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BARANOVSKII et al.
dichloromethane was added 0.012 ml (0.12 mmol) of
acetic anhydride and 18 mg (0.15 mmol) of dimethyl-
aminopyridine. The solution was stirred for 12 h, then
diluted with dichloromethane, washed with water, with a
solution of NaHCO3, a saturated solution of NaCl, and
dried on Na2SO4. On removal of the solvent the residue
was separated on a column packed with silica gel (eluent
toluenepetroleum ether, 1:1). We obtained 24 mg (79%)
filtered through a bed of Na2SO4. On removal of the
solvent the residue was separated on a column packed
with silica gel (eluent toluenepetroleum ether, 9:1). We
obtained 0.769 g (90%) of compound XIV, oily substance.
IR spectrum (film), cm : 2940, 2870, 1040. H NMR
spectrum, d, ppm: 0.05 s (6H, Me2Si), 0.88 s (9H, t-BuSi),
1.03 s (3H, 18-Me), 1.05 s (3H, 19-Me), 1.65 d (3H, 21-
Me, J 7.3 Hz), 3.36 m (1H, H4', Jw/2 23 Hz), 3.49 m (2H,
H3a and H6'', Jw/2 25 Hz), 3.72 m (1H, H4', Jw/2 25 Hz),
3.86 m (1H, H6'', Jw/2 24 Hz), 4.56 m (1H, H2'', Jw/2 8 Hz),
5.15 q.t (1H, H20, J1 7.3, J2 1.8 Hz), 5.33 br.d (1H, H6,
J 4.8 Hz).
1
1
1
of steroid XII, oily substance. IR spectrum (film), cm :
1
2940, 2870, 1750 (CO), 1740 (MeCO), 1260, 1095. H
NMR spectrum, d, ppm: 0.06 s (6H, Me2Si), 0.89 s (9H,
t-BuSi), 0.99 s (3H, 18-Me), 1.05 s (3H, 19-Me), 2.03 s
(3H, OAc), 3.49 m (1H, H3a, Jw/2 31 Hz), 4.06 t (2H, H4',
J 6.4 Hz), 5.35 br.d (1H, H6, J 4.9 Hz).
(17Z)-3b-(tert-Butyldimethylsilyloxy)-15b-(4-
pivaloyloxybutyl)pregna-5,17-diene (XV). Along the
procedure applied to the synthesis of compound XIII from
0.120 g (0.21 mmol) of ketone XI we obtained 0.080 g
(67%) of steroid XV, oily substance. IR spectrum (film),
(17Z)-3b-(tert-Butyldimethylsilyloxy)-15b-[(4-
tert-butylsilyldimethyloxy)butyl]-pregna-5,17-diene
(XIII). To a solution obtained by adding 1.36 ml (0.68
mmol) of 0.5 M solution of potassium bis(trimethylsilyl)-
amide in toluene to 0.303 g (0.81 mmol) of ethyltriphenyl-
phosphonium bromide in 1 ml of THF was added at
78°C 0.080 g (0.14 mmol) of steroid IX in 1 ml of THF.
The mixture was stirred for 30 min, the cooling was
removed, and the solution was heated at reflux for 6 h.
