Ozonolysis of alkenes and study of reactions of polyfunctional compounds: LXVI. Ozonolysis and hydrogenation of diacetonides of 24,25- and 25,26-anhydro-20-hydroxyecdysones. Synthesis of ponasterone A

Article abstract of DOI:10.1023/A:1016547122573

Ozonolysis of 2,3:20,22-diacetonides of 24.25-and 25,26-anhydro-20-hydroxyecdysones afforded the corresponding ω-carbonyl derivatives. The hydrogenation of the mentioned dehydration products of 20-hydroxyecdysone acetonide yielded diacetonide of ponasterone A that provided ponasterone A and its 29,22-acetonide at hydrolysis.

Full text of DOI:10.1023/A:1016547122573

Russian Journal of Organic Chemistry, Vol. 38, No. 4, 2002, pp. 525 529. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 4, 2002,
pp. 550 554.
Original Russian Text Copyright
2002 by Odinokov, Savchenko, Nazmeeva, Galyautdinov, Khalilov.
Ozonolysis of Alkenes and Study of Reactions of Polyfunctional
Compounds: LXVI.* Ozonolysis and Hydrogenation
of Diacetonides of 24,25-
and 25,26-Anhydro-20-hydroxyecdysones.
Synthesis of Ponasterone A**
V. N. Odinokov, R. G. Savchenko, S. R. Nazmeeva,
I. V. Galyautdinov, and L. M. Khalilov
Institute of Petrochemistry and Catalysis of Bashkortostan Academy of Sciences and Ufa Scientific Center
of the Russian Academy of Sciences, Ufa, Bashkortostan, 450075 Russia
Received July 20, 2001
Abstract Ozonolysis of 2,3:20,22-diacetonides of 24.25-and 25,26-anhydro-20-hydroxyecdysones afforded
the corresponding -carbonyl derivatives. The hydrogenation of the mentioned dehydration products of
20-hydroxyecdysone acetonide yielded diacetonide of ponasterone A that provided ponasterone A and its
29,22-acetonide at hydrolysis.
Ecdysteroids function as hormones of shedding,
metamorphosis, and diapause in insects and crusta-
ceans. They are also found in considerable concentra-
tions in many kinds of plants. Therefore the sub-
stances are promising for practical application in
medicine and agriculture [2].
hydrogenation of the peroxy products on Lindlar
catalyst afforded aldehyde IV, its hemiacetal V, and
ketone VI. The column chromatography on SiO2
provided a mixture of aldehyde IV with its hemiacetal
V (in 1: 3 ratio as showed the intensity ratio of CHO
1
and OCH3 signals in the H NMR spectrum), and
ketone VI. The presence in the 13C NMR spectrum of
compounds IV VI a single resonance of quaternary
20-Hydroxyecdysone, the main component of the
ecdysteroid composition of a number of plant species,
is among the most accessible phitoecdysteroids [3].
Chemical transformations of this phitoecdysteroid
open up new vistas for synthesis of other less
accessible ecdysteroids, in particular, proceeding
from products of its dehydration at 25-hydroxy group
abutasterone, pterosterone and their 24-epimers were
prepared [4, 5].
carbon at
107 ppm corresponding to the group
C
20.22-Pr-i (see the table) evidences that the
2,3-acetonide protection was removed obviously by
hydrogenolysis during the reduction of peroxides.
Actually, the diacetonide was conserved when the
ozonation of the mixture of olefins II and III was
performed in acetone in the presence of Ba(OH)2
when the peroxides reduction was not required
because their decomposition during the ozonolysis
was effected by the base [7]. Under conditions of this
We carried out ozonolysis of a mixture that formed
at treating 2,3:20,22-diacetonide of 20-hydroxy-
ecdysone (I) with mesyl chloride in the presence of
pyridine and N,N-diaminopyridine. The mixture
nonperoxide
ozonolysis arose
a
mixture of
1
according to H NMR spectrum contained in 3: 1
aldehyde VII and ketone VIII that was separated by
column chromatography. Ketone VIII was identical
to the compound we prepared from monoacetonide VI
by treating it with acetone under standard conditions
[8]. In the 13C NMR spectra of compounds VII and
VIII characteristic signals are observed at 200.3
(CHO) and 208.5 (CO) respectively (see the Scheme).
ratio 24,25-(II) and 25,26-anhydro-20-hydroxyecdy-
sones III. The ozonolysis afforded the corresponding
-carbonyl-containing compounds that would be used
in the syntheses of some ecdysteroids and their
analogs. On the other hand, the hydrogenation of
olefins II and III opened a simple route to the syn-
thesis of ponasterone A that was a hormone of
crustaceans and was also detected in plants [2, 6].
