Povarov reaction of glyoxylate imines derived from 12-aminodehydroabietic acid

Article abstract of DOI:10.1134/S1070428010100076

Glyoxylate and arylglyoxal imines based on 12-aminodehydroabietic acid undergo hetero-Diels-Alder (Povarov) reaction with ethyl vinyl ether, cyclopentadiene, and indene to give, respectively, methyl (8aR,9R,12aS)-3-aroyl- 5-isopropyl-9,12a-dimethyl-7,8,8a

Full text of DOI:10.1134/S1070428010100076

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 10, pp. 1479–1489. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Tarantin, V.A. Glushkov, K.Yu. Suponitskii, A.A. Kudryashov, O.A. Maiorova, A.G. Tolstikov, 2010, published in Zhurnal
Organicheskoi Khimii, 2010, Vol. 46, No. 10, pp. 1474–1484.
Povarov Reaction of Glyoxylate Imines Derived
from 12-Aminodehydroabietic Acid
A. V. Tarantina, V. A. Glushkova, K. Yu. Suponitskiib, A. A. Kudryashovc,
O. A. Maiorovaa, and A. G. Tolstikova
a Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences,
ul. Akademika Koroleva 3, Perm, 614013 Russia
e-mail: glusha55@gmail.com
b Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
c Perm State University, ul. Bukireva 15, Perm, 614990 Russia
Received August 12, 2009
Abstract—Glyoxylate and arylglyoxal imines based on 12-aminodehydroabietic acid undergo hetero-Diels–
Alder (Povarov) reaction with ethyl vinyl ether, cyclopentadiene, and indene to give, respectively, methyl
(8aR,9R,12aS)-3-aroyl-5-isopropyl-9,12a-dimethyl-7,8,8a,9,10,11,12,12a-octahydronaphtho[1,2-f]quinoline-9-
carboxylates, methyl (7R,10aS,10dR,13aS)-1-aroyl-3-isopropyl-7,10a-dimethyl-2,5,6,6a,7,8,9,10,10a,10d,13,13a-
dodecahydro-1H-naphtho[1,2-f]cyclopenta[c]quinoline-7-carboxylates, and methyl (6aS,11bS,11eS,15R,15aR)-
6-aroyl-4-isopropyl-11e,15-dimethyl-2,5,6,6a,7,11b,11e,12,13,14,15,15a-1H-dodecahydroindeno[2,1-c]-
naphtho[1,2-f]quinoline-15-carboxylates.
DOI: 10.1134/S1070428010100076
Chemical modification of known natural matrices
may be regarded as an approach to design of novel
biologically active substances. We anticipated that
introduction of a heterocyclic fragment into a chiral
diterpene molecule could give rise to compounds pos-
sessing unusual physical and chemical properties (for
example, liquid crystals and reagents for asymmetric
synthesis), as well as to biologically active compounds
with new kinds of activity.
The reaction conditions were optimized using as
model process the reaction of cyclopentadiene with
Schiff base I (abietic acid numbering) which was re-
ported in preliminary communication [11] (Scheme 1).
The reaction smoothly occurred in 2,2,2-trifluoro-
ethanol at room temperature in the presence of boron
trifluoride–ether complex as Lewis acid catalyst.
We also tried to use other solvents, such as aceto-
nitrile, methylene chloride, and 1,1,1,3,3,3-hexafluoro-
propan-2-ol. In the first series of experiments we
examined solvent effect on the conversion of imine I
and yields of the adducts. The reaction was carried out
with 3 equiv of cyclopentadiene and 15 mol % of
BF3·Et2O as catalyst. The optimal reaction temperature
was 20°C. The reaction at –20°C was slow, whereas
elevated temperature (above 20°C) favored tarring due
to oligomerization of cyclopentadiene. After 1 h, the
reaction was terminated by adding a saturated aqueous
solution of sodium hydrogen carbonate. The conver-
sion of I and yields of adducts IIa–IIc were deter-
mined by gas chromatography–mass spectrometry, and
the structure of diastereoisomers IIa–IIc (purified by
In terms of the concept implying synthesis of new
useful organic compounds from renewable natural
resources [1, 2] we synthesized substituted naphtho-
[1,2-f]quinolines incorporating abietane fragments. For
this purpose we used the Povarov reaction [3–5].
Following this approach we previously synthesized
naphtho[1,2-f]quinolines having a diterpene fragment
and an aryl group on C2 in the quinoline ring [6]. In the
present work we selected as starting compounds more
reactive Schiff bases derived from ethyl glyoxylate and
arylglyoxals, taking into account that such imines are
known to readily react with dienophiles according to
Povarov [7–10]. As dienophiles we used ethyl vinyl
ether, cyclopentadiene, and indene.
1
column chromatography) was determined by H and
1479

TARANTIN et al.
1480
Scheme 1.
O
OEt
N
O
OEt
NH
16
Me
(R)
Me
12
15
17
Me
BF3 ·Et2O, CF3CH2OH
20°C, 1 h
13
11
Me
20
Me
Me
+
14
1
4
9
6
2
3
10
8
7
5
18
Me
19
Me
COOMe
COOMe
IIa
I
O
OEt
O
OEt
13
1
(S)
2
NH
13a
Me
NH
Me
12
2a
10c
3
Me
+
Me
11
10
Me
Me
+
4
10b
10a
9
8
4a
5
6a
7
6
Me
Me
COOMe
COOMe
IIb
IIc
13C NMR spectroscopy using double resonance tech-
niques; in addition, data of [6] for structurally related
compounds derived from aromatic aldehydes were
taken into account. The structure of (1R)-isomer IIa
(cis) was proved by X-ray diffraction data (Fig. 1).
Presumably, cis isomer IIa separated as single crystals
due to conglomeration.
isomer IIc (1–2%) with exo-fused cyclopentene ring
is formed together with enantiomers IIa/IIb. The best
results were obtained in fluorinated alcohols, in keep-
ing with the data of [12, 13]. Taking into account re-
latively high cost of 1,1,1,3,3,3-hexafluoropropan-2-ol,
2,2,2-trifluoroethanol was used as solvent in our sub-
sequent experiment.
The data in Table 1 show that the conversion
reaches 100% only in 1,1,1,3,3,3-hexafluoropropan-
2-ol. Thus the optimal solvents for the reaction under
study are 2,2,2-trifluoroethanol (yield of diastereoiso-
mers IIa/IIb 82%) and 1,1,1,3,3,3-hexafluoropropan-
2-ol (yield of diastereoisomers IIa–IIc 80%). Aceto-
nitrile is less appropriate: the overall yield of adducts
IIa–IIc is 78%. In acetonitrile, as well as in 1,1,1,3,3,3-
hexafluoropropan-2-ol, a small amount of diastereo-
It is known that, apart from boron trifluoride–ether
complex, indium(III) chloride [14] and dysprosium
and ytterbium trifluoromethanesulfonates [15, 16] are
highly effective catalysts in the Povarov reaction.
