First example of trifluoromethylation in the ecdysteroid series. Synthesis of (20RS)-20-O-hydro-20-trifluoromethylpoststerone

Article abstract of DOI:10.1023/B:RUJO.0000019736.80902.6e

The title compound was synthesized by trifluoromethylation of poststerone derivatives with trimethyl(trifluoromethyl)silane in the presence of tetrabutylammonium fluoride.

Full text of DOI:10.1023/B:RUJO.0000019736.80902.6e

Russian Journal of Organic Chemistry, Vol. 39, No. 12, 2003, pp. 1733 1737. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 12, 2003,
pp. 1806 1810.
Original Russian Text Copyright
2003 by Odinokov, Nazmeeva, Savchenko.
First Example of Trifluoromethylation
in the Ecdysteroid Series. Synthesis of (20RS)-20-O-Hydro-
20-trifluoromethylpoststerone
V. N. Odinokov, S. R. Nazmeeva, and R. G. Savchenko
Institute of Petroleum Chemistry and Catalysis, Academy of Sciences of Bashkortostan
and Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
fax: (3472)312750; e-mail: ink@anrb.ru
Received April 12, 2003
Abstract The title compound was synthesized by trifluoromethylation of poststerone derivatives with tri-
methyl(trifluoromethyl)silane in the presence of tetrabutylammonium fluoride.
Replacement of a methyl group by trifluoromethyl,
which has a comparable size but is strongly electron-
acceptor and lipophilic, endows an organic molecule
with new physical, chemical, and biological properties
[1, 2]. Many procedures for introduction of trifluoro-
methyl group into organic compounds are known [3],
but the most promising is the use of trimethyl(tri-
fluoromethyl)silane as nucleophilic trifluoromethylat-
ing agent [2, 4]. This reagent is applicable to various
organic compounds, including keto steroids [4];
however, no examples of trifluoromethylation in the
series of ecdysteroids have so far been reported.
spectra. The fact that the addition of Me3SiCF3
occurred just at the C20 O group in V and VI is con-
firmed by the following data. The 13C NMR spectra
of the products lack signal at about
209 ppm, but
C
two quartets appear at
78 ppm* (J = 26 Hz) and
C
126 ppm (J = 288 Hz), which belong to the CCF3
1
fragment. In the H NMR spectra of compounds VII
and VIII we observed two singlets (1:1) in the
range from 1.2 to 1.7 ppm with an overall intensity
corresponding to three protons (C21H3) [instead of
the singlet at 2.0 ppm from the acetyl group in the
spectra of initial ketones V and VI), indicating that
a new chiral (RS) center appeared at C20.
We previously found [5, 6] that polyhydroxysterols
do not undergo trifluoromethylation if at least one
hydroxy group is not protected [6]. In this case, tri-
fluoromethylation of the hydroxy rather than keto
group occurs [5, 6]. We have succeeded in effecting
trifluoromethylation of 14 -O-trimethylsilylpost-
sterone diacetate V and acetonide VI. Compounds V
and VI were synthesized by oxidative cleavage at the
C20 C22 bond [7] of 20-hydroxyecdysone (I) isolated
from Serratula coronata [8]. The resulting poststerone
II was converted into diacetate III and acetonide
IV which were treated with Me3SiCF3 [5] to obtain
ketones V and VI. Subsequent reactions of the latter
with Me3SiCF3 in the presence of tetrabutylammo-
nium fluoride gave the corresponding products of
Hydrolysis of diacetate VII with sodium hydroxide
in aqueous methanol and of acetonide VIII with
70% acetic acid afforded diol IX which was treated
with 5% hydrochloric acid in tetrahydrofuran in the
presence of tetrabutylammonium fluoride to obtain the
target trifluoromethyl-substituted poststerone analog,
compound X (Scheme 1).
