Synthetic transformations of methylenelactones of eudesmanic type. Behavior of isoalantolactone under the conitions of heck reaction

Article abstract of DOI:10.1134/S1070428010110199

By Heck reaction of isoalantolactone with aryl bromides or aryl iodides (3aR,4aS, 8aR,9aR,E)-3-arylmethylidene-8a-methyl-5- methylidenedecahydronaphtho[2,3-b]furan-2(3H)-ones and (4aS,8aR,9aS)-3- arylmethyl-8a-methyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b] furan-2(4H)-ones, products of the double bond shift, were synthesized. The yields of the arylation products depend on the nature of the catalytic system and on the structure of the aryl halide. The structures of (3aR,4aS,8aR,9aR,E)- 3-(3,4-dimethoxybenzylidene)-8amethyl-5-methylidenedecahydronaphtho[2,3-b] furan-2(3H)-one and (4aS,8aR,9aS)-3-(2-methylsulfanylbenzyl)-8amethyl-5- methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-2(4H)-one were proved by XRD analysis. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070428010110199

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 11, pp. 1719−1734. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Belovodskii, E.E. Shults, M. M. Shakirov, I.Yu. Bagryanskaya, Yu.V. Gatilov, G.A. Tolstikov, 2010, published in Zhurnal Organiches-
koi Khimii, 2010, Vol. 46, No. 11, pp. 1710−1724.
Synthetic Transformations of Methylenelactones
of Eudesmanic Type. Behavior of Isoalantolactone
under the Conitions of Heck Reaction
A. V. Belovodskii, E. E. Shults, M. M. Shakirov, I. Yu. Bagryanskaya,
Yu. V. Gatilov, and G. A. Tolstikov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
e-mail: schultz@nioch.nsc.ru
Received December 30, 2009
Abstract—By Heck reaction of isoalantolactone with aryl bromides or aryl iodides (3aR,4aS, 8aR,9aR,E)-3-
arylmethylidene-8a-methyl-5-methylidenedecahydronaphtho[2,3-b]furan-2(3H)-ones and (4aS,8aR,9aS)-3-
arylmethyl-8a-methyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-2(4H)-ones, products of the
double bond shift, were synthesized. The yields of the arylation products depend on the nature of the catalytic system
and on the structure of the aryl halide. The structures of (3aR,4aS,8aR,9aR,E)-3-(3,4-dimethoxybenzylidene)-8a-
methyl-5-methylidenedecahydronaphtho[2,3-b]furan-2(3H)-one and (4aS,8aR,9aS)-3-(2-methylsulfanylbenzyl)-8a-
methyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-2(4H)-one were proved by XRD analysis.
DOI: 10.1134/S1070428010110199
Compounds containing in their structure an
α-methylidene-γ-lactone moiety, in particular, sesqui-
terpene lactones, attract attention due to their versatile
physiological activity, including anticancer action [1]. It
was established in the course of the study of structure–ac-
tivity interrelation in the series of sesquiterpene lactones
that the high cytotoxicity correlated with the presence
of an exocyclic double bond in the lactone ring [2]. An
available lactone of eudesmanic type is isoalantolactone
(I), a characteristic metabolite of various species of
elecampane Inula sp. [3]; the protocols of its complete
synthesis are described both for the racemic [4] and the
optically active form [5].
5-methylidenedecahydronaphtho[2,3-b]furan-2(3H)-ones
IIIa–IIIn and (4aS,8aR,9aS)-3-arylmethyl-8a-methyl-5-
methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]
furan- 2(4H)-ones IVb, IVd, IVe–IVl (Scheme 1,
Table 1). Compounds IIIa–IIIn, IVe, IVf, IVh, IVj,
IVk, IVl were isolated in the individual state by column
chromatography on silica gel. The ratio of compounds
III and the products IV of the double bond shift will be
further shown to depend on such factors as the type and
the structure of the aryl halide, the structure of the phos-
phine ligand and the palladium component of the catalyst.
Table 1 compiled the results of experiments on the
reaction of isoalantolactone with the aryl halides under
the action of the system Pd(OAc)2–(o-Tol)3P. The first
pemittable conclusion consist in the statement of the
increase in the yield of isomeric lactones IV at the use
of aryl iodides IIe–IIl. The bringing into the reaction
of bromo(iodo)arenes IId, IIm, IIn made it possible to
obtain only the corresponding lactones IIId, IIIm, IIIn.
The minimum yield of isomeric lactones IVa–IVd was
obtained in the runs with aryl bromides IIa–IId.
In a recent publication [6] we described the first ap-
plication of Heck reaction to the structural modification
of sesquiterpene methylenelactones. Here we report on
the C13-arylation of isoalantolactone (I).
Reaction of compound I with aryl bromides IIa–IId
or aryl iodides IIe–IIn catalyzed by the system palla-
dium acetate–phosphine ligand proceeds in DMF in the
presesnce of triethylamine. The main reaction products
are (3aR,4aS, 8aR,9aR,E)-3-arylmethylidene-8a-methyl-
In Table 2 by an example of the reaction of isoalan-
tolactone (I) with 3,4-dimethoxyiodobenzene (IIf) the
1719

BELOVODSKII et al.
Table 1. Effect of halide structure on the ratio of reaction productsa
1720
Initial halide
Br
Reaction products (yield, %)
Initial halide
Reaction products (yield, %)
I
IIIa (52), IVa (0)
IIIh (50), IVh (18)
F
F
IIa
IIh
Br
I
IIIb (75), IVb (6)
IIIi (57), IVi (21)
CH3
IIb
Br
CH3
IIi
I
IIIc (75), IVc (3)
IIId (55), IVd (0)
IIIe (85), IVe (9)
IIIj (60), IVj (25)
IIIk (55), IVk (20)
IIIl (79), IVl (17)
H3C
Cl
Br
IIc
IIj
Br
I
OH
OH
IIk
IId
I
I
OCH3
OCH3
OCH3
H3CS
I
IIe
IIl
I
IIIf (81), IVf (13)
IIIg (80), IVg (10)
IIIm (62), IVm (0)
IIIn (54), IVn (0)
H2N
IIf
IIm
I
I
CO2CH3
NHAc
OCH3
H3CO
IIg
IIn
a
Reaction conditions: 4 mol% Pd(OAc)2, 16 mol% (O-Tol)3P, 1.4 equiv Et3N, 120°C, 8–10 h, DMF. Conversion in all runs 80–100%.
effect of the phosphine structure and the temperature is
shown on the substrate conversion and the relative yields
of lactones IIIf and IVf. As seen, the highest yield of
arylation product IIIf was obtained at the use of tris(o-
tolylphosphine) as the ligand. The going over to trialkyl-
phosphines and tri(2-furyl)phosphine favored the increase
in the yield of the isomeric lactone IVf. Besides it turned
out that the formation of the product of the double bond
shift is favored by a higher reaction temperature (Table
2, runs nos. 1, 6, 7).
catalytic system Pd(dba)2–Ph3P (120°C). At isoalanto-
lactone (I) conversion 80% the ratio if eudesmanolides
IIIf and IVf was 2 : 1.
The reaction of isoalantolactone (I) with aryl iodides
IIf, IIk proceeded also in the absence of a phosphine
ligand under the action of the system Pd(OAc)2–Et3N–
CH3CN resulting in an enhanced yield of compounds
IVf and IVk [40 (IIIf), 27 (IVf), 70 (IIIk), 20% (IVk)].