Therefore, we tested the above catalysts in the above
model reaction. Insofar as dysprosium(III) and ytter-
bium(III) trifluoromethanesulfonates are fairly poorly
soluble in 2,2,2-trifluoroethanol, we used acetonitrile
as solvent in this series of experiments. The procedure
was analogous to that described above. The amount of
the catalyst was 20 mol %, and the results are collected
in Table 2. It is seen that the best catalysts for the
Povarov reaction with substrate I are indium(III)
chloride (conversion 100%, yield of IIa/IIb 96%),
ytterbium(III) trifluoromethanesulfonate (conversion
99%, yield of IIa/IIb 94%), and boron trifluoride–
diethyl ether complex (conversion 90%, yield of
IIa/IIb 84%). The conversion of I in the presence of
dysprosium(III) trifluoromethanesulfonate was lower
(61%), while the use of trifluoromethanesulfonic acid
Table 1. Povarov reaction of Schiff base I with cyclopenta-
diene in different solvents
Yield, %
Conversion of
Schiff base I, %
Solvent
IIa IIb IIc
Acetonitrile
093
089
090
100
46
32
46
40
30
23
36
39
2
–
–
1
Methylene chloride
2,2,2-Trifluoroethanol
1,1,1,3,3,3-Hexa-
fluoropropan-2-ol
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

POVAROV REACTION OF GLYOXYLATE IMINES...
1481
Scheme 2.
O
OEt
O
OEt
3
2
NH
Me
N4
Me
BF3 ·Et2O (15 mol %)
CF3CH2OH, 20°C, 1–4 h
4a
1
12c
5
[O]
EtO
Me
Me
I
+
OEt
H2C
Me
Me
–EtOH
6
12b
12a
12
9
11
10
6a
8a
7
8
Me
Me
COOMe
COOMe
III
A
reduced the conversion to 9%. Thus indium(III)
chloride and ytterbium(III) trifluoromethanesulfonate
ensured the best results, but we also tried BF3·Et2O as
catalyst with a view to compare our new results with
the data obtained by us previously [6, 11].
Under the optimized conditions (2,2,2-trifluoro-
ethanol as solvent; BF3·Et2O, 15 mol %) we performed
the reaction of Schiff base I with ethyl vinyl ether.
During the isolation procedure, intermediate A loses
ethanol molecule, and subsequent oxidation with at-
C27
C23
C26
C22
O4
O3
O3
O4
C25
C21
C18
C19
C26
C17
N1
C17
C20
N1
C16
C24
C24
C25
C16
C22
C12
C12
C23
C13
C11
C13
C14
C13
C15
C15
C11
C14
C9
C1
C8
C9
C2
C10
C8
C7
C30
C1
C7
C6
C10
C5
O1
C2
C3
C21
C4
C6
C5
C3
C4
C28
O2
O1
C27
C19
C20
C18
C29
O2
Fig. 1. Structure of the molecule of compound IIa according
Fig. 2. Structure of the molecule of compound III according
to the X-ray diffraction data.
to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

TARANTIN et al.
1482
relative to the methyl substituent on C30 (for atom
numbering, see Figs. 1 and 2); cis orientation of the
cyclopentene fragment should give rise to strong steric
repulsion. The shortest distance between the 15a-H and
30-H atoms is 2.12 Å, i.e. it is slightly smaller than the
sum of the corresponding van der Waals radii (2.2 Å)
[17]. In addition, compound IIa displayed a very short
contact (1.85 Å) between 15a-H and 1-HB. These
H···H contacts are likely to affect conformation of
the D ring. The crystal packing of both compounds is
determined by common van der Waals interactions.
Table 2. Povarov reaction of Schiff base I with cyclopenta-
diene in the presence of different catalysts
Yield, %
Conversion of
Schiff base I, %
Catalyst
BF3·OEt2
IIa
IIb
090
100
099
061
009
54
53
50
26
09
30
43
44
21
00
InCl3
Yb(CF3SO3)3·H2O
Dy(CF3SO3)3
CF3SO3H
In order to extend the series of new compounds, by
reaction of 12-aminodehydroabietic acid methyl ester
with arylglyoxals we obtained Schiff bases IVa–IVd
and examined their cyclocondensation with ethyl vinyl
ether, cyclopentadiene, and indene according to Pova-
rov. Schiff bases IVa–IVd reacted with ethyl vinyl
ether as shown in Scheme 3. As in the reaction of
compound I with ethyl vinyl ether, elimination of
ethanol molecule from intermediate B and subsequent
oxidation yields methyl (9R,12aS)-3-aroyl-5-isopropyl-
9,12a-dimethyl-7,8,8a,9,10,11,12,12a-octahydro-
naphtho[1,2-f]quinoline-9-carboxylates Va–Vd (for
atom numbering, see structure III in Scheme 2). The
structure of compounds Va–Vd was confirmed by the
1H NMR and mass spectra.
mospheric oxygen yields adduct III, as was described
previously for analogous reactions [3] (Scheme 2). The
1H NMR spectrum of compound III contained signals
from protons on C1 and C2 as doublets at δ 8.66 and
3
7.94 ppm, respectively, with a coupling constant J of
9 Hz, which indicates aromatization of the heteroring.
The structure of III was confirmed by the X-ray dif-
fraction data (Fig. 2).
Unlike IIa, compound III in crystal is represented
by two molecules with similar conformations in the
symmetry-independent part of unit cell. Figure 2
shows the structure of one independent molecule. Both
compounds IIa and III are characterized by almost
similar structures of the A, B, and C rings: the cyclo-
hexane fragment A has a chair conformation, the
aromatic ring C is planar, and the cyclohexene ring B
adopts half-chair conformation (distorted in molecule
III). The structure of the rings A–C is analogous to the
structure of the corresponding fragments in structurally
related Schiff base which was studied previously [6].
The D ring in molecule III is obviously planar, where-
as the D ring in IIa has a conformation intermediate
between twist and boat. The cyclopentene fragment E
in compound IIa is almost planar and is oriented trans
Schiff bases IVa–IVd also showed high reactivity
in the reactions with cyclopentadiene and indene. In
the reaction with cyclopentadiene we isolated methyl
1-aroyl-3-isopropyl-7,10a-dimethyl-2,5,6,6a,7,8,9,10,-
10a,10d,13,13a-dodecahydro-1H-naphtho[1,2-f]cyclo-
penta[c]quinoline-7-carboxylates VIa–VId (for atom
numbering, see Scheme 1) as mixtures of two dia-
stereoisomers with respect to C1 (Scheme 4). The
(1R)-to-(1S) (or cis/trans) isomer ratio in different
Scheme 3.
R
R
R
O
O
O
N
Me
NH
Me
N
Me
6
[O]
5
Me
EtO
Me
Me
7
+
OEt
H2C
Me
Me
Me
–EtOH
4
1
3
2
Me
Me
Me
COOMe
IVa–IVd
COOMe
COOMe
B
Va–Vd
R = H (a), Me (b), MeO (c), Cl (d).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

POVAROV REACTION OF GLYOXYLATE IMINES...
