J.-C. Jung et al. / Tetrahedron 58 02ꢀꢀ2) 3639±3646
3643
21 1
neat, NaCl) 2986, 1714, 1556, 1445, 1104 cm ; H NMR
ꢀ
6.72 Hz, 2H), 4.25±3.97 ꢀm, 2H), 3.84, 3.81 ꢀs, s, total
1
3
ꢀ
CDCl ) d 13.05 ꢀs, 1H), 4.27 ꢀq, J6.78 Hz, 2H), 2.43±
3H), 2.35, 1.97 ꢀs, s, total 3H), 1.24±0.95 ꢀm, 3H);
NMR ꢀCDCl ) d 193.7, 190.3, 177.9, 131.5, 131.3, 114.6,
C
3
2
0
1
.41 ꢀm, 1H), 2.28 ꢀs, 3H), 1.31 ꢀq, J6.78 Hz, 3H), 1.18±
3
1
.96 ꢀm, 4H); C NMR ꢀCDCl ), d 200.0, 168.1, 162.7,
3
114.0, 105.4, 61.3, 55.9, 20.3, 14.3; MS ꢀESI) ꢀm/z) 265
[M1H] , 135 ꢀbase peak); 287 [M1Na] , HRMS calcd
3
1
1
09.3, 61.1, 25.2, 16.9, 14.6, 12.4; HRMS ꢀESI) ꢀm/z)
1
1
for C H O : 265.1071 [M1H] , found 265.1059.
calcd for C H O Na: 221.0784 [M1Na] , found
4
1
0
14
14 16
5
2
21.0767.
3.2.10. Ethyl 2-*2,6-dimethoxypyridine-3-carbonyl)-3-
3
.2.4. Ethyl 2-*2,2-dimethylpropionyl)-3-hydroxy-2-
hydroxy-2-butenoate *2j). R 0.5 ꢀ10% ethyl acetate in
f
butenoate *2d). R 0.5 ꢀ15% ethyl acetate in hexanes);
hexanes); IR ꢀneat, NaCl) 3631, 2985, 1716, 1594,
1010 cm ; H NMR ꢀCDCl ) d 13.20, 5.32 ꢀbr s, br s,
f
2
IR ꢀneat, NaCl) 2974, 1746, 1722, 1478, 1242 cm ; H
1
1
21
1
3
NMR ꢀCDCl ) d 4.92 ꢀbr s, 1H), 4.06 ꢀq, J7.12 Hz, 2H),
total 1H), 7.76 ꢀd, J8.30 Hz, 1H), 6.35 ꢀd, J8.30 Hz,
3
1
3
2
.11 ꢀs, 3H), 1.11 ꢀs, J7.12 Hz, 3H), 1.02 ꢀs, 9H); C
NMR ꢀCDCl ) d 205.2, 198.5, 165.5, 67.5, 62.3, 46.1,
1H), 4.17 ꢀq, J7.12 Hz, 2H), 3.95 ꢀs, 3H), 3.81 ꢀs, 3H),
1
3
2.40 ꢀs, 3H), 1.24 ꢀq, J7.12 Hz, 3H); C NMR ꢀCDCl ) d
3
3
1
7.6, 29.1, 14.2; MS ꢀESI) ꢀm/z) 215 [M1H] , 173, 127,
2
194.1, 189.1, 167.3, 166.1, 162.3, 141.5, 113.0, 103.8,
101.8, 60.1, 53.6, 50.0, 24.6, 13.6; HRMS ꢀESI) ꢀm/z)
1
5, 57 ꢀbase peak); 237 [M1Na] , HRMS calcd for
8
C H O : 215.1278 [M1H] , found 215.1270.
1
1
calcd for C H O : 296.11128 [M1H] , found 296.1135.
1
1
18
4
14 17
6
3
.2.5.