Noteworthy that aryl bromides IIa–IId did not react with
lactone I both in the absence of phosphine ligand and
at the replacement of (o-Tol)3P by Ph3P, (2-Fu)3P, or by
Interesting results were obtained are the use of the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SYNTHETIC TRANSFORMATIONS OF METHYLENELACTONES
1721
Table 2. Effect of the ligand nature and the reaction conditions on the yield and reaction products ratio in reaction of isoalan-
tolactone (I) with 3,4-dimethoxyiodobenzene (IIf) in DMF in the presence of 1.4 equiv of Et3N
Yield, %
Conversion, %
of lactone (I)
Run no.
Ligand (16 mol%)
T, °C
Time, h
IIIf
81
50
55
55
40
85
70
IVf
13
15
25
20
25
8
1
2
3
4
5
6
7
(o-Tol)3P
Ph3P
120
120
100
120
120
90
8
8
95
80
(t-Bu)3P
(p-Bu)3P
(2-Fu)3P
(o-Tol)3P
(o-Tol)3P
16
8
100
90
8
80
8
75
140
8
92
20
alkylphosphines.
halides (according to the data of GC-MS analysis of the
reaction mixtures).Arylidene-susbstituted derivatives of
isoalantolactone IIIa–IIIn possess the (E)-configuration
of the double bond. In the reaction of isoalantolactone
(I) with 4-iodo-1-fluorobenzene (IIh) alongside the main
reaction products IIIh, IVh (Z)-isomer 13-arylideneiso-
alantolactone VI was isolated (yield 2%).
Hence the optimum catalytic system for the arylation
of isoalantolactone (I) is Pd(OAc)2–(o-Tol)3P.
The formation of some minor components that we
have detected is worth mentioning. For instance, in
reactions of isoalantolactone (I) with aryl iodides IIf
and IIg the products were additionally isolated of the
lactone arylation at the C4–C15 bond, compounds Vf and
Vg (Scheme 2). Similar bisadducts were also detected jn
reactions of compound I with aryl bromides IIa–IId (ac-
cording to 1H NMR spectra of the reaction mixtures). The
increase in the excess of the aryl halide to 20% did not
result in the notable growth of the yields of the products
of lactone diarylation; in these conditions increased the
content of the dimerization products of the initial aryl
Proceeding to discuss the causes and the ways of the
formation of isomeric lactones III and IV we wish to
draw attention to the change in the configuration at the
atom C8 in compounds IV. Using the main principles of
the palladium catalysis [7] it is possible to assume the
scheme of C8-epimerization proceeding through the in-
termediate σ-π complexes A–C (Scheme 3). Apparently
the driving force of the epimerization is the energy gain
Scheme 2.
CH3
H
H
H
O
O
Pd(OAc)2, (o-Tol)3P
I
IIa, IIg
IIIa, IIIg
+
IVa,
VIg
+
+
C
R3
Et3N, DMF
CH
H
R2
R3
R1
R2
R1
Va, Vg
R1 = R2 = OCH3, R3 = H (f); R1 = R3 = OCH3, R2 = H (g).
CH3
H
O
O
Pd(OAc)2, (o-Tol)3P
+
+
IVh
+
IIIh
I
IIh
H
Et3N, DMF
C
CH2
H
F
VI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

BELOVODSKII et al.
1722
Scheme 3.
H
CH3
H
H
H
H
O
O
O
ArPdL2X
_L
O
O
O
H
H
H
H
H
H
C
C
LPdX C
CH2
ArPdX
I
H
H
Ar
L
H
O
O
O
O
O
O
H
C
H
C
H
X
HPd
H
HPdX
Ar
X
H
H
Ar
L
LPd
H
L
C
H
Ar
C
A
H
O
H
O
O
O
O
O
H
CH2
Ar
H
HPdX
C
HPdX
L
H
Ar
HPdX
L
Ar
L
B
_LPdHX
_LPdHX
CH3
H
H
O
CH3
H
O
O
O
H
H
CH2Ar
C
CH2
CH2
H
Ar
IV
III
in this process resulting from a relief of the steric strains.
It was shown using the molecular mechanics method
MM-2 that the C ring of the C8-epimer should be in the
boat conformation whereas in compounds IV this ring
existed in more energy feasible chair conformation (ΔE ≈
5 kcal mol–1).
lactone I with iodoarene IIi. The 1H NMR spectrum and
the sign of the angle of the optical rotation of lactone VII
coincide with the data for the metabolite of the plant Aster
umbellatus, asterolide [8].
The attention should be drawn to the formation in
small yields of abnormal products of lactone I reaction
with aryl halides IId, IIf, IIm.
The assumed scheme of lactones epimerization is con-
firmed by the isolation of (4aS,8aR,9aS)-3,8a-dimethyl-5-
methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]
furan-2(4H)-one (VII) (yield 4%) in the condensation of
We observed a rare instance of the transfer of an aryl
substituent of the phosphine ligand on palladium with
the subsequent involvement of this substituent in the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SYNTHETIC TRANSFORMATIONS OF METHYLENELACTONES
1723
Scheme 4.
CH3
H
O
Pd(OAc)2, (o-Tol)3P
IIi
I
+
IIIi
IVi
+
+
O
Et3N, DMF
H
CH3
CH2
VII
formation of the reaction product [9]. For example, in
the reaction of isoalantolactone (I) with 4-iodoveratrol
(IIf) [Pd(dba)2–Ph3P–Et3N–DMF] alongside the expected
products IIIf and IVf lactone IIIa was isolated in 5%
yield, completely identical to the compound, obtained
in the reaction of isoalantolactone with bromobenzene
(Scheme 5). Analogous situation was observed in the
reaction of isoalantolactone (I) with 3,4-dihydroxybro-
mobenzene (IId) [Pd(OAc)2–(o-Tol)3P–Et3N–DMF]
where as a side product compound IIIc was isolated (yield
2%). In Scheme 5 the possible isomeric transformations
of arylpalladium intermediate D involving the aryl-aryl
exchange between the Pd(II) center and the coordinated
phosphine ligand. The subsequent reaction of aryl-palladi-
um complexes E, F with the methylidene group of lactone
I results in the formation of side products. Thus the pos-
sibility of the existence of arylpalladium intermediates
E, F (which is determined by their stability) governs the
formation of side products IIIa, IIIc.
In the reaction of isoalantolactone (I) with 2-iodoani-
line (IIm) alongside reaction product IIIm we isolated
diastereomers 3-(S)- and 3-(R)-3-(3-oxodecahydronaph-
Scheme 5.
H
H
CH3
H
H
H
O
O
O
O
O
H
O
H
+
+
CH2
H
C
C
CH2
OCH3
OCH3
CH3
H3CO
H3CO
IIf
Pd(dba)2, Ph3P,
Et3N, DMF
IVf, 20%
IIIa, 5%
IIIf, 40%
H
H
I
O
O
O
IId
O
H
H
+
Pd(OAc)2, (o-Tol)3P,
H
C
CH3
C
H
Et3N, DMF
CH2
OH
OH
IIId, 55%
IIIc, 2%
Ph
Ph
P
PPh3
PPh3
OCH3
OCH3
IIe
_
Pd
H3CO
H3CO
I
Pd I
PPh3
Pd(dba)2 PPh3
Pd
I
Oxidative addition
PPh3
PPh3
E
F
D
Substitution
I,
Et3N
+
IIIe + IVe IIIa (side product)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

BELOVODSKII et al.
Scheme 6.