1483
Scheme 4.
R
R
O
O
(R)
(S)
NH
Me
NH
Me
BF3 ·Et2O (15 mol %)
CF3CH2OH, 20°C, 1 h
Me
Me
IVa–IVd
+
+
Me
Me
Me
Me
COOMe
COOMe
(1R)-VIa–(1R)-VId
(1S)-VIa–(1S)-VId
Scheme 5.
R
O
6
7
5
NH
Me
8
11b
11c
Me
4
9
Me
IVa–IVd
+
11
12
3
10
11d
11e
13
14
2
15
1
15a
Me
COOMe
VIIa–VIId
experiments ranged from 1:1 to ~2:1 (5:6 for VIb).
The diastereoisomers were distinguished by the cou-
pling constant J1,13a for the 1-H proton which resonated
as a doublet. The J1,13a value was 4.5–4.8 Hz for the
(1R)-isomer and 5.1–5.4 Hz for the (1S)-isomer of VIb
and VIc (cf. [6]). Furthermore, the 11-H and 12-H
signals of the (1S)-isomers of VIa–VId appeared in
a weaker field. The 1-H protons in both diastereo-
isomers of VIa and VId had similar chemical shifts
(δ 4.22–4.27 ppm), and they resonated as broadened
doublets (J = 4.8–5.4 Hz); the stereoisomers were
distinguished by the 11-H and 12-H signals.
Likewise, the reaction of compounds IVa–IVd with
indene afforded in each case (according to the 1H NMR
data) a mixture of two diastereoisomeric (with respect
to C6) methyl (6aS,11bS,11eS,15R,15aR)-6-aroyl-4-iso-
propyl-11e,15-dimethyl-2,5,6,6a,7,11b,11e,12,13,14,-
15,15a-dodecahydro-1H-indeno[2,1-c]naphtho[1,2-f]-
quinoline-15-carboxylates VIIa–VIId, the (6R)/(6S)
ratio ranging from 1:1 to 3:2 (Scheme 5; steric config-
uration at C6 is not shown). Different stereoisomers
were distinguished by the J6,6a value for the doublet
signal of 6-H, which was larger for the (6S)-isomer; for
example, J6,6a = 6.6 and 7.5 Hz for the (1R)- and
(1S)-isomers of VIIa, respectively. The (6S)-isomers
of VIIa–VIId were also characterized by downfield
shift of the 11b-H signal in the H NMR spectrum:
1
δ 6.24 ppm (d, J = 6.9 Hz) for (6S)-VIIa and δ 5.19 ppm
(d, J = 8.1 Hz). This may be due to magnetic anisot-
ropy of the aroyl group. As a rule, signals from the NH
protons in compounds VI and VII are not observed in
their 1H NMR spectra recorded in CDCl3 as a result of
proton exchange, but their IR spectra contain broad-
ened absorption bands in the region 3390–3420 cm–1,
which belong to NH stretching vibrations.
Compounds VIIa–VIId may be regarded as partly
hydrogenated azanorhelicenes, and the described reac-
tion provides a convenient synthetic approach to these
unusual compounds. In the recent years, helicenes and
helicene-like structures have found increasing applica-
tions as photoactive materials and organic semicon-
ductors [18–20].
EXPERIMENTAL
The IR spectra were recorded on a Specord M-80
spectrometer from samples dispersed in mineral oil.
1
The H and 13C NMR spectra were measured from
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

TARANTIN et al.
1484
Table 3. Crystallographic data for compounds IIa and III and parameters of X-ray diffraction experiments
Parameter
IIa
III
Formula
C30H41NO4
479.64
C27H35NO4
437.56
Molecular weight
Color
Light yellow
Prisms
Light yellow
Plates
Shape of crystals
Crystal habit, mm
Crystal system
Space group
a, Å
0.25×0.15×0.15
Rhombic
P212121
09.3224(12)
11.1600(14)
24.833(3)00
2583.5(6)
4
0.25×0.25×0.05
Trigonal
P31
10.4074(3)
10.4074(3)
38.341(2)0
3596.5(2)
6
b, Å
c, Å
V, Å3
Z
d
calc, g/cm3
1.233
1.212
Absorption coefficient μ, mm–1
F(000)
0.081
0.080
1040
1416
Scan range θ, deg
1.64–30.06
29908
2.26–30.00
41759
Total number of reflections
Number of independent reflections
Rint
04204
06961
0.0796
0.0346
Number of refined parameters
Number of reflections with I > 2σ(I)
Completeness of reflection array, %
Goodness of fit
0322
0589
3183
6224
98.9
99.3
1.0180
1.0230
Divergence factor R1(F)a [reflections with I > 2σ(I)]
Divergence factor wR2(F2)b (all reflections)
Residual electronic density, min/max, e/Å3
0.0487
0.0522
0.1251
0.1220
0.312/–0.236
0.490/–0.323
a
R1 = Σ|Fo – |Fc||/Σ(Fo).
b
wR2 = (Σ[w(Fo2 – Fc2)2]/Σ[w(Fo2)2])1/2.
solutions in CDCl3 on a Varian Mercury Plus 300 in-
strument operating at 300 and 75 MHz, respectively.
The chemical shifts were determined relative to hexa-
methyldisiloxane as internal reference (1H) or deuterat-
ed solvent (13C). The progress of reactions and the
purity of products were monitored by thin-layer chro-
matography on Silufol plates using hexane–ethyl
acetate (9:1) as eluent; the chromatograms were devel-
oped by treatment with a solution of phosphomolybdic
acid in ethanol, followed by heating to 100–150°C.
The mass spectra (electron impact, 70 eV) were
obtained on an Agilent Technologies 5975B Network
mass spectrometer coupled with an Agilent Tech-
nologies 6890N gas chromatograph; HP-5MS capillary
column, 30000×0.25 mm; injector temperature 240°C;
oven temperature programming at a rate of 20–
40 deg/min; carrier gas helium. Column chromatog-
raphy was performed on Silicagel 60 (0.035–
0.070 mm, Merck) using hexane–ethyl acetate (19:1)
as eluent. Ethyl vinyl ether, indene, ethyl glyoxylate
(a 40% solution in toluene), 2,2,2-trifluoroethanol, and
1,1,1,3,3,3-hexafluoropropan-2-ol were commercial
products (Lancaster, Alfa Aesar).
Single crystals of compounds IIa and III, suitable
for X-ray analysis, were obtained by slow evaporation
of solutions of these compounds in hexane–ethyl ace-
tate (2:1, by volume). Experimental sets of reflection
intensities were acquired on a Smart 1000 CCD dif-
fractometer (λMoKα = 0.71073 Å, graphite mono-
chromator, ω-scanning) at 120 K. The initial intensity
arrays were processed using SAINT Plus [21] and
SADABS programs [22]. The structures were solved
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

POVAROV REACTION OF GLYOXYLATE IMINES...