Ethyl
2-cyclopentanecarbonyl-3-hydroxy-2-
3.2.11. Diethyl 2-*1-hydroxyethylidene)malonate *2k).
R 0.5 ꢀ20% ethyl acetate in hexanes); IR ꢀneat, NaCl)
butenoate *2e). R 0.6 ꢀ10% ethyl acetate in hexanes); IR
f
f
2
neat, NaCl) 2958, 1714, 1565, 1079 cm ; H NMR
1
1
21
2984, 1729, 1650, 1469, 1090 cm ; H NMR ꢀCDCl )
1
31b
ꢀ
3
ꢀ
CDCl ) d 4.25 ꢀq, J7.14 Hz, 2H), 3.27 ꢀt, J7.84 Hz,
d 13.45, 4.38 ꢀbr s, br s, total 1H), 4.23±4.13 ꢀm, 4H), 2.27,
2.13 ꢀs, s, total 3H), 1.27±1.19 ꢀm, 6H); C NMR ꢀCDCl3)
3
1
3
1
3
4
H), 2.28 ꢀs, 3H), 1.84±1.57 ꢀm, 8H), 1.32 ꢀq, J7.14 Hz,
1
H); C NMR ꢀCDCl ) d 200.9, 193.9, 167.2, 108.3, 60.3,
3
d 197.0, 171.6, 166.4, 100.2, 62.2, 61.4, 21.0, 14.4, 14.3;
MS ꢀESI) ꢀm/z) 203 [M1H] , 179, 157 ꢀbase peak); 225
3
1
5.2, 30.4, 29.5, 25.9, 25.3, 24.6, 13.7; HRMS ꢀESI) ꢀm/z)
1
1
[M1Na] .
calcd for C H O : 227.1278 [M1H] , found 227.1271.
4
1
2
18
3
.2.6. Ethyl 2-*furan-2-carbonyl)-3-hydroxy-2-butenoate
3.2.12. Diethyl 2-*1-hydroxy-2,2-methylpropylidene)-
malonate *2l). R 0.6 ꢀ10% ethyl acetate in hexanes); IR
*
2f). R 0.3 ꢀ10% ethyl acetate in hexanes); IR ꢀneat, NaCl)
f
f
2
136, 2983, 1746, 1720, 1471, 1255 cm ; H NMR
1
1
21
1
ꢀneat, NaCl) 2986, 1733, 1609, 1242 cm ; H NMR
3
ꢀ
CDCl ) d 13.17, 5.19 ꢀbr s, br s, total 1H), 7.55 ꢀd,
3
ꢀCDCl ) d 13.28, 4.62 ꢀbr s, br s, total 1H), 4.24±4.18 ꢀm,
3
1
3
J3.60 Hz, 1H), 7.19 ꢀd, J3.50 Hz, 1H), 6.61±6.52 ꢀm,
4H), 2.81 ꢀq, J6.95 Hz, 1H), 1.28±1.10 ꢀm, 12H);
C
NMR ꢀCDCl ) d 203.1, 186.3, 165.0, 98.9, 62.6, 61.6,
1
H), 4.24 ꢀq, J7.11 Hz, 2H), 2.27 ꢀs, 3H), 1.23 ꢀs,
3
1
3
J7.11 Hz, 3H); C NMR ꢀCDCl ) d 192.3, 179.5, 175.4,
41.3, 19.9, 18.5, 14.4, 14.3; HRMS ꢀESI) ꢀm/z) calcd for
C H O Na: 253.1046 [M1Na] , found 253.1028.
3
1
1
50.2, 146.7, 118.7, 113.5, 107.7, 61.8, 20.3, 14.4; HRMS
1
1
18
5
1
ꢀESI) ꢀm/z) calcd for C H O Na: 247.0577 [M1Na] ,
11 12 5
found 247.0573.
3.2.13. Diethyl 2-*cyclopropylhydroxymethylene)malo-
nate *2m). R 0.5 ꢀ10% ethyl acetate in hexanes); IR
f
2
ꢀneat, NaCl) 2992, 1733, 1714, 1281 cm ; H NMR
1
1
3
.2.7. Ethyl 3-hydroxy-2-*thiophene-2-carbonyl)-2-
butenoate *2g). R 0.3 ꢀ10% ethyl acetate in hexanes);
ꢀCDCl ) d 13.67, 4.55 ꢀbr s, br s, total 1H), 4.30±4.17 ꢀm,
3
f
2
IR ꢀneat, NaCl) 3095, 2983, 1741, 1660, 1243 cm ; H
1
1
13
4H), 2.14±2.05 ꢀm, 1H), 1.29±0.90 ꢀm, 10H); C NMR
NMR ꢀCDCl ) d 13.03, 3.90 ꢀbr s, br s, total 1H), 7.74±
3
ꢀCDCl ) d 199.6, 184.2, 165.0, 99.0, 62.6, 61.5, 20.9,
3
7
2
1
2
2
.64 ꢀm, 2H), 7.14±7.04 ꢀm, 1H), 4.20 ꢀq, J7.09 Hz, 2H),
13.9, 12.9, 10.0, 9.4; HRMS ꢀESI) ꢀm/z) calcd for
C H O Na: 251.0890 [M1Na] , found 251.0865.