1724
CH3
CH3
H
O
4'
5'
8'
O
H
3'
2'
Pd(OAc)2, (o-Tol)3P
4
5
1'
6
7
3
2
I
IIm
+
IIIm
+
NH
8a
Et3N, DMF
+
H
H
1
8
H
H
CH2
N
CH2
O
O
H
VIIIa
VIIIb
H
O
H
OH
O
O
Pd(OAc)2, (o-Tol)3P
I + IIm
NH
Et3N, DMF
PdX
NH2
H
H
H
Pd
X
H
G
H
O
H
O
HPdX
O
NH
H
H
H
H
N
O
VIIIa, VIIIb
isomers IIIa–IIIn is located in the region 7.23–7.48 ppm;
for (Z)-isomer VI, at 6.82 ppm. Characteristic feature of
1H NMR spectra of compounds IIIa–IIIn is the down-
field shift of the signal of H7 proton (δ 3.31–3.48 ppm)
compared with the corresponding proton in the spectrum
of isoalantolactone (I) or of (Z)-isomer VI (δ 2.93 ppm).
thalen-2-yl)-substituted 3,4-dihydroquinolin- 2(1H)-ones
(VIIIa, VIIIb) (yield 2 and 4% respectively) (Scheme 6).
Diastereomers VIIIa, VIIIb were separated by chro-
matography on silica gel. The formation of compounds
VIII is apparently favored by the stabilization of the
transition complex G through the coordination of the
carbonyl group with the covalently bound palladium and
the spatially approached amino group. Further follow the
transformations of complex G including the formation
of quinolone ring H and subsequent reduction with the
participation of palladium compounds.
The formation of compounds IVb, IVcc, IVe–IVl
is confirmed by the presence in the 1H NMR spectra of
the proton signals of the methylidene group at the atom
C13 [e.g., for compound IVk δ 3.50 and 3.56 ppm (d,
J 15.0 Hz)] and by the significantly increased difference
between the chemical shifts of protons H9 (Δδ ~1.2 ppm).
The axial-axial coupling constant of the upfield H9 proton
[δ 1.12 ppm (IVk)] with proton H8 is J 11.8 Hz.
The distinguishing features of the 1H NMR spectra of
the diarylation products Vf, Vg are the proton signals of
the second aryl substituent, the one-proton signal of H15
in the region 5.90–5.93 ppm, and also the downfield shift
of the proton signals of the methyl group and the proton
H3. The configuration of the center C15 is confirmed by
the data of the 1H–1H NOESY experiment. The presence
The structure of lactones IIIa–IIIn, IVb, IVc,
IVe–IVl was established based on the spectral data and
elemental analysis. The (E)-configuration of the double
bond C11–C13 in arylidenelactones IIIa–IIIn follows
from the presence in the 13C NMR spectrum registered
in the monoresonance mode the coupling carbon-proton
cis-constant of an olefin proton and the carbonyl carbon
atom of the lactone (3J 6.9–7.5 Hz); the respective trans-
3
constant J in (Z)-isomer VI amounts to 13.2 Hz. The
1
signal of H13 proton in the H NMR spectrum of (E)-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SYNTHETIC TRANSFORMATIONS OF METHYLENELACTONES
1725
of NOE-effect between the protons H15 and H6 of com-
pound Vg confirms the (E)-configuration of the double
bond C4–C15 of arylidenelactones Vf, Vg.
Compounds III–V have characteristic UV spectra
permitting assignments of the structures. For instance, the
spectrum of compound IIIb contains absorption bands
with the maxima at 202, 224, 228 (sh), and 294 nm of
similar intensity (log ε 4.12, 4.08, 4.04, and 4.32 respec-
tively); in the spectra of the diarylation products V the
absorption maxima are shifted to the longwave region
[e.g., for compound Vg: λmax (log ε) 204 (4.45), 248
(4.20), 296 (4.04), 327 (4.09) nm]. In the UV spectra of
compounds IV the absorption considerably changes in
the region 250–300 nm; the absorption maxima of the
aromatic ring are shifted, and their intensity significantly
decreases [e.g., in the spectrum of lactone IVh absorption
maxima are observed at λ 266 and 273 nm (log ε 3.16
and 3.12 respectively)].
Fig. 1. Spatial arrangement of the molecule of compound IIIf
by XRD data.
the C ring atoms C6, C7, C9, C10 are in the same plane
(mean-square deviation 0.003 Å), atoms C5 and C8 de-
viate from this plane in different directions by 0.710(3)
and 0.452(3) Å respectively. The lactone ring is strongly
twisted along the C7–C8 bond, torsion angle O1C8C7C11
–32.9(2)°. The lactone fragment has the usual geometry:
bonds O1–C12 1.355(3), O2–C12 1.202(3) Å, torsion angle
C8O1C12O2 172.4(2)°. All nonhydrogen atoms of the
aromatic substituent are in the same plane [mean-square
deviation 0.028 Å, maximum deviation from the plane
0.044(2) Å of the atom C5']. In the Cambridge Structural
Database [12] among 15 structures of versatile linear
methylidenelactones of eudesmanic type we did not find
compounds containing an aromatic substituent in the
position C13 of the eudesmanic skeleton. The structure
of the molecule of lactone IVl is shown in Fig. 2. The
bond lengths in molecule IVl are common. Same as in
lactone IIIf the six-membered rings are in the chair con-
formation. However the lactone ring in molecule IVl is
flat with the mean-square deviation of atoms 0.008 Å.
The same conformation of the rings was found in an
analogous compound, (±)-3,8a-dimethyl-5-methylidene-
9a-hydroxy-4,4a,5,6,7,8,8a,9-octahydronaphtho[2,3-b]
furan-2-one [(±)-hydroxyatractilolide] [13]. 2-(Methyl-
sulfanyl)sulfanylbenzyl fragment of molecule IVl is
brought out of the lactone ring plane, the angle between
these planes is 81.2(1)°.
The structure of stereoisomers 3-(3-oxodecahy-
dronaphthalen-2-yl)-3,4-dihydroquinolin-2(1H)-ones
1
(VIIIa, VIIIb) follows from the data of H and 13C
NMR spectra. The downfield shift of the proton H3 in the
1H NMR spectrum of compound VIIIa and the value of
the coupling constant between the protons H3,2' confirms
the (3S,2'R)-configuration of substituents (J2',3 10.2 Hz).
The pseudoequatorial orientation of the proton H3 also fol-
lows from the downfield shift of this proton (δ 3.22 ppm)
and small values of the coupling constants with protons
H4α and H4β. The cisoid position of protons H8a',2' fol-
lows from the existence of a NOE-effect between them.
Small values of the coupling constants between protons
H2',3 and the upfield shift of the proton H3 in the 1H NMR
spectrum of compound VIIIb (δ 2.90 ppm compared to
3.22 ppm for VIIIa) indicates the (3R,2'R)-configuration
of the substituents.
The structure of isomeric lactones III and IV was
proved by the XRD analysis of compounds IIIf and IVl.
The spatial arrangement of the molecule of compound
IIIf according to XRD data is shown in Fig. 1. The
analysis of the geometry and the intermolecular interac-
tions was performed using PLATON program [10]. The
bond lengths and bond angles in the molecule IIIf are
close to the average values [11]. The trans-joined six-
membered rings of the decahydronaphthalene fragment
have a chair form. In the A ring the atoms C1, C2, C4, C5
are in the same plane (mean-square deviation 0.003 Å),
atoms C3 and C10 deviate from this plane in different
directions by 0.637(4) and 0.688(3) Å respectively. In
In the crystal molecules IIIf form a 3D-network by
weak hydrogen bonds C7H⋯O2, C17–H⋯O2 (parameters
are given in Table 3). The crystal structure of compound
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

BELOVODSKII et al.
1726
Fig. 2. Spatial arrangement of the molecule of compound IVl
by XRD data
Fig. 3. Fragment of packing of compound IIIf molecules in
the crystal.
IIIf is additionally stabilized by the intermolecular inter-
action C–H⋯π [14], the distance C17–H⋯the center of the
π-system of the benzene ring is 2.67 Å. The packing of
molecules of compound IIIf in the crystal is shown in Fig.