Hydrogenation of the mixture of olefins II and III
on Raney nickel afforded diacetonide of ponasterone
IX that by hydrolysis with 70% AcOH was converted
It was established that ozonolysis of a mixture of
olefins II and III in dichloromethane followed by
1070-4280/01/3804-525$27.00 2002 MAIK Nauka/Interperiodica

526
ODINOKOV et al.
23.04.2002(a)
MsCl/Py/Me2NC5H4N;
(b)
O3/CH2Cl2 MeOH,
H2/Pd-CaCO3-PbO;
(c)
Me2CO/h+ ;
(d) O3/Ba(OH)2, Me2CO; (e) H2/Ni Ra; (f) AcOH, ZnCl2.
into monoacetonide X as evidenced the 13C NMR
spectrum of the latter compound containing a signal
at 106.7 ppm corresponding to the acetal atom of
the group 20,22-Pr-i. Both acetonide groups were
removed from compound IX by AcOH with ZnCl2
along procedure [9]. The treatment furnished a mix-
ture of monoacetonide X and ponasterone XI that was
upfield (
43 ppm) with respect to the signal of the
C25 atom of initial compound I.
EXPERIMENTAL
IR spectra were recorded on spectrophotometer
Specord 75IR from KBr pellets. H and 13C NMR
1
1
isolated by column chromatography. In the H NMR
of each compound are present two characteristic
spectra were registered on spectrometer Bruker
AM-300 at operating frequencies 300.13 and
doublets in the O.8 0.9 ppm region (J 6.5 Hz) belong- 75.25 MHz respectively, solvent CDCl3 or C5D5N,
ing to protons of geminal methyl groups attached to
the tertiary carbon C25. In the 13C NMR spectrum of
compounds IX XI the signals from C25 atom appear
internal reference TMS. Melting points were
determined on Boetius heating block. The optical
rotation was measured on polarimeter Perkin-Elmer-
141. TLC was performed on Silufol plates with SiO2,
at
28 29 ppm and thus are considerably shifted
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

OZONOLYSIS OF ALKENES...: LXVI.
13C NMR spectra ( , ppm) of compounds I XI
527
I
IIa
IIIa
IVa
Va
VI
VII
VIII
IX
X
XI
Atom
no.
CDCl3 CDCl3 CDCl3
C5D5N
C5D5N CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CD3OD
1
2
3
4
5
6
7
8
37.5
72.0
71.5
31.3
50.7
203.0
121.1
163.8
34.4
37.7
20.4
30.8
47.4
84.6
26.5
21.1
48.9
16.9
23.5
84.3
21.8
81.9
23.5
37.6
72.1
71.6
31.6
50.8
202.8
121.2
163.4
34.6
37.7
20.5
31.0
47.5
84.9
26.9
21.1
49.1c
17.0c
23.6
84.1
21.8
81.0c
26.7
37.6
72.1
71.6
31.6
50.8
202.8
121.2
163.4
34.6
37.7
20.5
31.0
47.5
84.9
29.6
21.1
49.2c
17.1c
23.6
84.1
21.8
80.7c
27.8
35.1
145.3
110.0
22.5
108.2
26.4
28.5
106.8
26.8
28.9
37.1
67.4
67.3
31.8
50.6
203.5
121.1
165.4
33.8
38.5
20.3
31.0
47.2
84.2
29.3
21.3
48.9
16.7c
23.7
83.6
21.9
75.5
42.3
200.4
37.1
67.4
67.3
31.8
50.6
203.5
121.1
165.4
33.8
38.5
20.3
31.0
47.2
84.2
29.3
21.3
48.9
16.6c
23.7
83.6
21.9
75.5
30.8
107.2
36.4
67.6
67.4
31.3
50.1
204.7
121.3
165.7
33.7
38.2
20.4