1485
1
by the direct method and were refined by F2hkl by the
full-matrix least-squares procedure in anisotropic ap-
proximation for non-hydrogen atoms. Hydrogen atoms
were placed into positions calculated on the basis of
geometry considerations (except for the hydrogen atom
on the nitrogen in IIa, which was localized by differ-
ence synthesis of electron density and then normalized
by a distance of 0.90 Å). The positions of all hydrogen
atoms were refined in terms of the riding model
[Uiso(H) = nUeq(C,N), where n = 1.5 for methyl carbon
atoms and n = 1.2 for the other carbon and nitrogen
atoms]. The structures were solved and refined using
SHELXTL software package [23]. The principal crys-
tallographic data and parameters of X-ray diffraction
experiments are collected in Table 3.
(from hexane–ethyl acetate). H NMR spectrum, δ,
ppm: 1.19 d (3H, Me, J = 6.9 Hz), 1.22 s (3H, Me),
1.27 s (3H, Me, J = 6.9 Hz), 1.35 d (3H, Me, J =
6.9 Hz), 1.39–1.90 m (7H, 4-Hax, 2-H, 3-H), 2.23 m
(1H, 10a-H), 2.31 m (1H, 4-Heq), 2.92 m (2H, 9-H),
3.42 m (1H, 7-CH), 3.66 s (3H, OMe), 6.89 s (1H,
5-H), 6.98 s (1H, 8-H), 7.48 m (2H, m-H), 7.60 m (1H,
p-H), 8.21 s (1H, CH=N), 8.33 m (2H, o-H). 13C NMR
spectrum, δC, ppm: 16.51 (Me), 18.47 (C3), 21.59
(C10), 23.04 (Me), 23.39 (Me), 25.10 (Me), 27.96
(7-CH), 29.83 (C9), 36.61 (C2), 37.23 (C4a), 38.05 (C4),
44.74 (C1), 47.61 (C10a), 51.93 (OMe), 112.69 (C5),
126.48 (C8), 128.24 (Cm), 130.71 (Co), 133.31 (Cp),
135.44 (Ci), 136.05 (C8a), 141.15 (C7), 145.15 (C4b),
148.03 (C6), 155.55 (CH=N), 178.92 (OC=O), 190.97
(C=O). Found, %: C 78.04; H 7.88; N 3.07.
C29H35NO3. Calculated, %: C 78.17; H 7.92; N 3.14.
Optimization of the Povarov reaction conditions.
a. Solvent. Compound I, 25.0 mg (0.056 mmol), was
dissolved in 3 ml of a solvent, 1.1 μl (0.0084 mmol,
15 mol %) of BF3 ·Et2O was added using a micro-
syringe, the mixture was stirred for 10 min, and 14 μl
(3 equiv) of cyclopentadiene was added. The mixture
was stirred for 1 h at room temperature, the reaction
was terminated by adding a saturated aqueous solution
of NaHCO3 to pH 7, the mixture was extracted with
20 ml of ethyl acetate, the extract was dried over
MgSO4, the solvent was removed under reduced pres-
sure, and the residue was analyzed by gas chromatog-
raphy–mass spectrometry.
Methyl (1R,4aS,10aR)-7-isopropyl-1,4a-dimeth-
yl-6-[(E)-2-(4-methylphenyl)-2-oxoethylidene-
amino]-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-
1-carboxylate (IVb). Yield 77%, yellowish oily sub-
stance. 1H NMR spectrum, δ, ppm: 1.19 d (3H, Me, J =
6.6 Hz), 1.22 s (3H, Me), 1.23 s (3H, Me, J = 6.9 Hz),
1.27 d (3H, Me, J = 6.9 Hz), 1.46–1.87 m (7H, 4-Hax,
2-H, 3-H), 2.22 d.d (1H, 10a-H, J = 12.3, 2.1 Hz),
2.30 m (1H, 4-Heq), 2.43 s (3H, p-Me), 2.90 m (2H,
9-H), 3.42 m (1H, 7-CH), 3.66 s (3H, OMe), 6.88 s
(1H, 5-H), 6.98 s (1H, 8-H), 7.30 d (2H, m-H, J =
8.1 Hz), 8.19 s (1H, CH=N), 8.26 d (2H, o-H, J =
8.1 Hz). Found, %: C 78.28; H 8.15; N 3.12.
C30H37NO3. Calculated, %: C 78.40; H 8.11; N 3.05.
b. Catalyst. Compound I, 25.0 mg (0.056 mmol),
was dissolved in 3 ml of acetonitrile, 0.0084 mmol
(15 mol %) of catalyst was added, the mixture was
stirred for 10 min, and 14 μl (3 equiv) of cyclopenta-
diene was added. The mixture was stirred for 1 h at
room temperature, the reaction was terminated, and the
mixture was treated and analyzed, as described above.
Methyl (1R,4aS,10aR)-7-isopropyl-6-[(E)-2-(4-
methoxyphenyl)-2-oxoethylideneamino]-1,4a-di-
methyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-
1-carboxylate (IVc). Yield 69%, yellow crystals,
1
mp 53–57°C (from hexane–ethyl acetate). H NMR
Compounds I–III were reported previously [11].
spectrum, δ, ppm: 1.20 d (3H, Me, J = 6.9 Hz), 1.22 s
(3H, Me), 1.23 s (3H, Me, J = 6.9 Hz), 1.26 d (3H, Me,
J = 6.9 Hz), 1.41–1.87 m (7H, 4-Hax, 2-H, 3-H),
2.22 m (1H, 10a-H, J = 12.3, 2.1 Hz), 2.30 m (1H,
4-Heq), 2.90 m (2H, 9-H), 3.43 m (1H, 7-CH), 3.66 s
(3H, OMe), 3.88 s (1H, OMe), 6.87 s (1H, 5-H), 6.97 d
(2H, m-H, J = 8.7 Hz), 6.98 s (1H, 8-H), 8.18 s (1H,
Schiff bases IVa–IVd (general procedure). A solu-
tion of 1 mmol of arylglyoxal in 30 ml of toluene was
added to 0.328 g (1 mmol) of 12-aminodehydroabietic
acid methyl ester in the presence of 100 mg of 4-Å
molecular sieves or 2–3 g of anhydrous MgSO4. The
mixture was stirred for 6–12 h at room temperature.
When the reaction was complete (TLC), the mixture
was filtered, the filtrate was evaporated under reduced
pressure, and the residue was purified by column chro-
matography.
13
CH=N), 8.40 d (2H, o-H, J = 8.7 Hz). C NMR spec-
trum, δC, ppm: 16.48 (Me), 18.46 (C3), 21.59 (C10),
23.02 (Me), 23.36 (Me), 25.05 (Me), 27.97 (7-CH),
29.80 (C9), 36.61 (C2), 37.22 (C4a), 38,04 (C4), 44.76
(C1), 47.59 (C10a), 51.87 (OMe), 55.45 (C6H4OMe),
112.76 (C5), 113.61 (Cm), 126.38 (C8), 128.34 (Co),
133.12 (C8a), 135.66 (Ci), 140.84 (C7), 145.42 (C4b),
148.01 (C6), 156.26 (CH=N), 163.95 (Cp), 178.90
Methyl (1R,4aS,10aR)-7-isopropyl-1,4a-dimeth-
yl-6-[(E)-2-oxo-2-phenylethylideneamino]-1,2,3,4,-
4a,9,10,10a-octahydrophenanthrene-1-carboxylate
(IVa). Yield 76%, yellow crystals, mp 134–136°C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

TARANTIN et al.