3. In the crystal of compound IVl the 3D-network also
formed by weak hydrogen bonds C–H⋯O (parameters
are given in Table 3) and by intermolecular interactions
C–H⋯π (the distance C1–H⋯the center of the benzene
ring 2.76, C7'–H⋯centroid 2.95 Å).
Hence a method is developed of the chemical modi-
fication of the structure of the available sesquiterpene
α-methylidene-γ-lactone isoalantolactone by means of
palladium-catalyzed reaction with versatile aryl halides.
For the first time the derivatives of α-methylidene-γ-
lactones containing aromatic substituents in the position
C13 were synthesized.
Bruker AV-300 [operating frequencies 300.13 (1H)
and 75.47 MHz (13C)], AV-400 [operating frequencies
400.13 (1H) and 100.78 MHz (13C)], DRX-500 [operating
frequencies 500.13 (1H) and 125.76 MHz (13C)], andAV-
600 [operating frequencies 600.30 (1H) and 150.96 MHz
(13C)].1 The assignment of signals in the NMR spectra
was performed with the use of various types of proton-
proton and carbon-proton correlation spectra (COSY,
COXH, COLOC, NOESY). The multiplicity of signals
in the 13C NMR spectra was established by recording the
spectra in the J-modulation mode.
For recording mass spectra, evaluation of molecular
mass and elemental composition mass spectrometer of
high resolution DFS Thermo Scientific was applied (en-
ergy of ionizing electrons 70 eV, vaporizer temperature
230–280°C). IR spectra were recorded on a spectropho-
tometer Vector-22 from pellets with KBr. UV absorption
spectra were taken on a spectrophotometer HP 8453 UV-
Vis in ethanol. The specific rotation [α]D20 was measured
with a polarimeter PolAAr3005. XRD experiment on
compounds IIIf and IVl was performed on a diffractom-
eter Bruker Kappa Apex II with two-coordinate CCD
detector using ω-φ scanning.
EXPERIMENTAL
NMR spectra were registered on spectrometers
Table 3. Parameters of hydrogen bonds in the crystals of
compounds IIIf and IVl
Angle
Compd. Bond
C–H, Å
CH⋯O,
H⋯O, Å C⋯O, Å
The reaction products were isolated by column chro-
matography on silica gel (Acros, 0.035–0.070 mm) and
when required, with the use of preparative TLC on an
non-fixed silica gel layer containing 1% of luminophor
Q-35, on plates of dimensions 20×20 cm with the sor-
bent layer 1 mm thick (eluents benzene–ethyl acetate,
chloroform–ethanol).
deg
C7–H⋯O2
C17–H⋯O2
C7'–H⋯O2
C15–H⋯O2
IIIf
0.98
0.98
0.98
0.95
2.53
2.55
2.53
2.55
3.287(2)
3.394(3)
3.361(6)
3.488(5)
132
144
143
171
IVl
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SYNTHETIC TRANSFORMATIONS OF METHYLENELACTONES
1727
In experiments freshly distilled solvents and reagents
of “pure” grade were used.
3.2 Hz), 4.76 br.s (1H, H15), 7.37–7.43 m (4H, H2',4',6',13),
7.51 d (2H, H3',5', J 8.1 Hz). 13C NMR spectrum, δ, ppm:
17.49 q (C14), 22.52 t (C2), 24.43 t (C6), 34.27 C (C10),
36.64 t (C3), 39.33 d (C7), 41.10 t (C9), 41.96 t (C1),
46.12 d (C5), 76.77 d (C8), 106.49 t (C15), 128.83 d (C3',5'),
129.43 d (C2',4',6'), 132.30 s (C11), 133.98 s (C1'), 134.75 d
(C13), 148.86 s (C4), 172.20 s (C12). Mass spectrum, m/z
(Irel, %): 310 (3), 309 (10), 308 (48), 172 (100), 129 (21),
128 (23), 115 (51), 91 (42), 79 (21), 41 (20). Found [M]+
308.1767. C21H24O2. Calculated M 308.1771.
Pd(OAc)2 was synthesized as described in [15],
Pd(dba)2, as described in [16], and they were used without
recrystallization. Lactone I was isolated by extraction
from vegetal matter with subsequent separation through
morpholine adducts by procedure [17]. 3,4-Dihydroxy-
bromobenzene (IId) was obtained by method [18],
2,4-dimethoxyiodobenzene (IIg), by method [19], 4-io-
dochlorobenzene (IIj) and 4-iodobromobenzene (IIk),
by method [20], methyl 2-(acetylamino)-5-iodobenzoate
(IIn), by procedure [21]. Spectral data of compounds IIIe,
IIIf, IIIl, IVe, IVf, IVl were published in [6].
(3aR,4aS,8aR,9aR,E)-3-(4-Methylbenzylidene)-
8a-methyl-5-methylidenedecahydronaphtho[2,3-b]-
furan-2(3H)-one (IIIb). Yield 75%, mp 220–222°C
(ethyl acetate), [α]D20 +516° (c 1.2, CHCl3). IR spectrum,
ν, cm–1: 3092, 1735, 1650, 1605, 1512, 1439, 1379, 1288,
1261, 1228, 1212, 1170, 1073, 1034, 1001, 945, 932, 889,
814, 532, 481. UV spectrum, λmax, nm (log ε): 202 (4.12),
Heck reaction. General procedure.Atwo-neck glass
ampule was filled with argon. In an argon flow the ampule
was charged in succession with 2.15 mmol (500 mg)
of isoalantolactone (I), 2.36 mmol of aromatic halide,
0.086 mmol (4 mol%) of palladium acetate, 0.34 mmol
(16 mol%) of tris(o-tolyl)-phosphine, 7 ml of DMF,
3.61 mmol of triethylamine, and molecular sieves (3 Å).
The ampule was sealed under a slight excessive pressure
of argon, the reaction mixture was heated for 8–10 h at
120°C. The condensation in the presence of the other
catalytic systems or without phosphine ligand was car-
ried out similarly (Table 2). On completion of the reac-
tion the ampule was cooled, opened, and its content was
poured into a Petri dish. The solid residue was dissolved
in a minimal amount of chloroform and was subjected to
chromatography on silica gel (eluent chloroform–ethanol,
100 : 0 → 10 : 1). In succession tris(o-tolyl)-phosphine,
initial lactone, a mixture of the lactone and the reaction
product, and a mixture of two reaction products were
eluted (eluent chloroform). Individual compounds III
and IV were obtained by repeated chromatography and
recrystallization from an appropriate solvent. In some
cases the purification of analytic samples was performed
by preparative TLC.
1
224 (4.08), 228 (4.04), 294 (4.32). H NMR spectrum
(CDCl3), δ, ppm: 0.86 s (3H, C14H3), 1.26 m (1H, H1),
1.39 d.d.d (1H, H6, J 13.7, 12.3, 12.3 Hz), 1.48–1.65 m
(4H, H1,2,2,9), 1.92 d (1H, H5, J 12.9 Hz), 1.95 m (2H,
H3,6), 2.25 d.d (1H, H9, J 15.5, 1.8 Hz), 2.33 m (1H, H3),
2.37 s (3H, C7'H3), 3.41 d.d.d (1H, H7, J 12.0, 6.0, 5.1 Hz),
4.41 d (1H, H15, J 1.5 Hz), 4.48 d.d.d (1H, H8, J 4.6, 4.5,
1.5 Hz), 4.76 d (1H, H15, J 1.5 Hz), 7.21 d (2H, H3',5'
,
J 8.2 Hz), 7.40 s (1H, H13), 7.42 d (2H, H2',6', J 8.2 Hz).