30.9
47.2
84.6
28.9
21.1
48.9
17.0
23.9
84.2
21.7
80.4
22.9
41.1
209.0
30.1
37.5
72.1
71.5
31.7
50.8
202.9
121.4
163.0
34.3
37.8
20.4
30.9
47.4
84.8
26.6
21.1
48.8
17.0
23.6
83.9
22.1
75.3
43.2
200.3
37.6
72.1
71.6
31.5
50.8
202.8
121.2
163.3
34.5
37.7
20.5
30.9
47.4
84.7
26.8
21.1
48.8
16.9
23.5
83.7
21.8
80.4
22.5
41.0
208.5
28.9
37.4
72.0
71.5
31.4
50.7
202.9
121.1
163.8
34.3
37.6
20.4
30.8
47.3
84.6
30.8
21.1
48.9
16.9
23.5
84.0
21.8
81.6
26.7
36.3
28.2
22.5
22.4
108.1
26.3
28.4
106.6
26.5
28.9
36.6
67.7
67.4
31.5
50.0
204.6
121.4
165.6
36.5
38.2
20.4
31.0
47.3
84.7
29.6
21.3
49.1
16.2
23.8
84.2
21.9
81.7
26.8
36.5
29.0
22.6
22.5
37.5
68.8
68.6
32.9
51.8
206.5
122.2
168.0
35.2
39.3
21.6
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
2,3-
32.6
b
85.3
31.8
21.6
50.5
18.1
24.4
77.9
21.0
78.0
30.5
37.7
29.3
23.4
22.8
41.3 120.3
70.3 133.5
28.9
28.4
25.6
18.0
108.2
26.4
28.5
106.8
26.8
108.2
108.3
26.4
28.5
108.0
26.9
31.0
108.3
27.0
28.5
106.9
26.6
29.0
i-PrO2 26.4
29.2
20,22- 106.9
i-PrO2 26.8
29.5
107.3
26.5
28.5
107.3
26.5
28.5
107.0
26.9
28.9
106.7
27.8
28.3
28.9
a
b
c
Assignment of signals was done for mixtures II and III, IV and V.
Superimposed on the multiplet of solvent ( 49 ppm).
The position of signals may be interchanged.
development with a solution of vanillin in ethanol
acidified with sulfuric acid. 13C NMR spectra of
compounds I XI are given in the table.
(III). To a solution of 1.55 g (2.78 mmol) of diaceto-
nide I (prepared by procedure [8] from 20-hydroxy-
ecdysone isolated from a plant Serratula coronata
[10]) in anhydrous pyridine (5 ml) was added while
stirring at 0 5 C 1 ml (12.78 mmol) of mesyl
chloride and then 0.05 g (15 mol%) of N,N-dimethyl-
aminopyridine. The reaction mixture was stirred for
20 min at 5 C and 4 h at room temperature. Then
5 ml of water was added, and the reaction products
were extracted into chloroform (3 35 ml). The extract
2,3:20,22-Diacetonide of stachysterone C, or
(20R,22R)-14 -hydroxy-2 ,3 :20,22-bis-O-iso-
propylidene-5 -cholesta-7,24-dien-6-one (II), and
2,3:20,22-diacetonide of 25,26-didehydroponaster-
one A, or (20R, 22R)-14 -hydroxy-2 ,3 :20,22-
bis-O-isopropylidene-5 -cholesta-7,25-dien-6-one
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

528
ODINOKOV et al.
was washed with water, dried with Na2SO4, and
evaporated in a vacuum. The residue was subjected
to column chromatography on silica gel (eluent
CHCl3 MeOH, 99: 1). We obtained 1.32 g (87%) of
a mixture of alkenes II and III (in the 3: 1 ratio
according to H NMR data). IR and NMR spectra
were consistent with previously published [4].
25.0 Hz), 5.82 d (1H, HC7, 4J 2.0). Found, %:
C 68.98; H 8.81. C29H44O7. Calculated, %: C 69.02;
H 8.79.
