P. Kwiatkowski et al. / Tetrahedron: Asymmetry 18 (2007) 215–223
221
13C NMR (125 MHz, CDCl3): d 174.7, 133.1, 125.5, 69.8,
65.0, 52.9, 48.8, 47.8, 44.6, 44.2, 38.1, 32.8, 28.1, 26.4,
25.3, 22.8, 22.1, 20.7, 19.8; HMRS calcd for (M+Na)+
C19H29NO4SNa: 390.1709, found: 390.1706; HPLC (Chira-
cel OD-H column, hexane/i-PrOH, 9:1, flow rate 1.0 mL/
min, k = 205 nm): tR[minor-(20R)-7a] = 11.3 min, tR[ma-
jor-(20S)-7a] = 19.5 min.
1H), 4.88 (dt, J = 10.8, 4.5 Hz, 1H), 4.71 (s, 1H), 3.41–
3.37 (m, 1H), 2.38 (d, J = 5.3 Hz, 1H), 2.19 (dd, J = 15.8,
3.1 Hz, 1H), 2.12–2.06 (m, 1H), 1.95 (dd, J = 15.8,
9.3 Hz, 1H), 1.87–1.82 (m, 2H), 1.73–1.67 (m, 1H), 1.54–
1.45 (m, 1H), 1.31 (s, 3H), 1.18–1.12 (m, 1H), 1.20 (s,
3H), 1.00 (s, 9H), 0.97–0.87 (m, 2H), 0.89 (d, J = 6.5 Hz,
3H); 13C NMR (125 MHz, CDCl3): d 174.4, 152.6, 151.7,
128.0, 125.2 · 2, 108.5, 75.6, 69.3, 50.3, 41.5, 39.4, 36.0,
35.8, 34.5, 31.2, 29.4, 29.1, 26.3, 23.2, 21.7; HMRS calcd
for (M+Na)+ C25H38O3Na: 409.2713, found: 409.2733.
4.3.7. (20S)-20-Hydroxy-40-phenylpent-40-enoic acid (1R,2S,
5R)-8-phenylmenthyl ester (20S)-2b. Oil; IR (CH2Cl2):
3505, 2955, 2924, 1724, 1600, 1444, 1265, 1214, 1092,
1
905, 777, 700 cmꢁ1; H NMR (500 MHz, CDCl3): d 7.34–
4.3.11.
(20S)-30-(Cyclopent-1-enyl)-20-hydroxy-propionic
7.27 (m, 5H), 7.24–7.16 (m, 4H), 7.00–6.97 (m, 1H), 5.31
(d, J = 1.0 Hz, 1H), 5.07 (d, J = 1.0 Hz, 1H), 4.84 (dt,
J = 10.8, 4.5 Hz, 1H), 3.30–3.26 (m, 1H), 2.70 (dd,
J = 14.6, 3.6 Hz, 1H), 2.42–2.38 (m, 2H), 2.08–2.02 (m,
1H), 1.84–1.78 (m, 1H), 1.75–1.65 (m, 2H), 1.50–1.40 (m,
1H), 1.26 (s, 3H), 1.18–1.10 (m, 1H), 1.17 (s, 3H), 0.94–
0.84 (m, 2H), 0.87 (d, J = 6.5 Hz, 3H); 13C NMR
(125 MHz, CDCl3): d 173.9, 151.5, 143.7, 140.6, 128.3,
127.9, 127.5, 126.4, 125.2, 125.1, 115.6, 75.7, 68.5, 50.3,
41.4, 40.0, 39.4, 34.4, 31.2, 29.2, 26.3, 23.4, 21.7; HMRS
calcd for (M+Na)+ C27H34O3Na: 429.2400, found:
429.2420.