1486
(OC=O), 189.08 (C=O). Found, %: C 75.97; H 7.79;
N 3.27. C30H37NO4. Calculated, %: C 75.79; H 7.79;
N 2.95.
hydronaphtho[1,2-f]quinoline-9-carboxylate (Vb).
Yield 25%, yellow oily substance. H NMR spectrum,
1
δ, ppm: 1.25 d (6H, Me, J = 6.6 Hz), 1.34 s (3H, Me),
1.50–1.92 m (7H, 8-H, 10-H, 11-H, 12-Hax), 1.67 s
(3H, Me), 2.23 m (1H, 12-Heq), 2.39 s (3H, p-CH3),
2.90 m (2H, 7-H), 3.11 m (1H, 8a-H), 3.68 s (3H,
OMe), 4.14 m (1H, 5-CH), 7.17 s (1H, 6-H), 7.25 d
(2H, m-H, J = 8.4 Hz), 7.82 d (2H, o-H, J = 8.4 Hz),
8.01 d (1H, 2-H, J = 9.0 Hz), 8.77 d (1H, 1-H, J =
9.0 Hz). Mass spectrum: m/z 483 [M]+. Found, %:
C 79.38; H 7.65; N 2.83. C32H37NO3. Calculated, %:
C 79.47; H 7.71; N 2.90,
Methyl (1R,4aS,10aR)-6-[(E)-2-(4-chlorophenyl)-
2-oxoethylideneamino]-7-isopropyl-1,4a-dimethyl-
1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-car-
boxylate (IVd). Yield 55%, yellowish oily substance.
1H NMR spectrum, δ, ppm: 1.19 d (3H, Me, J =
6.9 Hz), 1.22 s (3H, Me), 1.23 s (3H, Me, J = 6.9 Hz),
1.27 d (3H, Me, J = 6.9 Hz), 1.41–1.87 m (7H, 4-Hax,
2-H, 3-H), 2.22 d.d (1H, 10a-H, J = 12.3, 2.1 Hz),
2.30 m (1H, 4-Heq), 2.91 m (2H, 9-H), 3.40 m (1H,
7-CH), 3.66 s (3H, OMe), 6.90 s (1H, 5-H), 6.99 s
(1H, 8-H), 7.46 d (2H, m-H, J = 8.4 Hz), 8.19 s (1H,
CH=N), 8.32 d (2H, o-H, J = 8.4 Hz). Mass spectrum:
m/z 479 [M]+. Found, %: C 72.44; H 7.21; N 2.97.
C29H34ClNO4. Calculated, %: C 72.56; H 7.14; N 2.92.
Methyl (8aR,9R,12aS)-5-isopropyl-3-(4-methoxy-
benzoyl)-9,12a-dimethyl-7,8,8a,9,10,11,12,12a-octa-
hydronaphtho[1,2-f]quinoline-9-carboxylate (Vc).
1
Yield 26%, yellow oily substance. H NMR spectrum,
δ, ppm: 1.14 d (6H, Me, J = 6.9 Hz), 1.28 s (3H, Me),
1.40–1.95 m (7H, 8-H, 10-H, 11-H, 12-Hax), 1.60 s
(3H, Me), 2.20 m (1H, 12-Heq), 2.88 m (2H, 7-H),
3.10 m (1H, 8a-H), 3.68 s (3H, OMe), 3.89 s (3H,
OMe), 4.07 m (1H, 5-CH), 6.90 d (2H, m-H, J =
8.7 Hz), 7.09 s (1H, 6-H), 7.88 m (2H, o-H, J =
8.7 Hz), 8.04 d (1H, 2-H, J = 9.1 Hz), 8.78 d (1H, 1-H,
J = 8.7 Hz). Mass spectrum: m/z 499 [M]+. Found, %:
C 79.75; H 7.32; N 2.77. C32H37NO4. Calculated, %:
C 79.92; H 7.46; N 2.80.
Condensation of Schiff bases IVa–IVd with ac-
tivated olefins (general procedure). Schiff base IVa–
IVd, 0.27 mmol, was dissolved in 10 ml of 2,2,2-tri-
fluoroethanol, 0.005 ml (15 mol %) of BF3·Et2O was
added, the mixture was stirred for 10 min, and
0.81 mmol of activated olefin (ethyl vinyl ether,
freshly distilled cyclopentadiene, or indene) was ad-
ded. The mixture was stirred for ~1 h at room tem-
perature (TLC), the solvent was distilled off under
reduced pressure, the residue was treated with a solu-
tion of NaHCO3, 10 ml of ethyl acetate was added, and
the organic phase was separated and dried over
MgSO4. The solvent was distilled off, and the residue
was analyzed by GC–MS and subjected to column
chromatography. Solid products were additionally
purified by recrystallization from hexane–ethyl acetate.
Methyl (8aR,9R,12aS)-3-(4-chlorobenzoyl)-5-iso-
propyl-9,12a-dimethyl-7,8,8a,9,10,11,12,12a-octa-
hydronaphtho[1,2-f]quinoline-9-carboxylate (Vd).
1
Yield 37%, yellow crystals, mp 119–120°C. H NMR
spectrum, δ, ppm: 1.29 d (6H, Me, J = 6.9 Hz), 1.36 s
(3H, Me), 1.43–1.95 m (7H, 8-H, 10-H, 11-H, 12-Hax),
1.69 s (3H, Me), 2.23 m (1H, 12-Heq), 2.93 m (2H,
7-H), 3.15 m (1H, 8a-H), 3.70 s (3H, OMe), 4.10 m
(1H, 5-CH), 7.27 s (1H, 6-H), 7.46 m (2H, m-H, J =
9.0 Hz), 8.06 d (1H, 2-H, J = 9.3 Hz), 8.29 d (2H, o-H,
J = 9.0 Hz), 8.80 d (1H, 1-H, J = 9.3 Hz). Mass spec-
trum: m/z 503 [M]+. Found, %: C 73.85; H 6.77; N 2.74.
C31H34ClNO3. Calculated, %: C 73.87; H 6.80; N 2.78.
