3718
D. Virieux et al. / Tetrahedron 62 (2006) 3710–3720
NMR (100 MHz, CDCl3): 14.13 (CH3), 48.55 (CH2), 60.88
(CH2), 109.19 (7-CH), 120.30 (4-CH), 124.23 and 124.26
(2s, a-CHC5-CH), 127.86 (s, 6-CH), 132.84 (7a-C), 139.74
(b-CH), 146.13 (3a-C), 165.21 (C); FAB (C): m/z (%)Z
232 (100) [MCCH], 120 (10) [MCKC6H4N3CH]; HRMS:
calcd for C12H14N3O2 232.1086; found 232.1081.
nZ3115, 2971, 2880, 1726 (C]O) cmK1 1H NMR
;
3
(400 MHz, CDCl3): dZ0.88 (t, J(H,H)Z7.4 Hz, 3H, CH3),
1.85–2.18 (m, 2H, CH2), 3.69 (s, CH3), 4.57–4.62 (m, 1H,
3
4
CH), 5.68 (dd, J(H,H)Z15.6 Hz, J(H,H)Z1.7 Hz, 1H,
3
a-CH), 6.97 (dd, J(H,H)Z15.6, 5.6 Hz, 1H, b-CH), 6.89
(s, 1H, 4-CH), 7.07 (s, 1H, 5-CH), 7.49 (s, 1H, 2-CH); 13C
NMR (100 MHz, CDCl3): dZ10.46 (CH3), 27.75 (CH2),
51.78 (CH2), 59.87 (CH3), 117.06 (4-CH), 122.30 (a-CH),
129.80 (5-CH), 136.29 (2-CH), 145.79 (b-CH), 160.02 (C);
FAB (C): m/z (%)Z195 (100) [MCCH], 179 (3) [MCK
CH3], 135 (5) [MCKCOMe]; HRMS: calcd for
C10H15N2O2 195.1086; found 195.1087
4.2.8. (E)-Ethyl 4-(benzotriazol-20-yl)but-2-enoate (3h).
This regioisomer was obtained together with 3g. YieldZ
19% for 3h, oil; IR (NaCl film): 3068, 2982, 2939, 1722
(C]O), 1664 (C]N); 1H NMR (400 MHz, CDCl3): 1.27 (t,
3
3J(H,H)Z7.1 Hz, 3H, CH3), 4.16 (q, J(H,H)Z7.1 Hz, 2H,
CH2), 5.49 (dd, 3J(H,H)Z5.8 Hz, 4J(H,H)Z1.8 Hz, 2H, CH2),
3
4
5.87 (dt, J(H,H)Z15.7 Hz, J(H,H)Z1.8 Hz, 1H, a-CH),
4.2.11. (E/Z)-Ethyl-4-(20-formylpyrrol-10-yl)-but-2-
enoate (3o). The two isomers were separated with
dichloromethane–ethanol eluent (100/0–98/2). Yield: 63%
(112 mg (Z isomer), 146 mg (E isomer), and 118 mg
(mixture of E,Z isomers)), oils; IR (KBr film): E isomer
nZ3111, 2982, 2938, 2808, 1721 (C]Oester), 1662
(C]Oaldehyde) cmK1; Z isomer nZ3110, 2982, 2806,
3
7.18 (dt, J(H,H)Z15.7, 5.8 Hz, 1H, b-CH), 7.39 (ddd,
3J(H,H)Z8.7, 6.8 Hz, J(H,H)Z1.0 Hz, 2H, 5-CHC6-CH),
4
3
4
5
7.87 (ddd, J(H,H)Z8.7 Hz, J(H,H)Z1.0 Hz, J(H,H)
Z
1.0 Hz, 2H, 4-CHC7-CH); 13C NMR (100 MHz, CDCl3):
14.16 (CH3), 56.66 (CH2), 60.78 (CH2), 118.15 (4-CH
C7-CH), 124.79 (a-CH), 126.74 (5-CH C6-CH), 139.42
(b-CH), 144.64 (3a-CC7a-C), 165.24 (C); FAB (C): m/z
(%)Z232 (100) [MCCH], 186 (14) [MCKOC2H5], 158
(13) [MCKCO2 C2H5]; HRMS: calcd for C12H14N3O2
232.1086; found 232.1087.