Then the solution was cooled and treated with a saturated
solution of NH4Cl. The organic substances were extracted
into EtOAc, the extract was washed with a saturated
solution of NaCl, and dried on Na2SO4. On removal of
the solvent the residue was dissolved in hexane, 0.5 ml
of methyl iodide was added, and the reaction mixture
was stirred for 24 h. The precipitate was filtered off, the
filtrate was evaporated, and the obtained oily substance
was separated on a column packed with silica gel (eluent
toluenepetroleum ether, 9:1). We obtained 0.063 g
(77%) of reaction product XIII, oily substance. IR
1
1
cm : 2940, 2870, 1745 (CO), 1040. H NMR spectrum,
d, ppm: 0.05 s (6H, Me2Si), 0.88 s (9H, t-BuSi), 1.03 s
(3H, 18-Me), 1.04 s (3H, 19-Me), 1.18 s (9H, Me3C),
1.66 d (3H, 21-Me, J 7 Hz), 3.48 m (1H, H3a, Jw/2 31 Hz),
4.03 t (2H, H4', J 6.4 Hz), 5.15 q.t (1H, H20, J1 7, J2
1.5 Hz), 5.32 m (1H, H6, Jw/2 9 Hz). 13C NMR spectrum,
d, ppm: 4.6 q, 13.4 q, 18.3 s, 19.3 q, 20.2 q, 21.1 t,
25.9 q, 26.1 t, 27.2 q, 28.8 t, 28.9 d, 30.9 t, 31.6 t, 32.1 t,
36.8 s, 37.0 d, 37.4 t, 38.7 s, 39.2 t, 39.2 t, 42.7 t, 43.5 s,
50.8 d, 59.3 d, 64.4 t, 72.6 d, 114.1 d, 120.9 d, 141.8 s,
150.7 s, 178.6 s. Further elution with the mixture toluene
petroleum ether, 9:1, furnished 0.004 g (4%) of (17Z)-
3b-(tert-butyldimethylsilyloxy)-15b-(4-hydroxy-
butyl)pregna-5,17-diene (XVI), oily substance. IR
1
1
spectrum (film), cm : 3500, 2940, 2870, 1040. H NMR
spectrum, d, ppm: 0.06 s (6H, Me2Si), 0.89 s (9H, t-BuSi),
1.04 s (3H, 18-Me), 1.06 s (3H, 19-Me), 1.66 d (3H, 21-
Me, J 7 Hz), 3.49 m (1H, H3a, Jw/2 31 Hz), 3.62 t (2H, H4',
J 6.4 Hz), 5.15 q.t (1H, H20, J1 7, J2 1.5 Hz), 5.34 m (1H,
H6, Jw/2 9 Hz).
1
spectrum (film), cm : 2940, 2870, 1095. 1H NMR
spectrum, d, ppm: 0.04 s (6H, Me2Si), 0.05 s (6H, Me2Si),
0.88 s (18H, t-BuSi), 1.02 s (3H, 18-Me), 1.05 s (3H, 19-
Me), 1.65 d (3H, 21-Me, J 7.3 Hz), 3.48 m (1H, H3a),
3.58 t (2H, H4', J 6.4 Hz), 5.15 q.t (1H, H20, J1 7.3, J2
1.5 Hz), 5.33 m (1H, H6, Jw/2 9 Hz).
(17Z)-3b-(tert-Butyldimethylsilyloxy)-15b-(4-
pentenyl)pregna-5,17-diene (XVII). To a solution
obtained from 0.324 g (0.87 mmol) of ethyltriphenyl-
phosphonium bromide and 0.137 g (0.75 mmol) of sodium
bis(trimethylsilyl)amide in 1 ml of THF was added at
78°C 0.115 g (0.24 mmol) of steroid IV in 1 ml of THF.
After stirring for 1 h the cooling was removed, the solution
was heated at reflux for 10 h, then the reaction mixture
was cooled, diluted with hexane, washed with a saturated
solution of NH4Cl, a saturated solution of NaCl, and dried
on Na2SO4. On removal of the solvent the residue was
separated on a column packed with silica gel (eluent
toluenepetroleum ether, 9:1). We obtained 0.052 g of
(17Z)-3b-(tert-Butyldimethylsilyloxy)-15b-[4-
(tetrahydropyran-2-yloxy)butyl]-pregna-5,17-diene
(XIV). To a solution of ylide prepared by stirring 0.560 g
(5 mmol) of potassium tert-butylate and 2.4 g (6.5 mmol)
of ethyltriphenylphosphonium bromide in 6 ml of benzene
at 40°C for 0.5 h was added 0.836 g (1.5 mmol) of steroid
X in 8 ml of benzene at 10°C. The solution obtained was
heated at reflux for 4 h, cooled, and excess acetone was
added. In 30 min the solution was treated with 3 ml of
saturated NH4Cl solution, diluted with hexane, and
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004