1
3
1
.24 ꢀs, 3H), 1.23 ꢀs, J7.09 Hz, 3H); C NMR ꢀCDCl ) d
3
11 16
5
85.8, 177.9, 167.4, 145.9, 136.4, 135.3, 128.2, 105.7, 61.5,
0.4, 14.3; HRMS ꢀESI) ꢀm/z) calcd for C H O SNa:
3.2.14. Diethyl 2-*1-hydroxy-2,2-dimethylpropylidene)-
malonate *2n). R 0.5 ꢀ10% ethyl acetate in hexanes); IR
1
1
12
4
1
63.0348 [M1Na] , found 263.0345.
f
2
1 1
neat, NaCl) 3654, 2978, 1736, 1478, 1038 cm ; H NMR
ꢀ
3
.2.8. Ethyl 2-benzoyl-3-hydroxy-2-butenoate *2h).
ꢀCDCl ) d 4.83 ꢀbr s, 1H), 4.15 ꢀq, J7.12 Hz, 4H), 1.19 ꢀq,
3
1
3
R 0.5 ꢀ20% ethyl acetate in hexanes); IR ꢀneat, NaCl)
J7.12 Hz, 6H), 1.10 ꢀs, 9H); C NMR ꢀCDCl ) d 203.9,
f
3
2
372, 2983, 1715, 1244, 1071 cm ; H NMR ꢀCDCl )
1
1
31a
1
165.0, 62.5, 60.1, 45.8, 26.1, 14.2; MS ꢀm/z) 245 [M1H] ,
3
d 13.24, 5.37 ꢀbr s, br s, total 1H), 7.54±7.34 ꢀm, 5H), 4.09±
3
1
161, 84 ꢀbase peak); 267 [M1Na] , HRMS calcd for
1
C H O : 245.1384 [M1H] , found 245.1366.
3
.90 ꢀm, 2H), 2.38, 2.04 ꢀs, s, total 3H), 0.96±0.82 ꢀm, 3H);
C NMR ꢀCDCl ) d 199.0, 194.0, 168.3, 137.8, 131.9,
1
2
20
5
1
3
3
1
29.3, 129.0, 128.7, 127.7, 109.1, 61.3, 24.6, 14.0; MS
ESI) ꢀm/z) 235 [M1H] , 171, 104 ꢀbase peak); 257
3.2.15. Diethyl 2-*cyclopentylhydroxymethylene)malo-
nate *2o). R 0.6 ꢀ15% ethyl acetate in hexanes); IR
1
ꢀ
f
1
M1Na] .
21
ꢀneat, NaCl) 3583, 2963, 1730, 1601, 1241, 1035 cm ;
[
1
31c
H NMR ꢀCDCl ) d 13.28, 4.52 ꢀbr s, br s, total 1H),
3
3
.2.9. Ethyl 3-hydroxy-2-*4-methoxybenzoyl)-2-buteno-
4.22±4.23 ꢀm, 4H), 3.05±2.90 ꢀm, 1H), 1.78±1.52 ꢀm,
8H), 1.27±1.18 ꢀm, 6H); C NMR ꢀCDCl ) d 202.1,
1
3
ate *2i). R 0.5 ꢀ20% ethyl acetate in hexanes); IR ꢀneat,
f
3
2
NaCl) 3335, 2981, 1744, 1715, 1258 cm ; H NMR
1
1
171.4, 165.0, 99.5, 62.5, 61.5, 43.1, 31.3, 29.9, 26.7, 26.3,
14.6, 14.3; MS ꢀESI) ꢀm/z) 257 [M1H] , 202, 115, 96, 55
1
ꢀ
ꢀ
CDCl ) d 13.06, 5.31 ꢀbr s, br s, total 1H), 7.83, 7.51
3
ddd, J8.79, 8.82, 8.70 Hz, 2H), 6.88 ꢀdd, J7.56,
1
ꢀbase peak); 279 [M1Na] .