1715 (C]O), 1665 (C]Oaldehyde) cmK1
;
1H NMR
3
(400 MHz, CDCl3): E isomer dZ1.28 (t, J(H,H)Z7.1 Hz,
3
3H, CH3), 4.18 (q, J(H,H)Z7.1 Hz, 2H, CH2), 5.16 (dd,
4
3J(H,H)Z4.8 Hz, J(H,H)Z2.0 Hz, 2H, CH2), 5.53 (dt,
4
3J(H,H)Z15.5 Hz, J(H,H)Z2.0 Hz, 1H, a-CH), 6.32 (dd,
4.2.9. (E/Z)-Ethyl 4-(indol-10-yl)-but-2-enoate (3i). The
two isomers were separated with hexane–ethyl acetate
eluent (98/2). Yield: 53% (142 mg (Z isomer), 95 mg (E
isomer)), colorless oils; IR (NaCl film): E isomer nZ3102,
2982, 2937, 2881, 1716 (C]O) cmK1; Z isomer nZ3055,
2982, 2880, 2820, 1714 (C]O) cmK1; 1H NMR (250 MHz,
3J(H,H)Z3.9, 2.5 Hz, 1H, 4-CH), 6.94 (ddd, 3J(H,H)Z2.5 Hz,
3
4J(H,H)Z1.0, 1.8 Hz, 1H, 3-CH), 7.00 (dd, J(H,H)Z3.9 Hz,
4J(H,H)Z1.8 Hz, 1H, 5-CH), 7.06 (dt, 3J(H,H)Z15.5, 4.8 Hz,
1H, b-CH), 9.56 (d, 4J(H,H)Z1.0 Hz, CH); Z isomer dZ1.32
(t, 3J(H,H)Z7.2 Hz, 3H, CH3), 4.23 (q, 3J(H,H)Z7.2 Hz, 2H,
CH2), 5.54 (dd, 3J(H,H)Z6.1 Hz, 4J(H,H)Z2.0 Hz, 2H, CH2),
5.87 (dt, 3J(H,H)Z11.3 Hz, 4J(H,H)Z2.0 Hz, 1H, a-CH), 6.25
3
CDCl3): E isomer dZ1.27 (t, J(H,H)Z7.1 Hz, 3H,
3
CH3), 4.18 (q, J(H,H)Z7.1 Hz, 2H, CH2), 4.91 (dd,
3
3
(dd, J(H,H)Z4.1, 2.5 Hz, 1H, 4-CH), 6.27 (dt, J(H,H)
Z
3J(H,H)Z4.6 Hz, 4J(H,H)Z1.9 Hz, 2H, CH2), 5.62 (dt, 3J(H,H)
-
3
11.4, 6.1 Hz, 1H, b-CH), 6.96 (dd, J(H,H)Z4.1 Hz,
4
Z15.6 Hz, J(H,H)Z1.9 Hz, 1H, a-CH), 6.59 (dd, 3J(H,H)
Z
3
4J(H,H)Z1.6 Hz, 1H, 5-CH), 7.01 (ddd, J(H,H)Z2.5 Hz,
3.1 Hz, 5J(H,H)Z0.8 Hz, 1H, 3-CH), 7.10 (dt, 3J(H,H)Z15.6,
4.6 Hz, 1H, b-CH), 7.05–7.31 (m, 4H, 2-CHC5-CHC6-
4
4J(H,H)Z1.6, 1.0 Hz, 1H, 3-CH), 9.56 (d, J(H,H)Z1.0 Hz,
CH); 13C NMR (100 MHz, CDCl3): E isomer dZ14.19
(CH3), 49.14 (CH2), 60.59 (CH2), 110.45 (4-CH), 122.23
(a-CH), 124.86 (5-CH), 131.22 (3-CH), 131.26 (2-C),
143.33 (b-CH), 165.76 (C), 179.45 (CHO); Z isomer
dZ14.22 (CH3), 47.21 (CH2), 60.41 (CH2), 110.06
(4-CH), 120.92 (a-CH), 124.80 (5-CH), 131.19 (2-C),
131.51 (3-CH), 144.85 (b-CH), 165.87 (C), 179.36
(CHO); FAB (C): E isomer m/z (%)Z208 (40) [MCC
H], 134 (100) [MCKCO2C2H5]; Z isomer m/z (%)Z208
(52) [MCCH], 134 (100) [MCKCO2C2H5]; HRMS: calcd
for C11H14NO3 208.0974; found 208.0977 (E isomer),
208.0965 (Z isomer).