EXPERIMENTAL
The IR spectra were recorded on a Specord 75IR
spectrometer in mineral oil. The UV spectra were
measured on a Specord M-40 spectrophotometer from
1
solutions in methanol and chloroform. The H and
nucleophilic addition of CF3 group at the C20
O
____________
*
Insofar as the quartet signal from C20 at about
78 ppm in
carbonyl group, (20RS)-14 ,20-di-O-trimethylsilyl-
20-(trifluoromethyl)poststerone diacetate VII and
acetonide VIII. Here, the C6 O group remains intact,
C
the 13C NMR spectrum is partially overlapped by the solvent
signal (CDCl3), the spectrum of VII was also measured in
benzene-d6.
1
as follows from the IR, UV, and H and 13C NMR
1070-4280/03/3912-1733$25.00 2003 MAIK Nauka/Interperiodica

1734
ODINOKOV et al.
Scheme 1.
III, V, VII, R = R = Ac; IV, VI, VIII, RR = Me2C; IX, R = SiMe3.
13C NMR spectra were obtained on a Bruker AM-300
instrument at 300.13 and 75 MHz, respectively, using
chloroform-d, methanol-d4, or benzene-d6 as solvent;
the chemical shifts were measured relative to tetra-
methylsilane as internal reference. The melting points
were determined on a Boetius microdevice. The
optical rotations were measured with the aid of
a Perkin Elmer 141 polarimeter. TLC analysis was
performed on Silufol plates; spots were visualized
by treatment with a solution of 4-hydroxy-3-methoxy-
benzaldehyde in ethanol, acidified with sulfuric acid.
2,3-Di-O-acetylpoststerone (or 2 ,3 -diacetoxy-
14 -hydroxy-5 -pregn-7-ene-6,20-dione) (III). Post-
sterone (II) was prepared according to the procedure
described in [7] from 20-hydroxyecdysone (I) isolated
from Serratula coronata [8]; mp 233 235 C (cf. [7]),
1
[ ]1D8 = +137.2 (c = 1.13, MeOH); the IR and H
and 13C NMR spectra of II were identical to those
reported in [9]. Compound II, 0.2 g (0.55 mmol),
was dissolved in 2 ml of pyridine, 0.34 g (3.31 mmol)
of acetic anhydride was added to the solution, and
0.1 mg of 4-dimethylaminopyridine was then added
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

FIRST EXAMPLE OF TRIFLUOROMETHYLATION IN THE ECDYSTEROID SERIES.
1735
under stirring. After 3 h (TLC, eluent CHCl3 MeOH,
5:1), the mixture was poured onto ice and extracted
with CHCl3 (3 10 ml), and the extract was washed
with a saturated solution of sodium chloride ( 5 ml),
dried over MgSO4, and evaporated under reduced
pressure. The residue was purified by column chroma-
tography on silica gel (5 g; eluent CHCl3). Yield of
III 0.23 g (94%), Rf 0.58 (CHCl3 MeOH, 5:1),
mp 111 114 C, [ ]2D4 = +106.1 (c = 1.48, CHCl3).
21.2 t (C16), 23.6 q (C19), 26.5 q (Me2CO2), 26.7 t
(C15), 28.6 q (Me2CO2), 30.0 t (C12), 31.5 q (C21),
32.0 t (C4), 34.6 d (C9), 37.6 t (C1), 37.9 s (C10),
47.9 s (C13), 50.8 d (C5), 58.8 d (C17), 71.6 d (C3),
72.1 d (C2), 84.7 s (C14), 108.4 s (Me2CO2), 121.8 d
(C7), 162.3 s (C8), 202.8 s (C6), 209.6 s (C20). Found,
%: C 71.84; H 8.42. C24H34O5. Calculated, %:
C 71.61; H 8.51.
1
IR spectrum, , cm : 1250 (OCOCH3); 1670, 1710
2,3-Di-O-acetyl-14-O-trimethylsilylpoststerone
(or 2 ,3 -acetoxy-14 -trimethylsiloxy-5 -pregn-7-
ene-6,20-dione) (V). Tetrabutylammonium fluoride,
0.9 mg, was added with stirring at 0 C to a mixture
of 0.2 g (0.45 mmol) of compound III and 0.19 g
(1.35 mmol) of Me3SiCF3 in 3 ml of anhydrous THF.
