262
KHRIPACH et al.
KOH (0.60 g, 10.7 mmol) was stirred for 24 h, silica gel
(2 ml) was then added, and the mixture was evaporated
in a vacuum. The residue was chromatographed on a
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column eluted with 9 : 1
3 : 1 petroleum ether–
ethyl acetate gradient to give 134 mg (89%) of (II);
mp 173–176°ë (methanol) (lit. [16] mp 181–182°ë);
1H NMR (δ, ppm, J, Hz): 5.34 (1 H, m, H6), 3.52 (1 H,
m, H3), 3.30 (1 H, m, H24), 1.00 (3 H, s, H19), 0.95–
0.88 (9 H, m, H21, H26 and H27), 0.68 (3 H, s, H18);
13C NMR (δ, ppm): 140.90, 121.78, 77.55, 71.88,
56.86, 56.07, 50.24, 42.45, 42.37, 39.89, 37.37, 36.62,
36.05, 33.23, 32.32, 32.03, 32.01, 31.72, 30.81, 28.31,
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(24R)-24-Acetoxy-5b-cholestan-3-one (XIV) was
obtained from alcohol (XIII) in 85% yield according to
1
6. Lutjohann, D. and von Bergmann, K., Pharmacopsychi-
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the procedure described above for (IV); H NMR (δ,
ppm, J, Hz): 4.69 (1 H, m, H24), 2.05 (3 H, s OAc),
1.01 (3 H, s, H19), 0.91–0.85 (9 H, m, H21, H26, and
H27), 0.67 (3 H, s, H18); 13C NMR (δ, ppm): 214.40,
170.98, 78.65, 56.41, 55.98, 44.30, 42.69, 42.33, 40.70,
40.03, 37.18, 36.98, 35.49, 35.33, 34.85, 31.41, 31.32,
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(24R)-24-Acetoxycholest-4-en-3-one (XV) was
obtained from ketone (XIV) in 43% yield as described
for the synthesis of (X) from (VIII); 1H NMR (δ, ppm,
J, Hz): 5.72 (1 H, s, H4), 4.69 (1 H, m, H24), 2.05 (3 H,
s, OAc), 1.18 (3 H, s, H19), 0.92–0.87 (9 H, m, H21,
H26, and H27), 0.70 (3 H, s, H18); 13C NMR (δ, ppm):
199.65, 171.66, 171.02, 123.75, 78.66, 55.85, 55.80,
53.78, 42.39, 39.61, 38.59, 35.69, 35.60, 35.32, 33.98,
32.93, 32.02, 31.47, 31.34, 28.02, 27.36, 24.14, 21.17,
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(24R)-24-Acetoxycholest-5-en-3b-ol (XVI) was
obtained from enone (XV) in 48% yield as described
for the synthesis of (XII) from (X); mp 94–96°ë (metha-
nol); 1H NMR (δ, ppm, J, Hz): 5.35 (1 H, m, H6), 4.69
(1 H, m, H24), 3.52 (1 H, m, H3), 2.05 (3 H, s, OAc),
1.00 (3 H, s, H19), 0.91 (3 H, d, J 6.6 Hz, H21), 0.89
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13
H27 or H26), 0.67 (3 H, s, H18); C NMR (δ, ppm):
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171.06, 140.77, 121.66, 78.75, 71.75, 56.74, 55.83,
50.10, 42.31, 42.29, 39.76, 37.25, 36.49, 35.38, 31.88,
31.63, 31.44, 31.41, 28.08, 27.38, 24.25, 21.17, 21.07,
19.39, 18.56, 17.73, 11.85.
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24R-Cholest-5-en-3b,24-diol (XVII) (24-epicere-
brosterol) was obtained from acetate (XVI) in 90%
yield according to the procedure of synthesis of (II)
described above: mp 177–180°ë (methanol); 1H NMR
(δ, ppm, J, Hz): 5.34 (1 H, m, H6), 3.52 (1 H, m, H3),
3.31 (1 H, m, H24), 1.00 (3 H, s, H19), 0.95–0.90 (9 H,
m, H21, H26, and H27), 0.68 (3 H, s, H18); 13C NMR
(δ, ppm): 140.77, 121.68, 77.08, 71.77, 56.75, 56.02,
50.11, 42.34, 42.29, 39.77, 37.26, 36.49, 35.70, 33.55,
32.06, 31.90, 31.89, 31.64, 30.57, 28.28, 24.28, 21.08,
19.40, 18.91, 18.66, 17.24, 11.88.
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