2,3:20,22-Diacetonide of 24-oxo-25,26,27-tris-
norponasterone A, or (20R,22R)-14 -hydroxy-
2 ,3 :20,22-bis-O-isopropylidene-24-oxo-25,26,27-
trisnor-5 -cholest-7-en-6-one (VII), and 2,3:20,22-
diacetonide of 25-oxo-27-norponasterone A, or
1
20,22-Acetonide of 24-oxo-25,26,27-trisnorpon-
asterone A, or (20R,22R)-2 ,3 ,14 -trihydroxy-
20,22-O-isopropylidene-24-oxo-25,26,27-trisnor-5 -
(20R,
22R)-14 -hydroxy-2 3, :20,22-bis-O-iso-
propylidene-25-oxo-27-nor-5 -cholest-7-en-6-one
(VIII). Through a mixture of 0.2 g (0.37 mmol) of
alkenes II and III, 0.13 g (0.41 mmol) of Ba(OH)2,
0.5 ml of H2O, and 3 ml of acetone at room tempera-
ture while vigorous stirring was passed a flow of
cholest-7-en-6-one
(IV),
20,22-acetonide
of
24-hydroxy-24-methoxy-25,26,27-trisnorponaster-
one A, or (20R,22R)-2 ,3 ,14 ,24-tetrahydroxy-
20, 22-O-isopropylidene-24-methoxy-25,26,27-
trisnor-5 -cholest-7-en-6-one (V), and 20,22-aceto-
nide of 25-oxo-27-norponasterone A, or (20R,22R)-
2 ,3 ,14 -trihydroxy-20,22-O-isopropylidene-25-
oxo-27-nor-5 -cholest-7-en-6-one (VI). Through a
solution of 0.15 g (0.28 mmol) of a mixture of
alkenes II and III in 12.9 ml of CH2Cl2 MeOH (2: 1)
at 70 C was bubbled an ozone-oxygen mixture at a
1
ozone-oxygen mixture at a rate of 70 ml min for
240 s (till 0.37 mmol of ozone was consumed). After
completion of the reaction the precipitate was filtered
off, the filtrate was evaporated in a vacuum, and the
residue was subjected to chromatography on a column
charged with 8 g of SiO2 (eluent CHCl3 MeOH,
19: 1). We isolated 0.03 g of aldehyde VII (Rf 0.13)
and 0.04 g of ketone VIII (Rf 0.37).
1
rate 70 ml min for 180 s (till 0.28 mmol of O3 was
consumed). The reaction mixture was flushed with
argon, 2 mg of Lindlar catalyst was added, and the
mixture was stirred under hydrogen atmosphere till
all the peroxides were reduced (test with iodo-starch
indicator). The catalyst was then filtered off, the
filtrate was evaporated, and the residue was subjected
to chromatography on a column charged with 5 g of
SiO2 (eluent CHCl3 MeOH, 20: 1). We isolated
0.04 g of a mixture of aldehyde IV (Rf 0.27) and
hemiacetal V (Rf 0.27), and 0.05 g of ketone VI (Rf
0.45).
Aldehyde (VII). mp 129 131 C, [ ]2D2 +56.9
(c 2.5, CHCl3). IR spectrum (KBr), , cm : 1650 s,
1
1720v.s, 2720w, 3450(wh/2 180). 1H NMR (CDCl3),
, ppm, J, Hz: 0.79s (3H, H3C18), 0.98 s (3H,
H3C19), 1.18 s (3H, H3C21), 1.23 s, 1.33 s, 1.37 s
and 1.43 s [12H, 4CH3 from 2(i-PrO2)], 1.15 2.73 m
(16H, CH, CH2), 2.82 m (1H, HC9, w1/2 24.0 Hz),
4.18 4.31 m (3H, HC2, HC3, HC22), 5.81 d (1H,
HC7, 4J 2.0), 9.83 br.s (1H, CHO, w1/2 6.0 Hz).
Found, %: C 69.62; H 8.73. C30H44O7. Calculated,
%: C 69.74; H 8.58.
