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JZ11.5, 8.0 Hz), 3.31 (1H, dd, JZ17.7, 8.9 Hz), 3.04 (1H,
dd, JZ11.5, 1.0 Hz), 2.65 (1H, bs), 2.38 (1H, sext, JZ
6.7 Hz), 1.74 (3H, d, JZ1.3 Hz), 1.72 (3H, d, JZ1.3 Hz),
1.08 (3H, d, JZ6.9 Hz), 0.99 (3H, d, JZ6.9 Hz); 13C NMR
(CDCl3) d 203.1 (C), 172.9 (C), 136.2 (C), 125.7 (CH), 71.6
(CH) 65.3 (CH), 45.8 (CH2), 31.0 (CH), 30.8 (CH2), 25.9
(CH3), 19.2 (CH3), 18.5 (CH3), 17.9 (CH3). ES HRMS m/z
(MKH2O)C calcd 270.0986, obs 270.0985.
sext, JZ6.8 Hz), 1.08 (3H, d, JZ6.8 Hz), 0.99 (3H, d, JZ
7.0 Hz), 0.95 (9H, s); 13C NMR (CDCl3) d 203.4 (C), 174.2
(C), 75.4 (CH), 71.7 (CH), 41.2 (CH2), 34.7 (C), 31.1 (CH),
30.8 (CH2), 26.0 (3CH3), 19.3 (CH3), 18.0 (CH3).
4.1.7. 1-[(4S)-tert-Isopropyl-2-thioxo-thazolidine-3-yl]-
(3S)-hydroxy-4,4-diphenyl-butan-1-one (7). Rf 0.30 (7:3,
petroleum ether/ethyl acetate); [a]DZC271.0 (c 1.0,
CHCl3); IR 3548, 3022, 2965, 1688, 1457, 1163 cmK1; 1H
NMR (300 MHz, CDCl3) d 7.40–7.15 (10H, m), 5.10 (1H, t,
JZ6.7 Hz), 4.96 (1H, td, JZ9.0, 2.4 Hz), 4.00 (1H, d, JZ
8.7 Hz), 3.48 (1H, dd, JZ11.4, 7.9 Hz), 3.45 (1H, dd, JZ
17.6, 2.6 Hz), 3.29 (1H, dd, JZ17.6, 9.2 Hz), 2.99 (1H, dd,
JZ11.4, 1.0 Hz), 2.67 (1H, bs), 2.33 (1H, sext, JZ6.7 Hz),
1.02 (3H, d, JZ6.7 Hz), 0.94 (3H, d, JZ6.8 Hz); 13C NMR
(CDCl3) d 203.0 (C), 172.8 (C), 141.9 (C), 141.2 (C), 128.9
(2CH), 128.8 (2CH), 128.7 (2CH), 128.4 (2CH), 126.8
(2CH), 71.6 (CH), 70.4 (CH), 57.6 (CH), 44.2 (CH2), 31.0
(CH3), 30.7 (CH2), 19.2 (CH3), 17.9 (CH3). ES HRMS m/z
(MCH)C calcd 400.1405, obs 400.1413.
4.1.3. 1-[(4S)-tert-Isopropyl-2-thioxo-thazolidine-3-yl]-
(3R)-hydroxy-7-bromo-hepta-4,6-diene-1-one (3). Rf
0.32 (7:3, petroleum ether/ethyl acetate); [a]DZC292.2
(c 1.0, CHCl3); IR 3437, 3058, 1690, 1470, 1168 cmK1; 1H
NMR (CDCl3) d 6.72 (1H, dd, JZ13.3, 11.0 Hz), 6.35 (1H,
d, JZ13.3 Hz), 6.26 (1H, ddd, JZ15.3, 11.0, 1.2 Hz), 5.80
(1H, dd, JZ15.3, 5.6 Hz), 5.17 (1H, t, JZ6.8 Hz), 4.70 (1H,
m), 3.69 (1H, dd, JZ17.8, 3.1 Hz), 3.53 (1H, dd, JZ11.5,
7.9 Hz), 3.29 (1H, dd, JZ17.6, 8.6 Hz), 3.05 (1H, d, JZ
11.5 Hz), 2.97 (1H, bs), 2.36 (1H, sext., JZ6.8 Hz), 1.07
(3H, d, JZ6.7 Hz), 0.99 (3H, d, JZ6.8 Hz); 13C NMR
(CDCl3) d 203.0 (C), 172.2 (C), 136.6 (CH), 134.6 (CH),
127.8 (CH), 109.5 (CH), 71.3 (CH), 67.9 (CH), 45.0 (CH2),
31.0 (CH), 30.7 (CH2), 19.0 (CH3), 17.8 (CH3).