acid (1R,2S,5R)-8-phenylmenthyl ester (20S)-6b. Oil; IR
(CH2Cl2): 3544, 2958, 1720, 1600, 1495, 1444, 1223, 1091,
1030, 977, 561 cmꢁ1 1H NMR (500 MHz, CDCl3): d
;
7.31–7.26 (m, 4H), 7.16–7.11 (m, 1H), 5.35 (br s, 1H),
4.85 (dt, J = 10.8, 4.5, 1H), 3.35–3.31 (m, 1H), 2.45 (d,
J = 5.1, 1H), 2.29–2.24 (m, 2H), 2.21–2.06 (m, 5H), 1.86–
1.79 (m, 4H), 1.73–1.66 (m, 1H), 1.53–1.42 (m, 1H), 1.29
(s, 3H), 1.20–1.12 (m, 1H), 1.19 (s, 3H), 0.96–0.87
(m, 2H), 0.87 (d, J = 6.5 Hz, 3H); 13C NMR (125 MHz,
CDCl3): d 174.2, 151.7, 139.5, 127.9, 127.1, 125.2, 125.2,
75.6, 68.7, 50.3, 41.6, 39.4, 35.8, 35.0, 34.5, 32.3, 31.2,
29.3, 26.3, 23.4, 23.2, 21.7; HMRS calcd for (M+Na)+
C24H34O3Na: 393.2400, found: 393.2397.
4.3.8. (20S)-20-Hydroxy-40-methylpent-40-enoic acid (1R,
2S,5R)-8-phenylmenthyl ester (20S)-3b. Oil; IR (CH2Cl2):
3505, 2955, 1723, 1650, 1443, 1263, 1209, 1097, 891, 765,
4.3.12. (20S)-30-(Cyclohex-1-enyl)-20-hydroxy-propionic acid
(1R,2S,5R)-8-phenylmenthyl ester (20S)-7b. Oil; IR
(CH2Cl2): 3492, 2925, 1723, 1600, 1496, 1443, 1370, 1258,
1
701 cmꢁ1; H NMR (500 MHz, CDCl3): d 7.32–7.26 (m,
1
4H), 7.18–7.11 (m, 1H), 4.87 (dt, J = 10.8, 4.5 Hz, 1H),
4.78 (s, 1H), 4.67 (s, 1H), 3.31–3.26 (m, 1H), 2.40 (d,
J = 5.6 Hz, 1H), 2.14–2.08 (m, 2H), 1.97 (dd, J = 14.2,
8.8 Hz, 1H), 1.89–1.82 (m, 2H), 1.74–1.68 (m, 1H), 1.64
(s, 3H), 1.53–1.45 (m, 1H), 1.30 (s, 3H), 1.22–1.14 (m,
1H), 1.19 (s, 3H), 0.99–0.91 (m, 2H), 0.88 (d, J = 6.5 Hz,
3H); 13C NMR (125 MHz, CDCl3): d 174.2, 151.8, 141.1,
128.0, 125.3, 125.2, 113.5, 75.7, 68.2, 50.3, 42.3, 41.5,
39.4, 34.5, 31.2, 29.6, 26.2, 22.9, 22.2, 21.7; HMRS calcd
for (M+Na)+ C22H32O3Na: 367.2244, found: 367.2233.
1210, 1096, 764, 700 cmꢁ1; H NMR (500 MHz, CDCl3):
d 7.30–7.26 (m, 4H), 7.15–7.12 (m, 1H), 5.36 (br s, 1H),
4.85 (dt, J = 10.8, 4.4 Hz, 1H), 3.32–3.28 (m, 1H), 2.37
(d, J = 5.8 Hz, 1H), 2.11–2.03 (m, 2H), 1.97–1.89 (m,
3H), 1.85–1.79 (m, 3H), 1.77–1.67 (m, 2H), 1.61–1.45 (m,
6H), 1.29 (s, 3H), 1.19 (s, 3H), 1.20–1.12 (m, 1H), 0.97–
0.89 (m, 2H), 0.88 (d, J = 6.5 Hz, 3H); 13C NMR
(125 MHz, CDCl3): d 174.4, 151.7, 133.2, 127.9, 125.2,
125.1, 124.6, 75.6, 68.5, 50.4, 43.0, 41.7, 39.4, 34.5, 31.2,
29.2, 28.2, 26.3, 25.2, 23.3, 22.8, 22.2, 21.8; HMRS calcd
for (M+Na)+ C25H36O3Na: 407.2557, found: 407.2568.