Methyl (8aR,9R,12aS)-3-benzoyl-5-isopropyl-
9,12a-dimethyl-7,8,8a,9,10,11,12,12a-octahydro-
naphtho[1,2-f]quinoline-9-carboxylate (Va). Yield
20%, mp 121–122°C. IR spectrum, ν, cm–1: 1720
(C=O, ester), 1660 (C=O), 1600 (C=C), 1318, 1310,
1
1280, 1250, 1170, 1145, 1002, 954, 884. H NMR
Methyl (7R,10aS,10dR,13aS)-1-benzoyl-3-isopro-
pyl-7,10a-dimethyl-2,5,6,6a,7,8,9,10,10a,10d,13,13a-
dodecahydro-1H-naphtho[1,2-f]cyclopenta[c]quino-
line-7-carboxylate (VIa). Yield 38%, yellow oily sub-
stance. 1H NMR spectrum, δ, ppm: (1R)-isomer: 1.17 d
(3H, Me, J = 6.6 Hz), 1.20 d (3H, Me, J = 6.6 Hz),
1.29 s (3H, Me), 1.53 s (3H, Me), 1.55–1.82 m (7H,
6-H, 8-H, 9-H, 10-Hax), 2.25 m (2H, 13-H), 2.32 m
(1H, 10-Heq), 2.68 m (2H, 5-H), 2.92 m (2H, 6a-H,
3-CH), 3.46 m (1H, 13a-H), 3.68 s (3H, OMe), 4.27 d
(1H, 1-H, J = 4.8 Hz), 4.40 br.s (1H, NH), 4.85 m (1H,
10d-H), 5.32 m (1H, 11-H), 5.74 m (1H, 12-H), 6.74 s
spectrum, δ, ppm: 1.28 d (6H, Me, J = 6.9 Hz), 1.36 s
(3H, Me), 1.40–1.94 m (7H, 8-H, 10-H, 11-H, 12-Hax),
1.70 s (3H, Me), 2.24 m (1H, 12-Heq), 2.93 m (2H,
7-H), 3.15 m (1H, 8a-H), 3.70 s (3H, OMe), 4.12 m
(1H, 5-CH), 7.26 s (1H, 6-H), 7.48 m (2H, m-H),
7.59 m (1H, p-H), 8.06 d (1H, 2-H, J = 9.0 Hz), 8.29 m
(2H, o-H), 8.80 d (1H, 1-H, J = 9.0 Hz). Found, %:
C 79.27; H 7.45; N 2.84. C31H35NO3. Calculated, %:
C 79.28; H 7.51; N 2.98.
Methyl (8aR,9R,12aS)-5-isopropyl-9,12a-dimeth-
yl-3-(4-methylbenzoyl)-7,8,8a,9,10,11,12,12a-octa-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

POVAROV REACTION OF GLYOXYLATE IMINES...
1487
(1H, 4-H), 7.46 m (2H, m-H), 7.56 m (1H, p-H),
7.87 m (2H, o-H); (1S)-isomer: 0.98 d (3H, Me, J =
6.9 Hz), 1.08 d (3H, Me, J = 6.9 Hz), 1.25 s (3H, Me),
1.44 s (3H, Me), 1.55–1.82 m (7H, 6-H, 8-H, 9-H,
10-Hax), 2.25 m (2H, 13-H), 2.32 m (1H, 10-Heq),
2.68 m (2H, 5-H), 2.92 m (2H, 6a-H, 3-CH), 3.46 m
(1H, 13a-H), 3.68 s (3H, OMe), 4.27 d (1H, 1-H, J =
4.8 Hz), 4.40 br.s (1H, NH), 4.85 m (1H, 10d-H),
5.60 m (1H, 11-H), 5.94 m (1H, 12-H), 6.90 s (1H,
4-H), 7.46 m (2H, m-H), 7.76 m (1H, p-H), 8.05 m
(2H, o-H). Mass spectrum: m/z 509 [M – 2]+. Found
(for isomer mixture), %: C 79.67; H 7.96; N 2.65.
C34H41NO3. Calculated, %: C 79.81; H 8.08; N 2.74.
4.5 Hz), 4.88 m (1H, 10d-H), 5.05 m (1H, 11-H),
5.62 m (1H, 12-H), 6.68 s (1H, 4-H), 6.93 d (2H, m-H,
J = 8.7 Hz), 7.88 m (2H, o-H, J = 8.7 Hz); (1S)-iso-
mer: 1.16 d (3H, Me, J = 6.9 Hz), 1.20 d (3H, Me, J =
6.9 Hz), 1.25 s (3H, Me), 1.47 s (3H, Me), 1.24–
1.82 m (7H, 6-H, 8-H, 9-H, 10-Hax), 2.16–2.35 m (3H,
13-H, 10-Heq), 2.73 m (2H, 5-H), 2.90 m (3H, 6a-H,
3-CH), 3.50 m (1H, 13a-H), 3.68 s (3H, OMe), 3.86 s
(3H, OMe), 4.22 d (1H, 1-H, J = 5.1 Hz), 4.88 m (1H,
10d-H), 5.33 m (1H, 11-H), 5.76 m (1H, 12-H), 6.74 s
(1H, 4-H), 6.96 d (2H, m-H, J = 8.7 Hz), 7.93 m (2H,
o-H, J = 8.7 Hz). Found, %: C 77.56; H 7.93; N 2.64.
C35H43NO4. Calculated, %: C 77.60; H 8.00; N 2.59.
Methyl (7R,10aS,10dR,13aS)-3-isopropyl-7,10a-
dimethyl-1-(4-methylbenzoyl)-2,5,6,6a,7,8,9,10,-
10a,10d,13,13a-dodecahydro-1H-naphtho[1,2-f]-
cyclopenta[c]quinoline-7-carboxylate (VIb). Yield
78% (mixture of diastereoisomers). IR spectrum, ν,
cm–1: 3400 (NH), 1730 (C=O, ester), 1686 (C=O),
1686 w, 1606 (C=C), 1584, 1520, 1212, 1160, 1080,
Methyl (7R,10aS,10dR,13aS)-1-(4-chloroben-
zoyl)-3-isopropyl-7,10a-dimethyl-2,5,6,6a,7,8,9,10,-
10a,10d,13,13a-dodecahydro-1H-naphtho[1,2-f]-
cyclopenta[c]quinoline-7-carboxylate (VId). Yield
76% (mixture of diastereoisomers). IR spectrum, ν,
cm–1: 3420 (NH), 1738 (C=O, ester), 1696 (C=O),
1678 w, 1608 (C=C), 1246, 1180, 1154. 1H NMR spec-
trum, δ, ppm: (1R)-isomer: 0.98 d (3H, Me, J =
7.2 Hz), 1.09 d (3H, Me, J = 7.2 Hz), 1.31 s (3H, Me),
1.44 s (3H, Me), 1.58–1.79 m (7H, 6-H, 8-H, 9-H,
10-Hax), 2.13 m (2H, 13-H), 2.29 m (1H, 10-Heq),
2.57 m (2H, 5-H), 2.82 m (1H, 6a-H), 2.98 m (1H,
13a-H), 3.49 m (1H, 3-CH), 3.69 s (3H, OMe), 4.22 d
(1H, 1-H, J = 5.4 Hz), 4.62 m (1H, 10d-H), 5.35 m
(1H, 11-H), 5.85 m (1H, 12-H), 6.89 s (1H, 4-H),
7.41 d (2H, m-H, J = 8.4 Hz), 8.01 d (2H, o-H, J =
8.4 Hz); (1S)-isomer: 0.98 d (3H, Me, J = 6.9 Hz),
1.13 d (3H, Me, J = 6.9 Hz), 1.28 s (3H, Me), 1.44 s
(3H, Me), 1.58–1.79 m (7H, 6-H, 8-H, 9-H, 10-Hax),
2.13 m (2H, 13-H), 2.29 m (1H, 10-Heq), 2.57 m (2H,
5-H), 2.82 m (1H, 6a-H), 2.98 m (1H, 13a-H), 3.49 m
(1H, 3-CH), 3.67 s (3H, OMe), 4.22 d (1H, 1-H, J =
5.4 Hz), 4.41 m (1H, 10d-H), 5.58 m (1H, 11-H), 5.93 m
(1H, 12-H), 6.91 s (1H, 4-H), 7.41 d (2H, m-H, J =
8.4 Hz), 8.01 d (2H, o-H, J = 8.4 Hz). Mass spectrum:
m/z 543 [M]+. Found, %: C 74.68; H 7.35; N 2.62.