4.1.8. 1-[(4S)-tert-Isopropyl-2-thioxo-thazolidine-3-yl]-
(3R)-hydroxy-pentan-1-one (8). Rf 0.42 (3:2, petroleum
ether/ethyl acetate); [a]DZC470.1 (c 1.0, CHCl3); IR
3456, 2964, 2876, 1689, 1466, 1165, 1040 cmK1; 1H NMR
(CDCl3) d 5.17 (1H, t, JZ6.8 Hz), 4.07 (1H, m), 3.65 (1H,
dd, JZ17.8, 2.3 Hz), 3.53 (1H, dd, JZ11.5, 7.8 Hz), 3.12
(1H, dd, JZ17.8, 9.5 Hz), 3.04 (1H, d, JZ11.5 Hz), 2.69
(1H, bs), 2.37 (1H, sext, JZ6.8 Hz), 1.68–1.47 (2H, m),
1.07 (3H, d, JZ6.8 Hz), 0.99 (3H, d, JZ6.7 Hz), 0.98 (3H,
t, JZ7.4 Hz); 13C NMR (CDCl3) d 203.2 (C), 173.4 (C),
71.5 (CH), 69.4 (CH), 45.2 (CH2), 31.0 (CH), 30.7 (CH2),
29.4 (CH2), 19.2 (CH3), 18.0 (CH3), 10.1 (CH3).
4.1.4. 1-[(4S)-4-Isopropyl-2-thioxo-thiazolidine-3-yl]-
(3R)-hydroxy-4-phenyl-propanone (4). Rf 0.45 (3:2,
petroleum ether/ethyl acetate); [a]DZC386.7 (c 1.0,
CHCl3); IR 3476, 2965, 1682, 1042 cmK1 1H NMR
;
(CDCl3) d 7.45–7.37 (4H, m), 7.32 (1H, m), 5.30 (1H, dd,
JZ9.3, 2.8 Hz), 5.16 (1H, t, JZ7.0 Hz), 3.82 (1H, ddd, JZ
17.5, 2.7, 0.8 Hz), 3.63 (1H, dd, JZ17.5, 9.3 Hz), 3.51 (1H,
ddd, JZ11.6, 8.0, 0.6 Hz), 3.22 (1H, t, JZ3.2 Hz), 3.05
(1H, d, JZ11.6 Hz), 2.40 (1H, sext, JZ6.7 Hz), 1.10 (3H,
d, JZ6.8 Hz), 1.02 (3H, d, JZ6.9 Hz); 13C NMR (CDCl3) d
203.1 (C), 172.7 (C), 142.6 (C), 128.7 (2CH), 127.9 (CH),
125.9 (2CH), 71.6 (CH), 70.3 (CH), 47.0 (CH2), 31.0 (CH),
30.9 (CH2), 19.2 (CH3), 18.0 (CH3). ES HRMS m/z (MC
Na)C calcd 332.0755, obs 332.0754.
4.1.9. 1-[(4S)-tert-Isopropyl-2-thioxo-thazolidine-3-yl]-
(3R)-hydroxy-5-phenyl-pentan-1-one (9). Rf 0.42 (3:2,
petroleum ether/ethyl acetate); [a]DZC321.7 (c 1.0,
CHCl3); IR 3519, 3023, 2961, 1686, 1153 cmK1 1H
;
NMR (CDCl3) d 7.38–7.17 (5H, m), 5.17 (1H, m), 4.15
(1H, m), 3.67 (1H, dd, JZ17.8, 2.5 Hz), 3.53 (1H, dd, JZ
11.5, 8.0 Hz), 3.18 (1H, dd, JZ17.8, 9.2 Hz), 3.04 (1H, dd,
JZ11.5, 1.0 Hz), 2.97–2.68 (3H, m), 2.37 (1H, sext, JZ
6.7 Hz), 1.98–1.75 (2H, m), 1.08 (3H, d, JZ6.8 Hz), 0.99
(3H, d, JZ7.0 Hz); 13C NMR (CDCl3) d 203.1 (C), 173.1
(C), 141.8 (C), 128.5 (2CH), 128.4 (2CH), 125.9 (CH), 71.4
(CH), 67.2 (CH), 45.6 (CH2), 37.9 (CH2), 31.8 (CH2), 30.9
(CH), 30.6 (CH2), 19.1 (CH3), 17.8 (CH3). ES HRMS m/z
(MCNa)C calcd 360.1068, obs 360.1060.
