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9: m.p. 117–122 ◦C. 1H NMR (300 MHz, CDCl3) ␦ 5.00-
4.90 (1H, m, H-3), 2.89 (1H, d, J = 4.3 Hz, H-6), 2.13 (1H,
dd, J = 11.8 Hz, H-4), 2.05-1.75 (7H, m, including 1s (3H,
CH3COO ) at 2.01 ppm), 1.75-0.90 (27H, m, including 1s
(3H, H-19) at 1.07 ppm), 0.89 (3H, d, J = 6.5 Hz, H-21),
0.84 (3H, t, J = 7.2 Hz, H-29), 0.82 (3H, d, J = 6.4 Hz, H-
26), 0.80 (3H, d, J = 6.5 Hz, H-27), 0.60 (3H, s, H-18). 13C
NMR (75 MHz, CDCl3) ␦ 170.22, 71.40, 65.18, 59.17, 56.77,
55.76, 45.81, 42.43, 42.32, 39.35, 36.13, 34.98, 33.88, 32.12,
29.85, 29.13, 28.75, 28.09, 27.21, 26.09, 24.05, 23.04, 21.34,
20.57, 19.81, 19.02, 18.69, 15.85, 11.96, 11.84. [␣]2D0 −22◦
(c 1, CHCl3). Anal. calcd for C31H52O3: C 78.76, H 11.09.
Found C 78.73, H 11.23.
compound 7 as a white solid (560 mg, 1.18 mmol, 89% yield):
m.p. 67–68 ◦C. 1H NMR (300 MHz, CDCl3) ␦ 5.30 (1H, br
s, H-6), 4.70-4.50 (1H, m, H-3), 3.84 (1H, d, J = 7.8 Hz,
H-7), 2.40-2.25 (2H, m), 2.05-1.95 (4H, m, including 1s
(3H, CH3COO ) at 2.03 ppm), 1.95-1.75 (4H, m), 1.75-1.00
(24H, m, including 1s (3H, H-19) at 1.05 ppm), 0.92 (3H, d,
J = 6.5 Hz, H-21), 0.84 (3H, t, J = 7.2 Hz, H-29), 0.83 (3H, d,
J = 6.6 Hz, H-26), 0.81 (3H, d, J = 6.7 Hz, H-27), 0.68 (3H, s,
H-18). 13C NMR (75 MHz, CDCl3) ␦ 170.47, 142.34, 126.30,
73.44, 73.20, 55.89, 55.34, 48.17, 45.83, 42.91, 40.77, 39.50,
37.59, 36.65, 36.50, 36.09, 33.96, 29.13, 28.54, 27.70, 26.40,
26.09, 23.05, 21.37, 21.02, 19.80, 19.07, 19.02, 18.82, 11.97,
11.81. IR (CCl4), 3606, 2958, 2872, 1734, 1466, 1374, 1243,
1135, 1085, 1033, 951, 903 cm−1. [␣]D20 −6◦ (c 1, CHCl3).
Anal. calcd for C31H52O3: C 78.76, H 11.09. Found C 78.54,
H 11.18.
10: m.p. 110–111 ◦C; 1H NMR (300 MHz, CDCl3) ␦ 4.85-
4.70 (1H, m, H-3), 3.07 (1H, br s, H-6), 2.20-1.75 (9H,
m, including 1s (3H, CH3COO ) at 2.03 ppm), 1.75-0.95
(26H, m, including 1s (3H, H-19) at 0.99 ppm), 0.89 (3H, d,
J = 6.4 Hz, H-21), 0.84 (3H, t, J = 7.2 Hz, H-29), 0.83 (3H,
d, J = 6.7 Hz, H-26), 0.80 (3H, d, J = 6.5 Hz, H-27), 0.63
(3H, s, H-18). 13C NMR (75 MHz, CDCl3) ␦ 170.55, 71.34,
63.58, 62.51, 56.16, 56.06, 50.96, 45.80, 42.27, 39.76, 38.00,
36.66, 36.08, 35.01, 33.87, 32.46, 29.72, 29.12, 28.16, 27.20,
26.02, 24.18, 23.04, 21.91, 21.32, 19.80, 18.73, 17.03, 11.97,
11.75. IR (CCl4), 2959, 2872, 1737, 1467, 1435, 1418, 1386,
1377, 1363, 1243, 1125, 1037, 952, 935 cm−1. Anal. calcd
for C31H52O3: C 78.76, H 11.09. Found C 78.77, H 11.21.