C34H40ClNO3. Calculated, %: C 74.77; H 7.38; N 2.56.
1
1040, 936. H NMR spectrum, δ, ppm: (1R)-isomer:
1.15 d (3H, Me, J = 6.9 Hz), 1.21 d (3H, Me, J =
6.9 Hz), 1.31 s (3H, Me), 1.47 s (3H, Me), 1.55–
1.85 m (7H, 6-H, 8-H, 9-H, 10-Hax), 2.12–2.35 m (3H,
13-H, 10-Heq), 2.42 s (3H, C6H4Me), 2.67–2.99 m (4H,
5-H, 6a-H, 3-CH), 3.50 m (1H, 13a-H), 3.67 s (3H,
OMe), 4.33 d (1H, 1-H, J = 4.8 Hz), 4.86 m (1H,
10d-H), 5.05 m (1H, 11-H), 5.61 m (1H, 12-H), 6.69 s
(1H, 4-H), 7.28 d (2H, m-H, J = 8.1 Hz), 7.83 d (2H,
o-H, J = 8.1 Hz); (1S)-isomer: 1.16 d (3H, Me, J =
6.6 Hz), 1.20 d (3H, Me, J = 6.6 Hz), 1.29 s (3H, Me),
1.53 s (3H, Me), 1.55–1.85 m (7H, 6-H, 8-H, 9-H,
10-Hax), 2.12–2.35 m (3H, 13-H, 10-Heq), 2.40 s (3H,
C6H4Me), 2.67–2.99 m (4H, 5-H, 6a-H, 3-CH), 3.50 m
(1H, 13a-H), 3.68 s (3H, OMe), 4.24 d (1H, 1-H, J =
5.1 Hz), 4.86 m (1H, 10d-H), 5.34 m (1H, 11-H), 5.74 m
(1H, 12-H), 6.74 s (1H, 4-H), 7.26 d (2H, m-H, J =
8.4 Hz), 7.78 d (2H, o-H, J = 8.4 Hz). Mass spectrum:
m/z 523 [M]+. Found, %: C 79.69; H 8.05; N 2.70.
C35H43NO3. Calculated, %: C 79.96; H 8.24; N 2.66.
Methyl (7R,10aS,10dR,13aS)-3-isopropyl-1-(4-
methoxybenzoyl)-7,10a-dimethyl-2,5,6,6a,7,8,9,10,-
10a,10d,13,13a-dodecahydro-1H-naphtho[1,2-f]-
cyclopenta[c]quinoline-7-carboxylate (VIc). Yield
96% (mixture of diastereoisomers). 1H NMR spectrum,
δ, ppm: (1R)-isomer: 1.15 d (3H, Me, J = 6.9 Hz),
1.21 d (3H, Me, J = 6.9 Hz), 1.31 s (3H, Me), 1.53 s
(3H, Me), 1.24–1.82 m (7H, 6-H, 8-H, 9-H, 10-Hax),
2.16–2.35 m (3H, 13-H, 10-Heq), 2.73 m (2H, 5-H),
2.90 m (3H, 6a-H, 3-CH), 3.44 m (1H, 13a-H), 3.67 s
(3H, OMe), 3.87 s (3H, OMe), 4.30 d (1H, 1-H, J =
Methyl (6aS,11bS,11eS,15R,15aS)-6-benzoyl-4-
isopropyl-11e,15-dimethyl-2,5,6,6a,7,11b,11e,12,-
13,14,15,15a-dodecahydro-1H-indeno[2,1-c]naph-
tho[1,2-f]quinoline-15-carboxylate (VIIa). Yield
88% (mixture of diastereoisomers), mp 175–176°C. IR
spectrum, ν, cm–1: 3392 (NH), 1724 (C=O, ester), 1692
1
(C=O), 1600 (C=C). H NMR spectrum, δ, ppm:
(6R)-isomer: 0.99 d (3H, Me, J = 6.6 Hz), 1.10 d (3H,
Me, J = 6.6 Hz), 1.33 s (3H, Me), 1.55 s (3H, Me),
1.64–1.90 m (7H, 1-H, 13-H, 14-H, 12-Hax), 2.26 d
(1H, 15a-H, J = 11.1 Hz), 2.42 m (1H, 12-Heq), 2.60–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

TARANTIN et al.
1488
3.06 m (5H, 7-H, 6a-H, 2-H), 3.36 m (1H, 4-CH),
3.69 s (3H, OMe), 4.44 d (1H, 6-H, J = 6.6 Hz), 5.19 d
(1H, 11b-H, J = 8.1 Hz), 6.73 s (1H, 3-H), 6.88–
7.05 m (4H, Harom), 7.41–7.62 m (4H, Harom), 7.96 m
(1H, Harom); (6S)-isomer: 1.00 d (3H, Me, J = 7.2 Hz),
1.05 d (3H, Me, J = 7.2 Hz), 1.31 s (3H, Me), 1.58 s
(3H, Me), 1.64–1.90 m (7H, 1-H, 13-H, 14-H, 12-Hax),
2.26 d (1H, 15a-H, J = 11.1 Hz), 2.42 m (1H, 12-Heq),
2.60–3.06 m (5H, 7-H, 6a-H, 2-H), 3.36 m (1H, 4-CH),
3.71 s (3H, OMe), 4.32 d (1H, 6-H, J = 7.5 Hz), 6.24 d
(1H, 11b-H, J = 6.9 Hz), 6.82 s (1H, 3-H), 6.88–
7.05 m (4H, Harom), 7.41–7.62 m (4H, Harom), 7.96 m
(1H, Harom). Mass spectrum: m/z 559 [M – 2]+. Found,
%: C 81.04; H 7.61; N 2.35. C38H43NO3. Calculated,
%: C 81.25; H 7.72; N 2.49.