13C NMR spectrum, δ, ppm: 17.52 q (C14), 21.24 q
(C7'), 22.57 t (C2), 24.40 t (C6), 34.32 s (C10), 36.69 t
(C3), 39.37 d (C7), 41.20 t (C9), 42.03 t (C1), 46.18 d
(C5), 76.74 d (C8), 106.50 t (C15), 129.52 d (C2',3',5',6'),
131.18 s and 131.26 s (C1',11), 134.84 d (C13), 140.06 s
(C4'), 148.94 s (C4), 172.41 s (C12). Found, %: C 81.48;
H 7.95. C22H26O2. Calculated, %: C 81.95; H 8.13.
(3aR,4aS,8aR,9aR,E)-3-(2-Methylbenzylidene)-
8a-methyl-5-methylidenedecahydronaphtho[2,3-b]-
furan-2(3H)-one (IIIc). Yield 85%, mp 125–126°C
(ethyl acetate), [α]D20 +327° (c 2.1, CHCl3). IR spectrum,
ν, cm–1: 2927, 1743, 1645, 1440, 1224, 1211, 1173, 1033,
1001, 894, 762, 717. UV spectrum, λmax, nm (log ε):
(3aR,4aS,8aR,9aR,E)-3-Benzylidene-8a-methyl-5-
methylidenedecahydronaphtho[2,3-b]furan-2(3H)-
one (IIIa). Yield 52%, mp 202–204°C (ethyl acetate),
[α]589 +539° (c 1.2, CHCl3). IR spectrum, ν, cm–1: 3090,
1743, 1650, 1450, 1224, 1198, 1171, 1000, 936, 900,
891, 689. UV spectrum, λmax, nm (lgε): 201 (4.18), 220
(4.06), 228 (3.80), 285 (4.29). 1H NMR spectrum(CDCl3),
δ, ppm: 0.87 s (3H, C14H3), 1.27 m (1H, H1), 1.42 d.d.d
(1H, H6, J 13.5, 12.6, 12.3 Hz), 1.50–1.63 m (4H, H1,2,2,9),
1.96–2.07 m (3H, H3,5,6), 2.24 d (1H, H9, J 15.5 Hz),
2.34 d (1H, H3, J 14.0 Hz), 3.43 d.d.d (1H, H7, J 12.0,
6.0, 5.1 Hz), 4.42 br.s (1H, H15), 4.49 d.d (1H, H8, J 4.4,
1
202 (4.19), 223 (4.00), 284 (4.12). H NMR spectrum
(CDCl3), δ, ppm: 0.86 s (3H, C14H3), 1.26 d.d.d (1H,
H1, J 12.2, 11.2, 4.7 Hz), 1.38–1.48 m (2H, H1,6), 1.51–
1.61 m (3H, H2,2,9), 1.83–1.89 m (2H, H5,6), 1.99 d.d.d
(1H, H3, J 12.5, 11.9, 6.0 Hz), 2.22 d.d (1H, H9, J 15.6,
1.7 Hz), 2.33 d.m (1H, H3, J 12.6 Hz), 2.38 s (3H, CH3
at C2'), 3.27 d.d.d (1H, H7, J 11.8, 5.2, 4.9 Hz), 4.41 d.d
(1H, H15, J 3.0, 1.5 Hz), 4.48 d.d.d (1H, H8, J 6.5, 4.6,
1.8 Hz), 4.75 d.d (1H, H15, J 3.0, 1.5 Hz), 7.20–7.25 m
(3H, H3',4',5'), 7.43 d.d (1H, H6', J 7.6, 2.0 Hz), 7.64 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

BELOVODSKII et al.
1728
H13, J 1.1 Hz). 13C NMR spectrum, δ, ppm: 17.31 q (C14),
19.66 q (CH3 пpand C2'), 22.30 t (C2), 25.15 t (C6), 34.04 s
(C10), 36.42 t (C3), 38.82 d (C7), 40.98 t (C9), 41.77 t
(C1), 46.00 d (C5), 76.76 d (C8), 106.23 t (C15), 125.80
d (C5'), 127.05 d (C4'), 129.03 d (C3'), 130.35 d (C6'),
132.70 d (C13), 132.98 s (C1'), 133.20 s (C11), 137.71 s
(C2'), 148.71 s (C4), 171.80 s (C12). Found, %: C 81.59;
H 7.88. C22H26O2. Calculated, %: C 81.95; H 8.13.
13C NMR spectrum, δ, ppm: 17.62 q (C14), 22.70 t (C2),
24.97 t (C6), 34.48 C (C10), 36.82 t (C3), 39.49 d (C7),
41.39 t (C9), 42.15 t (C1), 46.40 d (C5), 55.30 q (OCH3),
55.50 q (OCH3), 76.74 d (C8), 98.23 d (C3'), 105.21 d
(C5'), 106.52 t (C15), 116.19 s (C1'), 129.19 d, 129.47 d
(C6',13), 130.22 s (C11), 149.22 s (C4), 159.88 s (C2'),
162.37 s (C4'), 172.92 s (C12). Mass spectrum, m/z (Irel,
%): 368 [M]+ (100), 323 (11), 245 (16), 232 (15), 175 (15),
151 (15), 115 (51), 91 (42), 79 (21), 41 (20). Found [M]+
368.1977. C23H28O4. Calculated M 368.1982.
(3aR,4aS,8aR,9aR,E)-3-(3,4-Dihydroxyben-
zylid-ene)-8a-methyl-5-methylidenedecahydro-
naphtho[2,3-b]furan-2(3H)-one (IIId). Yield 55%, mp
171–173°C (chloroform), [α]D20 +511° (c 0.7, CHCl3). IR
spectrum, ν, cm–1: 3090, 1718, 1645, 1604, 1517, 1443,
1374, 1337, 1293, 1259, 1219, 1166, 1113, 1089, 1033,
1000, 968, 889, 811. UV spectrum, λmax, nm (lgε): 201
(4.15), 221 (3.99), 238 (3.89), 334 (4.17). 1H NMR spec-
trum (CD3OD), δ, ppm: 0.82 s (3H, C14H3), 1.17–1.36 m
(2H, H1,6), 1.51–1.62 m (4H, H1,2,2,9), 1.96 d (1H, H5,
J 12.5 Hz), 1.95–2.15 m (3H, H3,6,9), 2.32 d.m (1H,
H3, J 12.5 Hz), 3.48 d.d.d (1H, H7, J 11.5, 5.6, 5.6 Hz),
4.41 d (1H, H15, J 1.2 Hz), 4.44 d.d.d (1H, H8, J 4.8, 4.5,
1.3 Hz), 4.74 d (1H, H15, J 1.3 Hz), 4.91 br.s (2H, OH,
J1/2W 8.0 Hz), 6.83 d (1H, H5', J 8.3 Hz), 6.98 d.d (1H,
H6', J 8.3, 2.0 Hz), 7.12 d (1H, H2', J 2.0 Hz), 7.23 d
(1H, H13, J 1.0 Hz). 13C NMR spectrum, δ, ppm: 18.16 q
(C14), 23.94 t (C2), 25.72 t (C6), 35.43 s (C10), 37.93 t
(C3), 40.49 d (C7), 42.23 t (C9), 43.20 t (C1), 47.09 d (C5),
79.00 d (C8), 106.48 t (C15), 116.77 d (C2'), 117.18 d (C5'),
124.96 d (C6'), 127.27 s (C1'), 129.94 s (C11), 136.96 d
(C13), 146.83 s (C3'), 149.17 s (C4'), 150.68 s (C4),
175.34 s (C12). Found, %: C 73.79; H 7.12. C21H24O4.
Calculated, %: C 74.09; H 7.11.