2.6.7. Sitost-5-ene-3β,7β-diol (7β-hydroxysitosterol) (8)
The same procedure as for compound 4 was used: com-
pound 7 (560 mg, 1.18 mmol), MeOH/H2O (9:1, 50 mL),
Na2CO3 (741 mg, 6.99 mmol). After workup, the reaction
afforded compound 8 as a white solid (332 mg, 0.77 mmol,
76% yield): m.p. 156–158 ◦C. 1H NMR (300 MHz, CDCl3) ␦
5.28 (1H, br s, H-6), 3.83 (1H, dd, J = 7.5 Hz, H-7), 3.60-3.45
(1H, m, H-3), 2.40-2.15 (2H, m), 2.05-1.95 (1H, m), 1.90-
0.95 (29H, m, including 1s (3H, H-19) at 1.04 ppm), 0.92
(3H, d, J = 6.5 Hz, H-21), 0.84 (3H, t, J = 7.2 Hz, H-29), 0.83
(3H, d, J = 6.6 Hz, H-26), 0.81 (3H, d, J = 6.7 Hz, H-27), 0.69
(3H, s, H-18). 13C NMR (75 MHz, CDCl3) ␦ 143.46, 125.45,
73.34, 71.40, 55.96, 55.37, 48.26, 45.83, 42.92, 41.72, 40.89,
39.55, 36.94, 36.43, 36.09, 33.97, 31.55, 29.13, 28.54, 26.38,
26.09, 23.05, 21.07, 19.81, 19.15, 19.02, 18.83, 11.97, 11.82.
IR (CCl4), 3604, 3449, 2957, 2878, 1464, 1384, 1217, 1209,
1044, 1007, 947 cm−1. [␣]D20 +6◦ (c 1, CHCl3). Anal. calcd
for C29H50O2: C 80.87, H 11.70. Found C 80.38, H 11.58.
GC-MS-EI (as di-TMS ether), m/z (%): 575 (1), 485 (100),
470 (3), 396 (1), 253 (1), 129 (5), 105 (4), 73 (22), 43 (8).
2.6.9. 5,6α-Epoxy-5α-sitostan-3β-ol
(5,6α-epoxysitosterol) (11)
The same procedure as for compound 4 was used: com-
pound 9 (75 mg, 0.16 mmol), MeOH/H2O (9:1, 20 mL),
Na2CO3 (34 mg, 0.32 mmol). After workup, the reaction
afforded compound 11 as a white solid (60 mg, 0.14 mmol,
88% yield): m.p. 109–110 ◦C. 1H NMR (300 MHz, CDCl3)
␦ 4.00-3.80 (1H, m, H-3), 2.89 (1H, d, J = 4.4 Hz, H-6), 2.06
(1H, dd, J = 12.7 Hz), 2.00-1.75 (4H, m), 1.70-0.90 (28H, m,
including 1s (3H, H-19) at 1.05 ppm), 0.89 (3H, d, J = 6.6 Hz,
H-21), 0.84 (3H, t, J = 7.2 Hz, H-29), 0.82 (3H, d, J = 6.4 Hz,
H-26), 0.80 (3H, d, J = 6.6 Hz, H-27), 0.61 (3H, s, H-18).
13C NMR (75 MHz, CDCl3) ␦ 68.74, 65.67, 59.29, 56.85,
55.78, 45.81, 43.45, 42.55, 42.33, 39.87, 39.40, 36.13, 34.85,
33.89, 32.40, 31.10, 30.16, 29.89, 29.13, 28.82, 28.09, 26.89,
26.08, 24.05, 23.04, 20.64, 19.82, 19.02, 18.69, 15.92, 11.96,
11.85. IR (CCl4), 3620, 3438, 2940, 2870, 1466, 1377, 1089,
1037, 966 cm−1. [␣]D20 −40◦ (c 1, CHCl3). Anal. calcd for
C29H50O2: C 80.87, H 11.70. Found C 80.71, H 11.82. GC-
MS-EI (as TMS ether), m/z (%): 503 (15), 488 (7), 485 (6),
413 (46), 398 (20), 395 (60), 253 (25), 211 (18), 159 (27),
135 (35), 129 (12), 105 (70), 73 (100), 43 (25).
2.6.8. 5,6α-Epoxy-5α-sitostan-3β-ol acetate (9) and
5,6β-epoxy-5β-sitostan-3β-ol acetate (10)
m-CPBA (70% aqueous solution, 80 mg, 0.33 mmol) was
added to a solution of 2 (150 mg, 0.33 mmol) in CH2Cl2
(10 mL) containing NaHCO3 (50 mg, 0.59 mmol). The mix-
ture was stirred at room temperature for 24 h and then,
diluted with CH2Cl2 (20 mL). The organic layer was washed
successively with a saturated aqueous NaHCO3 solution
(5 × 10 mL), water (2 × 20 mL), and a saturated aqueous
NaCl solution (2 × 20 mL) and dried over MgSO4. The sol-
vents were evaporated under reduced pressure to give the
crude product (170 mg). NMR analysis indicated the sole
presence of the two epoxides 9 and 10 (9:10 = 3:1; 67% over-
all yield). In order to separate the two compounds, a fraction
(100 mg) of the crude product was purified on an alumina col-
umn treated with AgNO3 (75 × 1 cm i.d.) with hexane/ethyl
acetate (97:3) as an eluent to give 9 (fractions 55–78: 68 mg)
and 10 (fractions 118-148: 23 mg) as white solids.
2.6.10. 5,6β-Epoxy-5β-sitostan-3β-ol
(5,6β-epoxysitosterol) (12)
The same procedure as for compound 4 was used: com-
pound 10 (38 mg, 0.08 mmol), MeOH/H2O (9:1, 10 mL),
Na2CO3 (17 mg, 0.16 mmol). After workup, the reaction