Mixture of aldehyde IV and hemiacetal V. IR
Ketone (VIII). mp 113 115 C, [ ]2D21 +46.40
(c 1.7, CHCl3), IR spectrum (KBr), , cm : 1660 s,
1720 v.s., 3450 (wh/2 180). 1H NMR spectrum
(CDCl3), , ppm, J, Hz: 0.77 s (3H, H3C18), 0.96 s
(3H, H3C19), 1.13 s (3H, H3C21), 1.29 s, 1.31 s,
1.37 s and 1.39 s [12H, 4CH3 from 2(i-PrO2)],
1.12 2.76 m (18H, CH, CH2), 2.13 s (3H, H3C26),
2.81 m (1H, HC9, w1/2 25.0 Hz), 4.15 4.36 m (3H,
1
spectrum (KBr), , cm : 1680 s 1715 v.s, 3450,
1
(wh/2 180). H NMR spectrum (C5D5N), , ppm, J,
Hz: 1.01 s (3H, H3C18), 1.05 s (3H, H3C21), 1.32 s
(3H, H3C19), 1.15 2.85 m (15H, CH, CH2), 1.48 s
and 1.56 s (6H, 2CH3 from i-PrO2-20,22), 2.97 d.d
3
(1H, HC5, J 5.0 and 12.0), 3.61 m (1H, HC9, w1/2
26.0 Hz), 4.09 s (2.25 H, OCH3), 4.12 (1H, HC2,
w1/2 20.0 Hz), 4.31 m (1H, HC3, w1/2 18.0 Hz),
4.38 m (1H, HC22, w1/2 25.0 Hz), 4.56 m (0.75H,
4
HC2, HC3, HC22), 5.79 d (1H, HC7, J 2.0). Found,
%: C 70.28; H 8.95. C32H48O7. Calculated, %: C
70.56; H 8.88.
4
OCHO, w1/2 20.0 Hz), 6.27 d (1H, HC7, J 2.0),
9.98 t (0.25H, CHO, 3J 2.0).
Diacetonide of ketone VIII. To a solution of
0.05 g (0.1 mmol) of monoacetonide VI in 12 ml of
anhydrous acetone was added 1.4 mg of phosphomo-
lybdic acid. The mixture was stirred for 24 h at room
temperature, and then it was boiler till complete con-
version of the initial compoundVI (3h, TLC monitor-
ing). The reaction mixture was evaporated, diluted
with water, the reaction product was extracted into
1
Ketone VI. H NMR spectrum (CDCl3), , ppm,
J, Hz: 0.77 s (3H, H3C18), 0.95 s (3H, H3C19),
1.14 s (3H, H3C21), 1.39 s and 1.40 s (6H, 2 CH3
from i-PrO2-20,22), 1.21 2.81 m (16H, CH2), 2.16 s
(3H, H3C26), 2.50 m (3H, HC5, HC9, HC17), 3.58
3.86 m (2H, HC2, HC3), 4.56 m (1H, HC22, w1/2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

OZONOLYSIS OF ALKENES...: LXVI.
529
chloroform (3 20 ml), The combined organic solu-
tions were washed in succession with saturated solu-
tions of NaHCO3 and NaCl, dried with MgSO4, and
evaporated. The residue was subjected to chromato-
graphy on a column charged with 3 g of SiO2 (eluent
CHCl3 MeOH, 10: 1). We isolated 0.053 g (98%) of
diacetonide VIII identical to the above described.
Ponasterone A, or (20R,22R)-2 ,3 14 ,20,22-
pentahydroxy-5 -cholest-7-en-6-one(XI). A mixture
of 100 mg (0.18 mmol) of diacetonide IX and 1 ml of
70% acetic acid was stirred at room temperature for
1.5 h. Then 85 mg of zinc chloride was added, and
the stirring continued for 5 h. The reaction mixture
was diluted with 3 ml of water and extracted with
butanol (3 10 ml). The combined organic solutions
were washed with saturated solution of NaCl, dried
with MgSO4, evaporated in a vacuum, and the residue
was subjected to chromatography on a column
charged SiO2 (eluent CHCl3 MeOH, 30: 1). We
obtained 40 mg (43%) of compound X (Rf 0.32),
identical to that described above, and 20 mg (24%) of
compound XI (Rf 0.26), mp 255 258 C {259 260 C
(decomp.) [6]}, [ ]2D0 +59.2 (c 0.95, MeOH).