(4aS,8aR,9aS)-3-(2,4-Dimethoxybenzyl)-8a-
methyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octadeca-
hydronaphtho[2,3-b]furan-2(4H)-one (IVg). Yield
10% (from 1H NMR spectrum of reaction mixture). By
chromatography compound IVg was isolated in 80%
purity (impurity compound III g). Characteristic signals
of compound IVg in 1H NMR spectrum (CDCl3), δ, ppm:
0.87 s (3H, C14H3), 1.10 d.d (1H, H9, J 10.8, 10.8 Hz),
1.26 d.d.d (1H, H1, J 13.4, 13.4, 4.8 Hz), 1.49–1.65 m
(3H, H2,2,9), 1.76 d.d.d.d (1H, H5, J 12.5, 3.3. 1.7 Hz),
1.93 m (1H, H3, J 12.8, 12.8, 5.8 Hz), 2.28 m (2H, H6,9),
2.35 d.d.d.d (1H, H3, J 13.4, 3.8, 2.2, 1.8 Hz), 2.97 d.d
(1H, H6, J 13.8, 3.8 Hz), 3.46 d (1H, H13, J 13.5 Hz),
3.53 d (1H, H13, J 13.5 Hz), 3.75 s (3H, OCH3), 3.78 s
(3H, OCH3), 4.59 br.s (1H, H15), 4.78 d.d (1H, H8,
J 11.5, 6.3 Hz), 4.86 br.s (1H, H15), 6.42 d.d (1H, H6',
J 8.5, 2.0 Hz), 7.25 d (1H, H5', J 8.5 Hz), 7.26 d (1H, H2',
J 2.0 Hz). 13C NMR spectrum, δ, ppm: 16.41 q (C14),
22.23 t (C2), 23.21 t (C13), 25.58 t (C6), 36.21 t (C3),
36.83 s (C10), 40.74 t (C1), 47.57 t (C9), 50.06 d (C5),
54.81 q and 55.22 q (2×OCH3), 77.68 d (C8), 98.19 d (C3'),
103.75 d (C5'), 106.75 t (C15), 118.60 s (C1'), 130.93 d
(C6'), 148.54 s (C4), 159.57 s (C2'), 163.12 s (C4'), 174.19 s
(C12). Found, %: C 74.90; H 7.92. C23H28O4. Calculated,
%: C 74.97; H 7.66.
(3aR,4aS,8aR,9aR,E)-3-(2,4-Dimethoxy-
benzylidene)-8a-methyl-5-methylidenedecahydro-
naphtho[2,3-b]furan-2(3H)-one (IIIg). Yield 80%, mp
150–152°C (ether), [α]D20 +534° (c 1.0, CHCl3). IR spec-
trum, ν, cm–1: 3090, 1738, 1646, 1606, 1575, 1501, 1462,
1441, 1420, 1302, 1279, 1253, 1214, 1167, 1120, 1032,
1000, 939, 892. UV spectrum, λmax, nm (lgε): 201 (4.42),
221 (3.87), 241 (3.92), 296 (3.98), 335 (4.20). 1H NMR
spectrum (CDCl3), δ, ppm: 0.85 s (3H, C14H3), 1.25 d.d.d
(1H, H1, J 12.3, 12.3, 3.4 Hz), 1.39 d.d.d (1H, H6, J 13.6,
12.5, 12.2 Hz), 1.48–1.61 m (4H, H1,2,2,9), 1.89 d (1H,
H5, J 12.5 Hz), 1.93–2.04 m (2H, H3,6), 2.21 d (1H, H9,
J 15.3 Hz), 2.32 d.m (1H, H3, J 14.0 Hz), 3.31 d.d.d (1H,
H7, J 11.6, 5.8, 5.5 Hz), 3.82 s (2×3H, OCH3), 4.41 br.s
(1H, H15), 4.44 d.d.d (1H, H8, J 4.4, 3.5, 1.3 Hz), 4.74 br.s
(1H, H15), 6.44 d (1H, H3', J 2.4 Hz), 6.50 d.d (1H, H5',
J 8.6, 2.4 Hz), 7.46 d (1H, H6', J 8.6), 7.82 br.s (1H, H13).
(3E, 3aR, 4aR, 5E, 8aR, 9aR)-3, 5-bis(2, 4-
dimethoxybenzylidene)-8a-methyldecahydro-
naphtho[2,3-b]-furan-2(3H)-one (Vg). Yield 4%. Oily
20
substance, [α]D +534° (c 1.0, CHCl3). IR spectrum,
ν, cm–1: 3090, 1747, 1646, 1607, 1576, 1503, 1296,
1210, 1160, 1120, 1032, 992, 939, 900, 833, 758, 636.
UV spectrum, λmax, nm (log ε) (ethanol): 201 (4.66),
1
245 (4.18), 289 (4.04), 336 (4.16). H NMR spectrum
(CDCl3), δ, ppm: 0.94 s (3H, C14H3), 1.22 m (1H, H1),
1.51–1.61 m (5H, H1,2,2,6,9), 1.76 m (1H, H3), 2.04–2.10 m
(2H, H5,6), 2.28 d.d (1H, H9, J 15.4, 1.5 Hz), 2.80 br.d
(1H, H3, J 12.7 Hz), 3.34 d.d.d (1H, H7, J 12.0, 6.1,
4.7 Hz), 3.74 s (3H, OCH3), 3.78 s (3H, OCH3), 3.82
s (3H, OCH3), 3.83 s (3H, OCH3), 4.46 d.d.d (1H, H8,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SYNTHETIC TRANSFORMATIONS OF METHYLENELACTONES
1729
J 4.4, 4.4, 1.2 Hz), 5.90 br.s (1H, H15), 6.41–6.43 m (2H,
H3'',5''), 6.45 d (1H, H3', J 2.3 Hz), 6.52 d.d (1H, H5',
J 8.6, 2.3 Hz), 6.98 d (1H, H6'', J 9.0 Hz), 7.51 d (1H, H6',
J 8.6 Hz), 7.84 s (1H, H13). 13C NMR spectrum, δ, ppm:
17.92 q (C14), 22.64 t (C2), 25.11 t (C6), 30.89 t (C3),
35.26 s (C10), 39.81 d (C7), 41.70 t (C9), 42.65 t (C1),
47.48 d (C5), 55.24 q (OCH3), 55.32 q (OCH3), 55.36 q
(OCH3), 55.50 q (OCH3), 76.76 d (C8), 98.29 d (C3',3''),
103.71 d (C5''), 105.26 d (C5'), 116.36 s (C1'), 117.02 d
(C15), 119.84 s (C1''), 129.12 d (C13), 129.51 s (C11),
129.62 d (C6'), 130.53 d (C6''), 141.48 s (C4), 158.03 s
(C4''), 159.48 s (C2''), 159.90 s (C4'), 162.35 s (C2'),
173.02 s (C12). Found, %: C 73.54; H 7.06. C31H36O6.
Calculated, %: C 73.79; H 7.19.
4.8 Hz), 1.55–1.65 m (3H, H1,2,2), 1.81 d.m (1H, H5,
J 13.0 Hz), 1.94 d.d.d (1H, H3, J 12.9, 12.6, 6.2 Hz),
2.27–2.39 m (3H, H3,6,9), 2.73 d.d (1H, H6, J 14.0,
3.8 Hz), 3.51 d (1H, H13, J 14.8 Hz), 3.58 d (1H, H13,
J 14.8 Hz), 4.56 d (1H, H15, J 1.0 Hz), 4.84–4.89 m
(1H, H8), 4.86 d (1H, H15, J 1.0 Hz), 6.96 d.d.d.d (2H,
H3',5', J 8.9, 8.7, 2.3, 2.0 Hz), 7.20 d.d.d.d (2H, H2',6'
,
J 8.9, 8.7, 3.0, 2.4 Hz). 13C NMR spectrum, δ, ppm:
16.33 q (C14), 22.16 t (C2), 25.70 t (C6), 28.39 t (C13),
36.12 t (C3), 36.82 s (C10), 40.63 t (C1), 47.45 t (C9),
49.93 d (C5), 77.91 d (C8), 106.90 t (C15), 115.29 d (C3',5'
,
J 21.4 Hz), 123.42 s (C11), 129.75 d (C2',6'), 133.91 s
(C1'), 148.13 s (C4), 161.47 d (C4', JC-F 244.7 Hz),
163.70 C (C7), 173.85 s (C12). Found, %: C 77.08; H 7.25.
C21H23O2F. Calculated, %: C 77.27; H 7.10.