4.1.5. 1-[(4S)-tert-Isopropyl-2-thioxo-thazolidine-3-yl]-
(3R)-hydroxy-4-(p-bromophenyl)-propan-1-one (5). Rf
0.40 (3:2, petroleum ether/ethyl acetate); [a]DZC317.7
(c 1.0, CHCl3); mp 100–102 8C; IR 3468, 2955, 1686, 1359,
1
1300, 1243, 1219, 1157, 1008 cmK1; H NMR (CDCl3) d
7.50 (2H, d, JZ8.5 Hz), 7.29 (2H, d, JZ8.5 Hz), 5.27 (1H,
dd, JZ9.4, 2.7 Hz), 5.16 (1H, dd, JZ7.6, 6.6 Hz), 3.82 (1H,
dd, JZ17.6, 2.7 Hz), 3.51 (1H, ddd, JZ11.5, 7.8, 1.5 Hz),
3.50 (1H, ddd, JZ17.6, 9.4 Hz), 3.05 (1H, dd, JZ11.5,
1.1 Hz), 2.73 (1H, bs), 2.38 (1H, sext, JZ6.7 Hz), 1.08 (3H,
d, JZ6.8 Hz), 1.00 (3H, d, JZ7.0 Hz); 13C NMR (CDCl3) d
203.1 (C), 172.3 (C), 141.5 (C), 131.6 (2CH), 127.6 (2CH),
121.5 (C), 71.5 (CH), 69.6 (CH), 46.8 (CH2), 30.9 and 30.7
(CH and CH2), 19.1 (CH3), 17.8 (CH3). ES HRMS m/z (MK
H2OCH)C calcd 369.9935, obs 369.9930.
4.1.10. 1-[(4S)-tert-Isopropyl-2-thioxo-thazolidine-3-yl]-
(3S)-hydroxy-5-phenyl-pent-4-en-1-one (10). Rf 0.48
(7:3, petroleum ether/ethyl acetate); [a]DZC301.5 (c 1.0,
CHCl3); IR 3458, 3014, 2966, 1686, 1165 cmK1; 1H NMR
(CDCl3) d 7.39 (2H, m), 7.32 (2H, m), 7.24 (1H, m), 6.67
(1H, d, JZ15.8 Hz), 6.27 (1H, dd, JZ15.8, 5.9 Hz), 5.19
(1H, m), 4.78 (1H, m), 3.73 (1H, dd, JZ17.4, 8.8 Hz), 3.52
(1H, JZ11.5, 8.0 Hz), 3.48 (1H, dd, JZ17.4, 3.5 Hz), 3.34
(1H, bs), 3.04 (1H, dd, JZ11.5, 1.0 Hz), 2.37 (1H, sext, JZ
6.7 Hz), 1.07 (3H, d, JZ6.8 Hz), 0.99 (3H, d, JZ6.9 Hz);
13C NMR (CDCl3) d 203.2 (C), 172.9 (C), 136.7 (C), 130.9
(CH), 130.2 (CH), 128.7 (2CH), 127.9 (CH), 126.7 (2CH),
71.6 (CH), 69.4 (CH), 45.3 (CH2), 30.9 (CH), 30.8 (CH2),
4.1.6. 1-[(4S)-tert-Isopropyl-2-thioxo-thazolidine-3-yl]-
(3R)-hydroxy-4,4-dimethyl-pentan-1-one (6). Rf 0.42
(7:3, petroleum ether/ethyl acetate); [a]DZC454.5 (c 1.0,
CHCl3); IR 3524, 2961, 1686, 1161 cmK1 1H NMR
;
(CDCl3) d 5.16 (1H, t, JZ7.0 Hz), 3.83 (1H, ddd, JZ
10.4, 3.9, 1.8 Hz), 3.62 (1H, dd, JZ17.7, 2.0 Hz), 3.53 (1H,
dd, JZ11.4, 8.0 Hz), 3.15 (1H, dd, JZ17.7, 10.5 Hz), 3.03
(1H, dd, JZ11.5, 1.0 Hz), 2.67 (1H, JZ3.8 Hz), 2.38 (1H,