4.3.9.
(20S)-20-Hydroxy-50-methyl-40-methylene-hexanoic
acid (1R,2S,5R)-8-phenylmenthyl ester (20S)-4b. Oil; IR
4.3.13. (20S)-(4E)-20-Hydroxy-oct-40-enoic acid (1R,2S,5R)-
8-phenylmenthyl ester (20S)-8b. NMR data in agreement
with those described in the literature.4b
(CH2Cl2): 3504, 2959, 2871, 1724, 1643, 1457, 1260, 1212,
1
1091, 979, 764, 700 cmꢁ1; H NMR (500 MHz, CDCl3): d
7.30–7.27 (m, 4H), 7.15–7.11 (m, 1H), 4.87 (dt, J = 10.8,
4.5, 1H), 4.81 (s, 1H), 4.69 (s, 1H), 3.32–3.28 (m, 1H),
2.40 (d, J = 5.59 Hz, 1H), 2.18 (dd, J = 14.7, 3.8 Hz, 1H),
2.15–2.05 (m, 2H), 1.96 (dd, J = 14.7, 8.7 Hz, 1H), 1.88–
1.81 (m, 2H), 1.73–1.67 (m, 1H), 1.53–1.44 (m, 1H), 1.30
(s, 3H), 1.21–1.12 (m, 1H), 1.19 (s, 3H), 0.99 (d,
J = 6.8 Hz, 3H), 0.97 (d, J = 6.8 Hz, 3H), 0.96–0.86 (m,
2H), 0.88 (d, J = 6.5 Hz, 3H); 13C NMR (125 MHz,
CDCl3): d 174.2, 151.8, 150.9, 127.9, 125.2, 125.1, 109.6,
75.6, 68.6, 50.3, 41.5, 39.5, 39.4, 34.5, 32.9, 31.2, 29.5,
26.2, 23.0, 21.7, 21.5; HMRS calcd for (M+Na)+
C24H36O3Na: 395.2557, found: 395.2575.
4.4. Determination of the diastereomeric ratio
The compositions of the reaction mixtures in case of ene
products 2a–7a derived from the Oppolzer’s sultam were
determined independently by HPLC and by 1H NMR.
Both these methods suffer from a certain analytical error
(HPLC because of theoretically different absorbance coeffi-
cients of both diastereomers). In all the cases, the products
of the ene reactions have been reduced with LiAlH4 in
Et2O to the corresponding diols 2c–7c and analyzed by
HPLC (2c, 3c, 6c, 7c) or GC (4c, 5c, as a isopropylidene
derivatives). The obtained results were very close ( 2%
de) to the results of direct HPLC measurements of ene
products 2a–7a. In the case of 8-phenylmenthyl derivatives,
the asymmetric inductions were determined after the reduc-
tion to the corresponding diols 2c–8c. Isopropylidene
derivatives of diols 4c, 5c, 8c were obtained by treatment
4.3.10. (20S)-20-Hydroxy-50,50di-methyl-40-methylene-hexa-
noic acid (1R,2S,5R)-8-phenylmenthyl ester (20S)-5b. Oil;
IR (CH2Cl2): 3504, 2957, 2870, 1723, 1636, 1457, 1362,
1215, 1095, 905, 763, 700 cmꢁ1 1H NMR (500 MHz,
;
CDCl3): d 7.29–7.26 (m, 4H), 7.15–7.11 (m, 1H), 4.93 (s,