(3aR,4aS,8aR,9aR,E)-8a-Methyl-5-methylidene-
3-(4-fluorobenzylidene)decahydronaphtho[2,3-b]
furan-2(3H)-one (IIIh). Yield 5%, conversion of lactone
I 70%, mp 208–209°C, [α]D20 +454° (c 1.2, CHCl3). IR
spectrum, ν, cm–1: 3090, 1743, 1656, 1599, 1510, 1239,
1223, 1171, 1159, 999, 890, 833. UV spectrum, λmax, nm
(log ε): 201 (4.25), 220 (4.02), 226 (3.94), 284 (4.26),
292 (4.22). 1H NMR spectrum (CDCl3), δ, ppm: 0.84 s
(3H, C14H3), 1.25 m (1H, H1), 1.39 d.d.d (1H, H6, J 13.9,
12.6, 12.2 Hz), 1.48–1.61 m (4H, H1,2,2,9), 1.90–2.06 m
(3H, H3,5,6), 2.23 d.d (1H, H9, J 15.5, 1.7 Hz), 2.32 d.m
(1H, H3, J 13.4 Hz), 3.39 d.d.d (1H, H7, J 12.0, 6.0,
5.4 Hz), 4.39 d (1H, H15, J 1.2 Hz), 4.48 d.d.d (1H,
H8, J 4.7, 3.5, 1.3 Hz), 4.75 d (1H, H15, J 1.2 Hz),
7.08 d.d.d.d (2H, H3',5', J 8.8, 8.5, 2.8, 1.9 Hz), 7.36 br.s
(1H, H13), 7.49 d.d.d (2H, H2',6', J 8.8, 8.3, 2.7, 1.9 Hz).
13C NMR spectrum, δ, ppm: 17.56 q (C14), 22.59 t (C2),
24.47 t (C6), 34.38 s (C10), 36.72 t (C3), 39.29 d (C7),
41.20 t (C9), 42.06 t (C1), 46.22 d (C5), 76.82 d (C8),
106.61 t (C15), 116.07 d (C3',5'), 130.34 s (C1'), 131.41
d (C2',6'), 131.94 s (C11), 133.59 d (C13), 148.92 s (C4),
163.16 d (C4', JC-F 251.6 Hz), 172.15 s (C12). Found,
%: C 76.87; H 7.09; F 5.87. C21H23O2F. Calculated, %:
C 77.27; H 7.10; F 5.82.
(3aR,4aS,8aR,9aR,E)-3-(3-Methyl-4-fluoro-
benzylidene)-8a-methyl-5-methylidenedeca-
hydronaphtho[2,3-b]-furan-2(3H)-one (IIIi). Yield
57%, mp 188–191°C, [α]D20 +427° (c 1.0, CHCl3). IR
spectrum, ν, cm–1: 3089, 1744, 1657, 1501, 1298, 1246,
1230, 1206, 1173, 1120, 998, 932, 889, 816. UV spec-
trum, λmax, nm (log ε): 200 (4.28), 210 (4.10), 224 (4.13),
287 (4.31). 1H NMR spectrum (CDCl3), δ, ppm: 0.84 s
(3H, C14H3), 1.25 d.d.d (1H, H1, J 12.1, 11.9, 5.0 Hz),
1.39 d.d.d (1H, H6, J 13.6, 13.4, 11.4 Hz), 1.51–1.59 m
(4H, H1,2,2,9), 1.90–2.03 m (3H, H3,5,6), 2.23 d.d (1H,
H9, J 15.7, 1.0 Hz), 2.27 s (3H, CH3), 2.32 br.d (1H,
H3, J 12.0 Hz), 3.40 d.d.d (1H, H7, J 11.9, 6.1, 5.8 Hz),
4.39 br.s (1H, H15), 4.47 d.d.d (1H, H8, J 4.5, 3.2, 1.0 Hz),
4.74 br.s (1H, H15), 7.01 d.d (1H, H5', J 8.9, 8.8 Hz),
7.30–7.35 m (3H, H2',6',13). 13C NMR spectrum, δ, ppm:
14.55 q (CH3), 17.56 q (C14), 22.64 t (C2), 24.54 t (C6),
34.40 s (C10), 36.77 t (C3), 39.26 d (C7), 41.25 t (C9),
42.10 t (C1), 46.24 d (C5), 76.82 d (C8), 106.61 t (C15),
115.80 d (C5', J 21.2), 125.80 s (C3'), 128.42 d (C6'),
130.10 s (C1'), 131.68 s (C11), 133.32 d (C2'), 133.94 d
(C13), 148.98 s (C4), 163.08 d (C4', J 248.6 Hz), 172.15 s
(C12). Mass spectrum, m/z (Irel, %): 342 (3), 341 (20),
340 (76), 312 (5), 296 (5), 268 (5), 205 (18), 204 (100),
176 (20), 147 (29), 146 (18), 123 (17), 121 (15), 57 (20),
41 (17). Found [M]+ 340.1840. C22H25O2F. Calculated
M 340.1833.
(4aS,8aR,9aS)-8a-Methyl-5-methylidene-3-(4-
fluorobenzyl)-4a,5,6,7,8,8a,9,9a-octahydronaph-
tho-[2,3-b]furan-2(4H)-one (IVh). Yield 18%, mp
135–137°C (ethyl acetate), [α]D20 +134° (c 0.4, CHCl3).
IR spectrum, ν, cm–1: 3090, 1748, 1682, 1642, 1600,
1508, 1442, 1383, 1339, 1219, 1158, 1125, 1096, 1059,
1044, 1014, 896, 857, 843, 798, 744, 627, 614, 527, 492.
UV spectrum, λmax, nm (lgε): 202 (4.26), 210 (4.24),
(4aS,8aR,9aS)-3-(3-Methyl-4-fluorobenzyl)-8a-
methyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydro-
naphtho[2,3-b]furan-2(3H)-one (IVi). Oily substance.
1H NMR spectrum (CDCl3), δ, ppm (characteristic signals
from the mixture containing 80% of compound IVi):
0.84 s (3H, C14H3), 1.11 d.d (1H, H9, J 11.8, 11.8 Hz),
1.28 d.d.d (1H, H1, J 13.4, 13.2, 4.8 Hz), 1.52–1.62 m
1
221 (4.21), 266 (3.16), 273 (3.12). H NMR spectrum
(CDCl3), δ, ppm: 0.89 s (3H, C14H3), 1.14 d.d (1H,
H9, J 12.1, 11.8 Hz), 1.29 d.d.d (1H, H1, J 13.4, 13.4,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

BELOVODSKII et al.
