Jul-Aug 2002
Iodo Cyclofunctionalization of 2,4-Dialkenyl-1,3-Dicarbonyl Compounds
643
Anal. Calcd. for C H IO : C, 44.59; H, 5.47. Found: C,
Compound 4a was obtained in 78% yield; mp 89-90 °C.
Diastereomeric ratio: 1:1. H NMR: δ 1.88-1.95 (m, 1H), 2.25-
1
3
19
3
1
4
4.22; H, 5.58.
Ethyl (E)-2-(7-Iodoperhydrobenzo[b]-2-furylidene)-4-hexenoate
3f).
Compound 3f was obtained in 65% yield; H NMR: δ 1.28 (t,
J= 7.05 Hz, 3H), 1.63 (dd, J= 3.3 and 1.15 Hz, 3H), 1.40-1.96 (m,
2
(
2
.42 (m, 1H), 2.51-2.65 (m, 1H), 2.85-3.09 (m, 2H), 3.16-3.37
1
3
m, 5H), 4.41-4.57 (m, 2H). C NMR: δ 6.75, 6.89, 9.09, 8.98,
(
9.23, 29.74, 29.59, 31.61, 31.67, 75.11, 75.07, 82.98, 83.09,
1
93.97, 168.91, 171.38. IR: 2930, 1741, 1674, 1432, 1302, 1255,
1186, 1008, 860, 750 cm-1. MS: m/z 53, 79, 91, 125, 135, 147,
6
4
H), 2.61 (dd, J= 13.08 and 6.4 Hz, 1H), 2.96 and 2.98 (s, 3H),
.15 (J= 7.05 Hz, 2H), 4.42 (q, J= 5.20 Hz, 1H), 4.57 (t, J= 5.20
162, 179, 253, 265, 289, 321, 307 (100), 434 (M+).
Anal. Calcd. for C H I O : C, 27.65; H, 2.79. Found: C,
1
0 12 2 3
1
3
Hz, 1H), 5.44-5.48 (m, 2H). C NMR: δ 14.46, 17.93, 21.33,
27.95; H, 2.80.
2
1
1
1
5.98, [29.01, 29.12], 32.40, 34.62, 37.09, 59.62, 85.79, 104.06,
7
-Iodo-3-(5-iodomethyltetrahydro-2-furylidene)perhydrobenzo-
[b]-2-furanone (4b).
24.88, 129.14, 168.68, 168.94. MS: m/z 39, 67, 77, 95, 123, 147,
+
89, 217 (100), 263, 291, 391 (M ). IR: 2935, 1726, 1708, 1643,
-1
1
446, 1294, 1181, 1107, 1042, 875, 708, 622 cm .
Compound 4b was obtained in 19% yield; H NMR: δ 1.52-
1.56 (m, 1H); 1.64-1.70 (m, 2H), 1.86-1.99 (m, 4H), 2.29-2.36
(m, 1H), 2.96-3.05 (m, 1H), 3.28-3.42 (m, 4H), 4.28-4.62 (m,
Anal. Calcd. for C H IO : C, 49.29; H, 5.94. Found: C,
1
6
23
3
4
9.40; H, 5.53.
1
3
3
[
3
1
1
H). C NMR: δ [6.57, 7.40], [20.77, 21.11], [25.82, 26.12],
Ethyl 2-(1-Iodoethyl)-5-(3-pentenyl)-2,3-dihydro-4-furancar-
boxylate (2g).