3
4
CHC7-CH), 7.68 (ddd, J(H,H)Z7.6 Hz, J(H,H)Z1.2 Hz,
3
5J(H,H)Z0.8 Hz, 1H, 4-CH); Z isomer dZ1.39 (t, J(H,H)
Z
7.1 Hz, 3H, CH3), 4.31 (q, 3J(H,H)Z7.1 Hz, 2H, CH2), 5.41
3
4
(dd, J(H,H)Z5.8 Hz, J(H,H)Z2.1 Hz, 2H, CH2), 5.95 (dt,
4
3J(H,H)Z11.5 Hz, J(H,H)Z2.1 Hz, 1H, a-CH), 6.30 (dt,
3J(H,H)Z11.5, 5.8 Hz, 1H, b-CH), 6.57 (dd, 3J(H,H)Z3.2 Hz,
5J(H,H)Z0.8 Hz, 1H, 3-CH), 7.11–7.37 (m, 4H, 2-CHC
5-CHC6-CHC7-CH), 7.66–7.70 (m, 1H, 4-CH); 13C NMR
(100 MHz, CDCl3): E isomer dZ14.16 (CH3), 46.97
(CH2), 60.62 (CH2), 102.24 (3-CH), 109.29 (7-CH),
119.78–121.14–121.98–122.61 (a-CH, 4-CH, 5-CH,
6-CH), 127.82 (2-CH), 128.65 (3a-C), 135.94 (7a-C),
142.86 (b-CH), 165.85 (C); Z isomer dZ14.29 (CH3),
45.06 (CH2), 60.57 (CH2), 101.86 (3-CH), 109.42 (7-CH),
119.63–121.06–121.19–121.75 (a-CH, 4-CH, 5-CH, 6-CH),
127.73 (2-CH), 128.80 (3a-C), 135.92 (7a-C), 145.70
(b-CH), 166.04 (C); FAB (C): E isomer m/z (%)Z230
(55) [MCCH], 229 (100) [M]C, 200 (15) [MCKC2H5],
156 (40) [MCKCO2C2H5]; Z isomer m/z (%)Z230 (60)
[MCCH], 229 (100) [M]C, 156 (30) [MCKCO2C2H5];
HRMS: calcd for C14H15NO2 229.1103; found 229.1110 (E
isomer), 229.1102 (Z isomer).
4.2.12. Ethyl (3H-pyrrolizin-2-yl)-acetate (10). Yield: 6%
(36 mg), oil; IR (NaCl film): nZ3055, 2986, 1731
(C]O) cmK1 1H NMR (400 MHz, CDCl3): dZ1.31
;
3
4
(t, J(H,H)Z7.2 Hz, 3H, CH3), 3.44 (d, J(H,H)Z1.0 Hz,
2H, a-CH2), 4.19 (q, 3J(H,H)Z7.2 Hz, 2H, CH2), 4.51 (ddd,
4J(H,H)Z1.0, 1.0, 2.0 Hz, 2H, 3-CH2), 5.88 (dd, J(H,H)
Z
3
4
3
3.5 Hz, J(H,H)Z0.8 Hz, 1H, 7-CH), 6.24 (dd, J(H,H)Z2.5,
4
3.5 Hz, 1H, 6-CH), 6.44 (sextuplet, J(H,H)Z1.0 Hz, 1H,
1-CH), 6.92 (ddd, 3J(H,H)Z2.5 Hz, 4J(H,H)Z1.0, 0.8 Hz, 1H,
5-CH); 13C NMR (100 MHz, CDCl3): dZ14.22 (s, CH3),
35.62 (a-CH2), 53.58 (3-CH2), 61.09 (CH2), 97.05 (7-CH),
111.44 (6-CH), 116.95 (5-CH), 121.50 (1-CH), 134.19
(2-C), 140.87 (8-C), 170.40 (C); FAB (C): m/z (%)Z192
4.2.10. (E)-Ethyl 4-(imidazol-10-yl)hexa-2-enoate (3m).
The compound was eluted with hexane–ethyl acetate eluent
(98/2). Yield: 30% (228 mg (E isomer)), oil; IR (KBr film):