The reaction was complete in 3 min (TLC). The mix-
ture was evaporated under reduced pressure, and the
residue was subjected to column chromatography on
silica gel (3 g) using CHCl3 as eluent. Yield of V
0.22 g (95%), Rf 0.73 (CHCl3 MeOH, 10:1), mp 77
80 C, [ ]2D1 = +103 (c = 0.87, CHCl3) (cf. [6]). The
(C CC O); 1720 (C O); 1750 (COCH3). UV spec-
1
trum (CHCl3), max, nm ( ): 240 (12530). H NMR
spectrum (CDCl3), , ppm (J, Hz): 0.57 s (3H,
C18H3), 0.98 s (3H, C19H3), 1.50 2.40 m (12H, CH2),
1.97 s (3H, C21H3), 2.07 s and 2.11 s (6H, MeCO),
2.35 m (1H, 5-H), 3.12 m (1H, 9-H), 3.28 t (1H,
17-H, J = 8.0), 4.99 br.d (1H, 2-H, J = 12.1), 5.27 br.s
(1H, 3-H), 5.82 br.s (1H, 7-H). 13C NMR spectrum
(CDCl3), , ppm: 17.0 q (C18), 20.4 t (C11), 20.9 q
and 21.0 q (CH3CO), 21.1 t (C16), 23.7 q (C19), 28.9 t
(C15), 29.6 t (C12), 31.3 q (C21), 31.7 t (C4), 33.6 d
(C9), 33.8 t (C1), 38.2 s (C10), 47.5 s (C13), 50.8 d
(C5), 58.6 d (C17), 66.8 d (C3), 68.6 d (C2), 84.1 s
1
IR, UV, and H and 13C NMR spectra of the product
were identical to those reported in [6].
2,3-O-Isopropylidene-14-O-trimethylsilylpost-
sterone (or 2 ,3 -isopropylidenedioxy-14 -tri-
methylsiloxy-5 -pregn-7-ene-6,20-dione) (VI).
Tetrabutylammonium fluoride, 0.4 mg, was added
to a mixture of 0.074 g (0.18 mmol) of compound IV
and 0.078 g (0.55 mmol) of Me3SiCF3 in 3 ml of
anhydrous THF under stirring at 0 C. The reaction
was complete in 3 min (TLC). The mixture was
evaporated under reduced pressure, and the residue
was subjected to column chromatography on silica gel
(2 g) using CHCl3 as eluent. Yield of VI 0.085 g
(98%), Rf 0.79 (CHCl3 MeOH, 20:1), mp 70 72 C,
(C14), 121.7 d (C7), 163.8 s (C8), 170.2 s and 170.6 s
(CH3CO), 202.1 s (C6), 209.8 s (C20). Found, %:
C 67.32; H 7.62. C25H34O7. Calculated, %: C 67.25;
H 7.67.
2,3-O-Isopropylidenepoststerone (or 14 -hy-
droxy-2 ,3 -isopropylidenedioxy-5 -pregn-7-ene-
6,20-dione) (IV). Phosphomolybdic acid, 10.0 mg,
was added to a suspension of 0.25 g (0.7 mmol) of
poststerone (II) in 25 ml of anhydrous acetone. The
mixture was stirred for 20 min at room temperature
and evaporated under reduced pressure, 80 ml of
water was added to the residue, and the mixture was
neutralized with a saturated aqueous solution of
NaHCO3 and extracted with diethyl ether (3 10 ml).
The combined extracts were dried over MgSO4 and
evaporated under reduced pressure, and the residue
was purified by column chromatography on silica gel
(10 g; eluent CHCl3 MeOH, 20:1). Yield of IV 0.2 g
(73%), Rf 0.76 (CHCl3 MeOH, 5:1), mp 183 184 C,
[ ]2D31= +40 (c = 1.75, CHCl3) (cf. [6]). The IR, UV,
and H and 13C NMR spectra of the product were
identical to those reported in [6].