28.88, 29.12], [29.42, 29.49], 29.64, [31.40, 31.90], [35.99,
6.28], [81.26, 81.43], [82.52, 83.43], [99.78, 100.54], [168.44,
68.48], [171.59, 171.62]. IR: 2934, 2858, 1743, 1678, 1441,
1
Compound 2g was obtained in 62% yield; H NMR: δ 1.28 (t,
J= 7.0 Hz, 3H), 1.63 (d, J= 4.6 Hz, 3H), 1.90 (d, J= 6.8 Hz, 3H),
.20-2.28 (m, 2H), 2.51-2.65 (m, 1H), 2.69-2.78 (m, 2H), 3.00
-1
328, 1254, 1027, 915, 877,794, 738, 692, 628 cm . MS: m/z 55
2
(
+
(
100), 149, 165, 221, 331, 348, 475 (M ).
dd, J= 15.0 and 10.9 Hz, 1H), 3.40-3.54 (m, 1H), 4.17 (q, J= 7.0
Anal. Calcd. for C H I O : C, 29.49; H, 3.15. Found: C,
1
3 16 2 3
1
3
Hz, 2H), 4.33-4.42 (m, 1H), 5.43-5.54 (m, 2H). C NMR: δ
2
5
9.63; H, 3.18.
1
1
1
1
4.34, 17.85, 23.48, 27.88, 29.78, 30.55, 35.77, 59.53, 101.62,
-Iodomethyl-3-(5-iodomethyltetrahydro-2-furylidene)tetrahy-
dro-2-furanone (4c).
25.73, 129.74, 165.60, 170.05. MS: m/z 55 (100), 67, 95, 121,
+
89, 221, 237, 291, 365 (M ). IR: 2971, 2926, 1725, 1443, 1362,
-1
227, 1115, 1035, 875, 597 cm .
1
Compound 4c was obtained in 59% yield; H NMR: δ 1.81-
1.93 (m, 1H), 1.96 (d, J= 6.3 Hz, 3H), 2.31-2.45 (m, 1H), 2.62-
Anal. Calcd. for C H IO : C, 46.17; H, 5.81. Found: C,
1
4
21
3
4
6.22; H, 5.66.
2
(
2
[
1
8
2
.72 (m, 1H), 2.94-3.08 (m, 2H), 3.29-3.43 (m, 3H), 4.10-4.35
1
3
m, 2H), 4.56 (quint, J= 6,0 Hz, 1H). C NMR: δ [6.76, 6.96],
3.95, [29.28, 29.31], [29.83, 29.85], [30.80, 30.94], 31.82,
80.18, 80.23], [83.03, 83.17], 94.41, [168.70, 168.73], [171.16,
Ethyl 2-Iodomethyl-5-(3-pentenyl)-2,3-dihydro-4-furancarboxy-
late (2h).
1
Compound 2h was obtained in 50% yield; H NMR: δ 1.28 (t,
71.57]. IR: 2942, 1740, 1674, 1334, 1253, 1187, 1083, 1010,
J= 7.11 Hz, 3H), 1.63 (d, J= 4.86 Hz, 3H), 2.21-2.33 (m, 2H),
.55-2.73 (m, 3H), 3.03 (dd, J=10.48 and 6.43 Hz, 1H), 3.25-3.33
m, 2H), 4.17 (q, J= 7.12 Hz, 2H), 4.64-4.70 (m, 1H), 5.42-5.47
m, 2H). 13C NMR: δ 9.11, 14.81, 18.27, 27.97, 30.19, 36.47,
-1
57, 751 cm . MS: m/z 43, 55 (100), 69, 85, 113, 149, 181, 227,
2
(
(
5
4
3
1
+
67, 295, 321, 421, 448 (M ).
Anal. Calcd. for C H I O : C, 29.49; H, 3.15. Found: C,
11 14 2 3
2
9.27; H, 3.05.
9.96, 80.73, 101.95, 126.21, 130.08, 166.03, 170.52. MS: m/z
3 (100), 67, 81, 95, 113, 131, 149, 193, 223, 239, 253, 277, 293,
7-Iodo-3-(7-iodoperhydrobenzo[b]-2-furylidene)perhydrobenzo-
[b]-2-furanone (4d).