2.34 m (1H, 12-Heq), 2.62–3.02 m (5H, 7-H, 6a-H,
2-H), 3.35 m (1H, 4-CH), 3.68 s (3H, OMe), 3.87 s
(3H, OMe), 4.34 d (1H, 6-H, J = 6.0 Hz), 5.18 d (1H,
11b-H, J = 7.8 Hz), 6.78 s (1H, 3-H), 6.84–7.32 m
(5H, Harom), 7.84 m (3H, Harom). Found, %: C 78.98;
H 7.70; N 2.19. C39H45NO4. Calculated, %: C 79.15;
H 7.766; N 2.37.
Methyl (6aS,11bS,11eS,15R,15aR)-6-(4-chloro-
benzoyl)-4-isopropyl-11e,15-dimethyl-2,5,6,6a,7,-
11b,11e,12,13,14,15,15a-dodecahydro-1H-indeno-
[2,1-c]naphtho[1,2-f]quinoline-12-carboxylate
(VIId). Yield 86%, yellow oily substance. IR spec-
trum, ν, cm–1: 3430 (NH), 1730 (C=O, ester), 1690
(C=O), 1604 (C=C), 1258, 1180, 1142, 1100. 1H NMR
spectrum, δ, ppm: (6R)-isomer: 1.04 d (3H, Me, J =
6.9 Hz), 1.09 d (3H, Me, J = 6.9 Hz), 1.31 s (3H, Me),
1.58 s (3H, Me), 1.65–1.90 m (7H, 1-H, 13-H, 14-H,
12-Hax), 2.24 d (1H, 15a-H, J = 11.4 Hz), 2.44 m (1H,
12-Heq), 2.58–3.08 m (5H, 7-H, 6a-H, 2-H), 3.59 m
(1H, 4-CH), 3.71 s (3H, OMe), 4.39 d (1H, 6-H, J =
6.3 Hz), 5.19 d (1H, 11b-H, J = 7.2 Hz), 6.73 s (1H,
3-H), 6.86–7.09 m (4H, Harom), 7.46 d (2H, m-H, J =
9.0 Hz), 7.89 d (2H, o-H, J = 9.0 Hz); (6S)-isomer:
0.98 d (3H, Me, J = 6.6 Hz), 1.09 d (3H, Me, J =
6.6 Hz), 1.33 s (3H, Me), 1.55 s (3H, Me), 1.65–
1.90 m (7H, 1-H, 13-H, 14-H, 12-Hax), 2.24 d (1H,
15a-H, J = 11.4 Hz), 2.44 m (1H, 12-Heq), 2.58–3.08 m
(5H, 7-H, 6a-H, 2-H), 3.59 m (1H, 4-CH), 3.69 s (3H,
OMe), 4.27 d (1H, 6-H, J = 7.5 Hz), 6.23 d (1H,
11b-H, J = 7.5 Hz), 6.82 s (1H, 3-H), 6.86–7.09 m
(4H, Harom), 7.46 d (2H, m-H, J = 9.0 Hz), 7.89 d (2H,
o-H, J = 9.0 Hz). Mass spectrum: m/z 593 [M]+.
Found, %: C 76.77; H 6.77; N 2.24. C38H42ClNO3.
Calculated, %: C 76.55; H 7.10; N 2.35.
Methyl (6aS,11bS,11eS,15R,15aR)-4-isopropyl-
11e,15-dimethyl-6-(4-methylbenzoyl)-2,5,6,6a,7,-
11b,11e,12,13,14,15,15a-dodecahydro-1H-indeno-
[2,1-c]naphtho[1,2-f]quinoline-15-carboxylate
1
(VIIb). Yield 84%, mp 178–180°C. H NMR spec-
trum, δ, ppm: (6R)-isomer: 0.97 d (3H, Me, J =
6.6 Hz), 1.09 d (3H, Me, J = 6.6 Hz), 1.32 s (3H, Me),
1.49 s (3H, Me), 1.64–1.90 m (7H, 1-H, 13-H, 14-H,
12-Hax), 2.26 d (1H, 15a-H, J = 11.1 Hz), 2.44 m (4H,
p-Me, 12-Heq), 2.60–3.06 m (5H, 7-H, 6a-H, 2-H),
3.38 m (1H, 4-CH), 3.68 s (3H, OMe), 4.41 d (1H,
6-H, J = 6.0 Hz), 5.18 d (1H, 11b-H, J = 7.8 Hz),
6.72 s (1H, 3-H), 6.84–7.09 m (4H, Harom), 7.26–
7.34 m (3H, Harom), 7.86 m (1H, Harom); (6S)-isomer:
0.95 d (3H, Me, J = 6.9 Hz), 1.03 d (3H, Me, J =
6.9 Hz), 1.29 s (3H, Me), 1.55 s (3H, Me), 1.64–
1.90 m (7H, 1-H, 13-H, 14-H, 12-Hax), 2.26 d (1H,
15a-H, J = 11.1 Hz), 2.42 m (4H, 11b-H, p-Me), 2.60–
3.06 m (5H, 7-H, 6a-H, 2-H), 3.36 m (1H, 4-CH),
3.71 s (3H, OMe), 4.29 d (1H, 6-H, J = 7.2 Hz), 6.23 d
(1H, 11b-H, J = 7.2 Hz), 6.81 s (1H, 3-H), 6.84–
7.09 m (4H, Harom), 7.26–7.34 m (3H, Harom), 7.86 m
(1H, Harom). Mass spectrum: m/z 573 [M – 2]+. Found,
%: C 80.84; H 7.79; N 2.23. C39H45NO3. Calculated,
%: C 81.35; H 7.88; N 2.43.
The authors thank the staff of the Institute of Tech-
nical Chemistry, Ural Division, Russian Academy of
Sciences: V.I. Karmanov for recording the IR spectra,
E.V. Baigacheva for performing elemental analysis,
and A.A. Gorbunov for performing GC–MS analysis.
Methyl (6aS,11bS,11eS,15R,15aR)-4-isopropyl-6-
(4-methoxybenzoyl)-11e,15-dimethyl-2,5,6,6a,7,11b,-
11e,12,13,14,15,15a-dodecahydro-1H-indeno[2,1-c]-
naphtho[1,2-f]quinoline-15-carboxylate (VIIc).
Yield 86%, yellow crystals, mp 227–230°C. IR spec-
trum, ν, cm–1: 3420 (NH), 1736 (C=O, ester), 1686
(C=O), 1610 (C=C), 1590 w, 1520, 1260, 1178, 1142.
1H NMR spectrum, δ, ppm: (6R)-isomer: 1.01 d (3H,
Me, J = 6.6 Hz), 1.07 d (3H, Me, J = 6.6 Hz), 1.31 s
(3H, Me), 1.44 s (3H, Me), 1.58–1.90 m (7H, 1-H,
13-H, 14-H, 12-Hax), 2.22 d (1H, 15a-H, J = 11.1 Hz),
This study was performed under financial support
by the Presidium of the Russian Academy of Sciences,
program “Development of Methods for the Preparation
of Chemical Substances and Design of New Mate-
rials” (project coordinator Full Member of the Russian
Academy of Sciences V.A. Tartakovskii).
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