(20RS)-2,3-Di-O-acetyl-14 ,20-di-O-trimethyl-
silyl-20-trifluoromethylpoststerone [or (20RS)-
2 ,3 -diacetoxy-14 ,20-bis(trimethylsiloxy)-20-tri-
fluoromethyl-5 -pregn-7-en-6-one] (VII). Tetra-
butylammonium fluoride, 0.5 mg, was added to
a mixture of 0.134 g (0.23 mmol) of compound V
and 0.097 g (0.68 mmol) of Me3SiCF3 in 3 ml of
anhydrous THF under stirring at 0 C. The reaction
was complete in 3 min (TLC). The mixture was
evaporated under reduced pressure, and the residue
was subjected to column chromatography on silica gel
(2 g) using CHCl3 as eluent. Yield of VII 0.141 g
(94%), Rf 0.72 (CHCl3 MeOH, 20:1), mp 49 51 C,
1
[ ]2D3 = +58 (c = 2.09, CHCl3). IR spectrum, , cm :
1655 (C CC O), 1700 (C O). UV spectrum
1
(CHCl3), max, nm ( ): 240 (12390). H NMR spec-
trum (CDCl3), , ppm (J, Hz): 0.60 s (3H, C18H3),
0.96 s (3H, C19H3), 1.32 s and 1.48 s (6H, Me2C),
2.14 s (3H, C21H3), 1.20 2.40 m (13H, CH, CH2),
2.85 m (1H, 9-H), 3.29 t (1H, 17-H, J = 8.0), 4.20 m
(2H, 2-H, 3-H), 5.80 d (1H, 7-H, J = 2.5). 13C NMR
spectrum (CDCl3), C, ppm: 17.2 q (C18), 20.6 t (C11),
[ ]2D3 = +27.1 (c = 2.4, CHCl3). IR spectrum,
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

1736
ODINOKOV et al.
1
cm : 840 (SiCH3); 1250 (SiCH3, OCOCH3); 1160,
1350 (CF3); 1665 (C CC O). UV spectrum (CHCl3),
max, nm ( ): 242 (15 200). 1H NMR spectrum,
, ppm (J, Hz): in CDCl3: 0.07 s and 0.12 s (18H,
SiMe3), 0.71 s (3H, C18H3), 1.03 s (3H, C19H3),
1.34 s and 1.50 s (6H, Me2C), 1.46 s and 1.73 s (3H,
C21H3), 1.25 2.15 m (13H, CH, CH2), 2.35 d.d (1H,
17-H, J = 8.0, 8.0), 2.67 m (1H, 9-H), 4.18 m (1H,
2-H), 4.28 m (1H, 3-H), 5.81 br.s (1H, 7-H). 13C
NMR spectrum (CDCl3), C, ppm (J, Hz): 1.7 q and
SiMe3), 0.74 s (3H, C18H3), 1.23 s (3H, C19H3),
1.23 s and 1.41 s (3H, C21H3), 1.35 2.20 m (12H,
CH2), 1.99 s and 2.09 s (6H, MeCO), 2.35 m (2H,
5-H, 17-H), 2.98 m (1H, 9-H), 5.00 br.d (1H, 2-H,
J = 1.2), 5.36 br.s (1H, 3-H), 5.84 br.s (1H, 7-H);
in C6D6: 0.03 s and 0.60 s (18H, SiMe3), 0.54 s (3H,
2.9 q (SiMe3), 16.3 q (C18), 21.0 t (C11), 21.2 t
(C16), 23.3 q (C19), 26.2 t (C15), 26.3 q and 26.3 q
(Me2CO2), 28.5 q (C21), 29.7 t (C12), 31.5 t (C4),
35.9 d (C9), 37.1 t (C1), 37.4 s (C10), 48.9 d (C17),
49.9 s (C13), 50.2 d (C5), 71.5 d (C3), 72.4 d (C2),
C18H3), 0.87 s (3H, C19H3), 1.23 s (3H, C21H3),
1.72 s (6H, MeCO), 1.35 2.20 m (12H, CH2),
2.37 br.d (1H, 17-H, J = 8.0), 2.56 m (1H, 5-H),
3.00 m (1H, 9-H), 5.17 m (1H, 2-H), 5.56 br.s (1H,
2
78.1 q (C20, JCF = 26), 87.6 s (C14), 108.3 s
1
(Me2CO2), 122.1 d (C7), 126.2 q (CF3, JCF = 288),
162.6 s (C8), 202.1 s (C6). Found, %: C 60.41; H 8.28.