+
11, 321, 351 (M ). IR: 2976, 2933, 1709, 1643, 1445, 1375,
-1
243, 1171, 1055, 971, 764, 522 cm .
Anal. Calcd. for C H IO : C, 44.59; H, 5.47. Found: C,
1
Compound 4d was obtained in 10% yield; H NMR: δ 1.30-
1
3
19
3
2
(
.00 (m, 12H), 2.65-2.29 (m, 1H), 2.97-3.05 (m, 2H), 3.38-3.40
4
4.52; H, 5.30.
1
3
m, 1H), 4.26-4.66 (m, 4H). C NMR: δ [27.75, 27.89], [28.84,
Ethyl 7-Iodo-2-(3-pentenyl)-3a,4,5,6,7,7a-hexahydrobenzo[b]-3-
furancarboxylate (2i).
28.92], [34.61, 34.65], 35.82, [81.22, 81.45], [87.02, 87.21],
[102.41, 102.83], [168.00, 168.14], [171.55, 171.58]. IR: 2931,
2
860, 1739, 1674, 1449, 1253, 1157, 1011, 911, 742, 527, 508
1
Compound 2i was obtained in 54 % yield; H NMR: δ 1.28 (t,
-1
cm . MS: m/z 41 (100), 55, 79, 91, 121, 165, 187, 207, 241, 259,
J= 7.01 Hz, 3H), 1.63 (d, J= 5.3 Hz, 3H), 1.42-2.04 (m, 6H), 2.24
+
2
99, 387, 514 (M ).
(dd, J= 13.6 and 6.63 Hz, 2H), 2.54-5.63 (m, 1H), 2.67-2.75 (m,
Anal. Calcd. for C H I O : C, 37.38; H, 3.92. Found: C,
1
6 20 2 3
1
4
1
2
1
2
1
H), 3.18 (dd, J= 15.28 and 7.54 Hz, 1H), 4.13-4.22 (m, 2H),
3
7.56; H, 4.25.
.56 (dd, J= 10.6 and 4.53 Hz, 1H), 4.69 (dd, J= 7,36 and 4.9 Hz,
1
3
H), 5.30-5.53 (m, 2H). C NMR: δ 14.39, 17.88, 20.70, 27.01,
8.06, 28.74, 29.86, 32.25, 39.24, 59.43, 87.01, 109.36, 125.88,
29.64, 165.64, 170.93. MS: m/z 55, 79, 91, 121, 139, 171, 189,
5-Iodomethyl-3-(7-iodoperhydrobenzo[b]-2-furylidene)tetrahy-
dro-2-furanone (4e).
Compound 4e was obtained in 78% yield; mp 77-79 °C.
+
07, 217, 245, 263, 317, 345, 391(100) (M ). IR: 2938, 1697,
1
Diastereomeric ratio: 1:1:1. H NMR: δ 1.32-1.40 (m, 1H); 1.49-
-1
635, 1445, 1316, 1168, 1089, 972, 775, 620 cm .
Anal. Calcd. for C H IO : C, 49.24; H, 5.94. Found: C,
1
.56 (m, 1H), 1.65-1.68 (m, 1H), 1.72-1.78 (m, 1H), 1.95 (q, J= 5.3
Hz, 2H), 2.62-2.64 (m, 1H), 2.69-2.75 (m, 1H), 2.96-2.98 (m, 1H),
.04-3.10 (m, 2H), 3.25 (dd, J= 8.0 e 10.5 Hz, 1H), 3.39 (dd, J=
3.85 and 10.50 Hz, 1H), 4.45 (q, J= 5.1 Hz, 1H), 4.50-4.58 (m,
1
3
19
3
5
0.02; H, 5.82.
3
5
-Iodomethyl-3-(5-iodomethyltetrahydro-2-furylidene)tetrahy-
13
dro-2-furanone (4a).
1H), 4.69 (t, J= 5.1 Hz, 1H). C NMR: δ 9.17, 21.27, 25.99,