1H NMR spectrum (CD3OD), , ppm, J, Hz: 0.88 s
(3H, H3C18), 0.90 d and 0.91 d (6H, H3C26, H3C27,
3J 6.4), 0.96 s (3H, H3C19), 1.17 s (3H, H3C21),
1.10 2.42 m (19H, CH, CH2), 3.14 m (1H, HC9,
w1/2 27.0 Hz), 3.36 m (1H, HC22), 3.83 d.t (1H,
HC2, 3J 12.0 and 4.0), 3.93 m (1H, HC3, w1/2
14.0 Hz), 5.79 d (1H, HC7, 4J 2.0).
2,3:20,22-Diacetonide of ponasterone A, or
(20R,22R)-14 -hydroxy-2 ,3 :20,22-bis-O-iso-
propylidene-5 -cholest-7-en-6-one (IX). Through
a dispersion of 0.1 g of the mixture of alkenes II
and III, 0.05 g of Raney nickel, and 5 ml of ethanol
was passed hydrogen at room temperature for 16 h
(TLC monitoring). On completion of reaction the
catalyst was filtered off, the filtrate was evaporated,
and the residue was subjected to chromatography on a
column charged with 6 g of SiO2 (eluent CHCl3
MeOH, 20: 1). We isolated 0.01 g (98%) of com-
pound IX, Rf 0.51, mp 100 102 C, [ ]1D9 +31.8 (c
1
3.07, CHCl3). IR spectrum (KBr), , cm : 1660,
1
3500. H NMR spectrum (CDCl3), , ppm, J, Hz:
3
0.75 s (3H, H3C18), 0.86 d (6H, H3C26, H3C27, J
6.5), 0.94 s (3H, H3C19), 1.10 s (3H, H3C21), 1.29
s, 1.37 s and 1.45 s [2:1:1, 12H, 4CH3 from
2(i-PrO2)], 1.10 2.32 m (19H, CH, CH2), 2.79 m
(1H, HC9, w1/2 25.0 Hz), 3.58 m (1H, HC22, w1/2
13.0 Hz), 4.13 4.27 m (2H, HC2, HC3), 5.77 d (1H,
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1969, vol. 22, pp. 1045 1057.
9. Suksamrarn, A. and Pattanaprateep, P., Tetrahedron,
1995, vol. 51, pp. 10633 10650.
4
HC7, J 2.0). Found, %: C 72.79; H9.71. C33H52O6.
Calculated, %: C 72.75; H 9.62.
20,22-Acetonide of ponasterone A, or (20R,
22R)-2 ,3 14 -trihydroxy-20,22-O-isopropylidene-
5 -cholest-7-en-6-one (X). A mixture of 100 mg
(0.18 mmol) of diacetonide IX and 1 ml of 70%
acetic acid was stirred at room temperature till
complete conversion of the substrate (1.5 h, TLC
monitoring). The reaction mixture was diluted with
3 ml of water and extracted with butanol (3 10 ml).
The combined organic solutions were washed with
saturated solution of NaCl, evaporated in a vacuum,
and the residue was subjected to chromatography on
a column charged with 4 g of SiO2 (eluent CHCl3
MeOH, 10: 1). We isolated 0.091 g (98%) of com-
pound X, mp 142 145 C, [ ]2D2 +22.7 (c 2.48,
1
CHCl3). H NMR spectrum (CDCl3), , ppm, J, Hz:
3
0.78 s (3H, H3C18), 0.89 d (6H, H3C26, H3C27, J
6.4), 0.96 s (3H, H3C19), 1.14 s (3H, H3C21), 1.32 s
and 1.40 s (6H, 2CH3 from i-PrO2), 1.10 2.43 m
(19H, CH, CH2), 3.07 m (1H, HC9, w1/2 26.0 Hz),
3.62 m (1H, HC22, w1/2 16.0 Hz), 3.89 m (1H, HC2,
w1/2 25.0 Hz), 3.98m (1H, HC3, w1/2 17.0Hz), 5.82d
(1H, HC7, 4J 2.0). Found, %: C 71.37; H 9.62.
C30H48O6. Calculated, %: C 71.39; H 9.59.
10. Galyautdinov, I.V., Odinokov, V.N., Baltaev, U.A.,
Khalilova, A.Z., and Dzhemilev, U.M., RF Patent,
2151608, 2000; Byull. Izobr., 2000. no. 18.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002