C31H51F3O5Si2. Calculated, %: C 60.36; H 8.33.
3-H), 5.86 br.s (1H, 7-H). 13C NMR spectrum,
,
C
ppm (J, Hz): in CDCl3: 1.8 q and 2.0 q (SiMe3),
16.3 q (C18), 20.4 t (C11), 21.1 q and 21.1 q (CH3CO),
21.2 t (C16), 22.4 q (C19), 24.1 q (C21), 29.2 t (C15),
29.7 t (C12), 31.3 t (C4), 33.8 d (C9), 33.9 t (C1),
38.3 s (C10), 48.9 d (C17), 49.1 s (C13), 50.9 d (C5),
(20RS)-14 ,20-Bis-O-(trimethylsilyl)-20-tri-
fluoromethylpoststerone [or (20RS)- ,3 -dihy-
droxy-14 ,20-bis(trimethylsiloxy)-20-trifluoro-
methyl-5 -pregn-7-en-6-one (IX). a. To a solution of
0.098 g (0.15 mmol) of compound VII in 3 ml of
methanol we added with stirring 0.1 ml of a 20% so-
lution of sodium hydroxide. When the reaction was
complete (TLC), the solvent (methanol) was distilled
off, and the residue was diluted with water (5 ml)
and extracted with ethyl acetate (3 10 ml). The com-
bined extracts were washed with water (3 ml), dried
over MgSO4, and evaporated under reduced pressure.
Yield of IX 0.74 g (87%), Rf 0.56 (CHCl3 MeOH,
66.9 d (C3), 68.6 d (C2), 78.0 q (C20, JCF = 26.0),
2
87.3 s (C14), 122.8 d (C7), 126.2 q (CF3, JCF = 288),
1
163.7 s (C8), 170.2 s and 170.3 s (CH3CO), 201.8 s
(C6); in C6D6: 1.7 q and 2.0 q (SiCH3), 16.3 q (C18),
20.6 q and 20.7 q (CH3CO), 21.6 t (C11), 22.4 q
(C19), 23.1 t (C16), 24.2 q (C21), 29.8 t (C15), 30.1 t
(C12), 31.5 t (C4), 34.0 d (C9), 34.5 t (C1), 38.4 s
(C10), 49.2 s (C13), 49.3 d (C17), 51.4 d (C5), 67.2 d
10:1), mp 108 110 C, [ ]2D1 = +18.1 (c = 2.59,
(C3), 69.0 d (C2), 78.5 q (C20, JCF = 26.0), 87.6 s
2
1
(C14), 123.0 d (C7), 126.9 q (CF3, 1JCF = 287), 161.8 s
(C8), 169.4 s and 169.7 s (CH3CO), 199.9 s (C6).
Found, %: C 58.28; H 7.69. C32H51F3O7Si2. Calcu-
lated, %: C 58.15; H 7.78.
