1; 3362, 1705, 1627, 1618 cm-1. HRMS(EI) found
[M]+ 232.0850, C12H12O3N2 requires 232.0848.
13.4 Hz), 7.04 (1H, d, J = 9.8 Hz), 5.74 (1H, d, J = 14.9 Hz), 5.54
(1H, dd, J = 12.1, 10.6 Hz), 3.73 (2H, J = 5.6 Hz), 3.70 (3H, s),
2.48 (2H, t, J = 5.8 Hz), 1.75 -1.85 (4H, m). 13C NMR (100 MHz,
CDCl3) d = 169.9, 167.6, 139.2, 133.0, 120.7, 111.3, 51.6, 50.8,
32.6, 23.3, 20.8.
1
24E,E. H NMR (400 MHz, CDCl3) characteristic peaks d =
7.87 (1H, d, J = 14.5 Hz), 7.32 (1H, dd, J = 15.6, 10.8 Hz). 13C
NMR (100 MHz, CDCl3) d = 168.9, 167.6, 144.5, 136.6, 117.7,
108.4, 51.4, 45.4, 33.0, 22.4, 20.3. umax (neat)/cm-1; 1707, 1660,
1614 cm-1. HRMS(EI) found [M]+ 209.1057, C11H15O3N requires
209.1052.
(2E,4Z)-Methyl 5-(2-oxoazepan-1-yl)penta-2,4-dienoate, 25Z,
E, and (2E,4E)-Methyl 5-(2-oxoazepan-1-yl)penta-2,4-dienoate,
25E,E. Dienamides 25Z,E and 25E,E were prepared using the
general procedure, starting from a solution of imide 18 (200 mg,
1.42 mmol) in dichloromethane (15 mL) and using ylide 11 (1.53 g,
4.25 mmol). Purification by flash column chromatography (silica
gel, 10% ethyl acetate, 1% triethylamine/petroleum ether) afforded
176 mg of dienamide 25Z,E and 25E,E (56%) as a 4:1 mixture.
25Z,E 1H NMR (400 MHz, CDCl3) d = 7.40 (1H, ddd, J = 15.1,
12.1, 1.0 Hz), 6.85 (1H, d, J = 9.1 Hz), 5.79 (1H, d, J = 15.1 Hz),
5.58 (1H, ddd, J = 12.1, 9.0, 0.7 Hz), 3.68 (3H, s), 3.66–3.69 (2H,
(2E,4Z)-Methyl 5-(3-methylbut-2-enamido)penta-2,4-dienoate,
28. Dienamide 28 was prepared using the general procedure,
starting from a solution of imide 21 (165 mg, 1.29 mmol) in
dichloromethane (10 mL) and using ylide 11 (1.40 g, 3.89 mmol).
Purification by flash column chromatography (silica gel, 10% ethyl
acetate, 1% triethylamine/petroleum ether) afforded 110 mg of
dienamide 28 (41%) as a single Z,E-isomer.
m), 2.57–2.62 (2H, m), 1.77–1.80 (2H, m), 1.70–1.75 (4H, m). 13
C
NMR (100 MHz, CDCl3) d = 176.0, 167.4, 138.5, 135.4, 120.7,
113.2, 51.7, 37.3, 37.1, 29.6, 28.8, 23.4.
25E,E 1H NMR (400 MHz, CDCl3) d = 7.66 (1H, d, J =
14.5 Hz), 7.32 (1H, ddd, J = 15.0, 11.1, 0.8 Hz), 5.71 (1H, d,
J = 14.9 Hz), 5.70 (1H, appt, J = 12.0 Hz), 3.66 (3H, s), 3.66–3.69
(2H, m), 2.57–2.62 (2H, m), 1.77–1.80 (2H, m), 1.70–1.75 (4H,
m). 13C NMR (100 MHz, CDCl3) d = 174.5, 167.7, 144.8, 136.7,
117.0, 107.7, 51.4, 45.3, 37.0, 29.3, 27.4, 23.5. umax (neat)/cm-1;
1708, 1662, 1653, 1624 cm-1. HRMS(CI) found [M + H]+ 224.1284,
C12H18O3N requires 224.1287.
1H NMR (400 MHz, CDCl3) d: 7.71 (1H, bd, J = 11.6 Hz),
7.47 (1H, ddd, J = 14.9, 12.2, 0.9 Hz), 7.06 (1H, dd, J = 11.8,
9.0 Hz), 5.78 (1H, d, J = 14.9 Hz), 5.63 (1H, bs), 5.42 (1H, dd, J =
12.2, 9.0 Hz), 3.68 (3H, s), 2.16 (3H, d, J = 0.8 Hz), 1.85 (3H, d,
J = 1.2 Hz). 13C NMR (100 MHz, CDCl3) d: 168.0, 163.3, 137.2,
129.0, 125.9, 118.3, 117.1, 105.9, 51.8, 27.9, 20.5. umax (neat)/cm-1;
3010, 1730, 1701, 1658, 1639, 1624 cm-1. HRMS(CI) found [M +
H]+ 210.1128, C11H16O3N requires 210.1130.
(2E,4Z)-Methyl 5-benzamidopenta-2,4-dienoate, 26Z,E, and
(2E,4E)-Methyl 5-benzamidopenta-2,4-dienoate, 26E,E. Dien-
amides 26Z,E and 26E,E were prepared using the general proce-
dure, starting from a solution of imide 19 (100 mg, 0.67 mmol) in
dichloromethane (10 mL) and using ylide 11 (725 mg, 2.01 mmol).
Purification by flash column chromatography (silica gel, 10% ethyl
acetate, 1% triethylamine/petroleum ether) afforded 92.5 mg of the
Z,E-dienamide 26Z,E (60%) and 57.1 mg of the E,E-dienamide
26E,E (37%) as separable clear oils.
(2E,4Z)-Methyl 5-butyramidopenta-2,4-dienoate, 29. Dien-
amide 29 was prepared using the general procedure, starting from
a solution of imide 22 (100 mg, 0.87 mmol) in dichloromethane
(10 mL) and using ylide 11 (940 mg, 2.60 mmol). Purification by
flash column chromatography (silica gel, 10% ethyl acetate, 1%
triethylamine/petroleum ether) afforded 72.4 mg of dienamide 29
(42%) as a single Z,E-isomer.
2174 | Org. Biomol. Chem., 2009, 7, 2170–2175
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The Royal Society of Chemistry 2009
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