CHCl3). IR spectrum, , cm : 850, 1245 (SiMe);
1145, 1350 (CF3); 1665 (C CC O). UV spectrum
1
(CHCl3), max, nm ( ): 241 (13450). H NMR spec-
trum (CDCl3), , ppm (J, Hz): 0.06 s and 0.13 s
(18H, SiMe3), 0.69 s (3H, C18H3), 0.94 s (3H, C19H3),
1.25 s and 1.46 s (3H, C21H3), 1.30 2.40 m (13H,
CH, CH2), 2.48 m (1H, 5-H), 2.88 m (1H, 9-H),
3.80 m (1H, 2-H), 4.08 m (1H, 3-H), 5.84 br.s (1H,
7-H). 13C NMR spectrum (CDCl3), C, ppm (J, Hz):
(20RS)-2,3-O-Isopropylidene-14 ,20-di-O-tri-
methylsilyl-20-trifluoromethylpoststerone [or
(20RS)-2 ,3 -isopropylidenedioxy-14 ,20-bis(tri-
methylsiloxy)-20-trifluoromethyl-5 -pregn-7-en-6-
one] (VIII). Tetrabutylammonium fluoride, 0.6 mg,
was added to a mixture of 0.128 g (0.27 mmol) of
compound VI and 0.115 g (0.81 mmol) of Me3SiCF3
in 3 ml of anhydrous THF under stirring at 0 C. The
reaction was complete in 3 min (TLC). The mixture
was evaporated under reduced pressure, and the
residue was subjected to column chromatography on
silica gel (3 g) using CHCl3 as eluent. Yield of VIII
0.051 g (31%), Rf 0.63 (CHCl3 MeOH, 40 : 1),
mp 40 42 C, [ ]2D1 = +31.4 (c = 2.54, CHCl3). IR
1.7 q and 1.9 q (SiMe3), 16.2 q (C18), 21.1 t (C11),
22.3 q (C19), 22.6 t (C16), 24.1 q (C21), 29.3 t (C15),
29.6 t (C12), 31.2 t (C4), 33.8 d (C9), 36.7 t (C1),
38.1 s (C10), 48.9 d (C17), 49.1 s (C13), 49.8 d (C5),
2
67.2 d (C3), 68.0 d (C2), 78.0 q (C20, JCF = 26),
1
87.3 s (C14), 122.4 d (C7), 126.2 q (CF3, JCF = 288),
164.0 s (C8), 203.8 s (C6). Found, %: C 58.53; H 8.16.
C28H47F3O5Si2. Calculated, %: C 58.30; H 8.21.
1
spectrum, , cm : 850, 1245 (SiMe); 1145, 1350
b. A mixture of 0.05 g (0.08 mmol) of compound
VIII and 1 ml of 70% acetic acid was stirred for
1.5 h. The mixture was then diluted with 10 ml of
water and extracted with 1-butanol (3 5 ml). The
(CF3); 1650 (C CC O). UV spectrum (CHCl3),
max, nm ( ): 244 (12 500). 1H NMR spectrum
(CDCl3), , ppm (J, Hz): 0.08 s and 0.13 s (18H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

FIRST EXAMPLE OF TRIFLUOROMETHYLATION IN THE ECDYSTEROID SERIES.
1737
combined extracts were washed with water (5 ml) and
evaporated under reduced pressure. The residue was
purified by column cromatography on silica gel (3 g)
using CHCl3 MeOH (20:1) as eluent. Yield 0.028 g
(60%). The product was identical to a sample obtained
as described above in a.
are overlapped by the solvent signal ( 49 ppm).
Found, %: C 61.25; H 7.14. C22H31F3O5.CCalculated,
%: C 61.10; H 7.22.
This study was financially supported by the Rus-
sian Foundation for Basic Research (project nos. 00-
03-32811 and 02-03-064473 MAS).
(20RS)-20-O-Hydro-20-trifluoromethylpost-
sterone [or (20RS)-2 ,3 ,14 ,20-tetrahydroxy-20-
trifluoromethyl-5 -pregn-7-en-6-one (X). A mixture
of 0.046 g (0.08 mmol) of compound IX, 0.17 g of
tetrabutylammonium fluoride, one drop of water, one
drop of 5% hydrochloric acid, and 1 ml of THF was
stirred for 4 h. Ethyl acetate, 5 ml, was added, and
the mixture was washed with 3 ml of water, dried
over MgSO4, and evaporated under reduced pressure.
The residue was subjected to column chromatography
on silica gel (5 g) using CHCl3 MeOH (10:1) as
eluent. Yield of X 0.024 g (70%), Rf 0.22 (CHCl3
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2002, vol. 32, p. 161.
2
(C3), 68.7 d (C2), 76.0 q (C20, JCF = 25), 84.9 s
9. Lafont, R.D. and Wilson, I.D., The Ecdysone Hand-
book, Nottingham: Chromatographic Society, 2000,
3rd ed.
1
(C14), 122.4 d (C7), 128.1 q (CF3, JCF = 288),
167.5 s (C8), 206.5 s (C6); signals from C13 and C17
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003