1730
(3H, H1,2,2), 1.79 d.m (1H, H5, J 12.4 Hz), 1.94 d.d.d
(1H, H3, J 13.94, 13.2, 5.6 Hz), 2.19 br.s (1H, C3'CH3),
2.26–2.37 m (3H, H3,6,9), 2.73 d.d (1H, H6, J 14.0,
3.8 Hz), 3.46 d (1H, H13, J 14.8 Hz), 3.53 d (1H, H13,
J 14.8 Hz), 4.54 d (1H, H15, J 1.1 Hz), 4.81–4.85 m (1H,
H8), 4.84 d (1H, H15, J 1.1 Hz), 6.86 d.d (1H, H5', J 9.1,
8.6 Hz), 6.96 m (1H, H6'), 7.02 d.m (1H, H2', J 7.0 Hz).
13C NMR spectrum, δ, ppm: 16.34 q (C14), 22.18 t (C2),
25.69 t (C6), 28.34 t (C13), 36.13 t (C3), 36.81 s (C10),
40.65 t (C1), 47.49 t (C9), 49.94 d (C5), 77.86 d (C8),
106.89 t (C15), 114.85 d (C5', J 22.0 Hz), 123.50 s (C11),
124.72 s (C3'), 126.87 d (C6'), 131.34 d (C2'), 133.59 s
(C1'), 148.14 s (C4), 159.98 d (C4', JC-F 243.5), 163.63 s
(C7), 173.90 s(C12).
1.29 d.d.d (1H, H1, J 13.4, 13.4, 5.1 Hz), 1.53–1.66 m (3H,
H1,2,2), 1.79 d.m (1H, H5, J 12.9 Hz), 1.95 d.d.d (1H, H3,
J 12.6, 12.1, 4.8 Hz), 2.27–2.38 m (3H, H3,6,9), 2.73 d.d
(1H, H6, J 14.0, 3.8 Hz), 3.51 d (1H, H13, J 15.0 Hz),
3.58 d (1H, H13, J 15.0 Hz), 4.54 d (1H, H15, J 1.1 Hz),
4.82–4.87 m (1H, H8), 4.85 d (1H, H15, J 1.1 Hz),
7.15 d.d.d (2H, H2',6', J 8.6, 2.4, 2.1 Hz), 7.22 d.d.d (2H,
H3',5', J 8.6, 2.4, 2.1 Hz). 13C NMR spectrum, δ, ppm:
16.34 q (C14), 22.15 t (C2), 25.74 t (C6), 28.53 t (C13),
36.11 t (C3), 36.83 s (C10), 40.60 t (C1), 47.43 t (C9),
49.93 d (C5), 77.94 d (C8), 106.95 t (C15), 123.11 s (C11),
128.62 d (C2',6'), 129.66 d (C3',5'), 132.18 C (C4'), 136.72 s
(C1'), 148.10 s (C4), 163.95 s (C7), 173.80 s (C12). Found,
%: C 73.32; H 6.63; Cl 10.62. C21H23O2Cl. Calculated,
%: C 73.57; H 6.76; Cl 10.34.
(3aR,4aS,8aR,9aR,E)-8a-Methyl-5-methylidene-
3-(4-chlorobenzylidene)decahydronaphtho[2,3-b]-
furan-2(3H)-one (IIIj). Yield 60%, mp 207–209°C
(from ethanol–ethyl acetate, 10:1), [α]589 +357°
(c 0.7, CHCl3). IR spectrum, ν, cm–1: 3088, 1744, 1651,
1492, 1304, 1259, 1225, 1199, 1168, 1092, 1033, 1012,
999, 892, 829. UV spectrum, λmax, nm (lgε): 201 (4.23),
222 (4.11), 229 (4.04), 289 (4.37), 296 (4.35). 1H NMR
spectrum (CDCl3), δ, ppm: 0.86 s (3H, C14H3), 1.26 d.d.d
(1H, H1, J 12.8, 12.6, 4.7 Hz), 1.40 d.d.d (1H, H6, J 13.6,
13.2, 12.6 Hz), 1.51–1.62 m (4H, H1,2,2,9), 1.91–1.97 m
(2H, H5,6), 2.02 d.d.d (1H, H3, J 12.9, 12.8, 5.6 Hz),
2.25 d.d (1H, H9, J 15.5, 1.3 Hz), 2.34 br.d (1H, H3,
J 13.5 Hz), 3.39 d.d.d (1H, H7, J 11.9, 6.0, 5.0 Hz), 4.40 d
(1H, H15, J 0.9 Hz), 4.49 d.d.d (1H, H8, J 4.7, 4.7, 1.8 Hz),
4.76 d (1H, H15, J 0.9 Hz), 7.36 br.s (1H, H13), 7.37 d.d.d
(2H, H2',6', J 8.6, 2.3, 2.1 Hz), 7.44 d.d.d (2H, H3',5', J 8.6,
1.9, 1.3 Hz). 13C NMR spectrum, δ, ppm: 17.27 q (C14),
22.28 t (C2), 24.15 t (C6), 34.08 s (C10), 36.43 t (C3),
39.11 d (C7), 40.89 t (C9), 41.77 t (C1), 45.94 d (C5),
76.53 d (C8), 106.36 t (C15), 128.91 d (C3',5'), 130.38 d
(C2',6'), 132.29 s (C11), 132.62 s (C1'), 133.21 d (C13),
135.32 s (C4'),148.57 s (C4), 171.74 C (C12). Found, %:
C 73.25; H 6.87; Cl 9.82. C21H23O2Cl. Calculated, %:
C 73.57; H 6.76; Cl 10.34.
(3aR,4aS,8aR,9aR,E)-3-(4-Bromobenzylidene)-8a-
methyl-5-methylidenedecahydronaphtho[2,3-b]furan-
2(3H)-one (IIIk). Yield 55%, mp 196–198°C (ethyl
20
acetate), [α]D +388° (c 0.93, CHCl3). IR spectrum, ν,
cm–1: 3092, 1744, 1649, 1487, 1259, 1223, 1171, 1072,
1000, 894, 829, 818. UV spectrum, λmax, nm (log ε):
200 (4.29), 223 (4.02), 290 (4.32), 298 (4.31). 1H NMR
spectrum (CDCl3), δ, ppm: 0.86 s (3H, C14H3), 1.25 m
(1H, H1), 1.39 d.d.d (1H, H6, J 13.7, 13.5, 13.3 Hz), 1.50–
1.62 m (4H, H1,2,2,9), 1.91–2.07 m (3H, H3,5,6), 2.25 d.d
(1H, H9, J 15.5, 1.5 Hz), 2.34 br.d (1H, H3, J 14.2 Hz),
3.38 d.d.d (1H, H7, J 12.0, 5.9, 5.1), 4.40 d (1H, H15,
J 1.2 Hz), 4.49 d.d.d (1H, H8, J 4.7, 4.6, 1.5 Hz), 4.76 d
(1H, H15, J 1.2 Hz), 7.35 br.s (1H, H13), 7.37 br.d (2H,
H2',6', J 8.8 Hz), 7.53 br.d (2H, H3',5', J 8.8 Hz). 13C NMR
spectrum, δ, ppm: 17.58 q (C14), 22.61 t (C2), 24.45 t
(C6), 34.38 s (C10), 36.74 t (C3), 39.43 d (C7), 41.21 t
(C9), 42.08 t (C1), 46.25 d (C5), 76.84 d (C8), 106.66 t
(C15), 123.96 d (C4'), 130.88 d (C2',6'), 132.19 d (C3',5'),
133.05 s (C1'), 133.18 s (C11), 133.55 d (C13), 148.86 s
(C4), 171.99 s (C12). Found, %: C 64.48; H 5.64; Br 19.78.
C21H23O2Br. Calculated, %: C 65.12; H 5.99; Br 20.63.
(4aS,8aR,9aS)-3-(4-Bromobenzyl)-8a-methyl-5-
methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho-
[2,3-b]furan-2(4H)-one (IVk). Yield 20%. Oily
substance, [α]D20 +63° (C 0.12, CHCl3). UV spectrum,
λmax, nm (log ε): 204 (4.25), 223 (4.23), 277 (3.10).
1H NMR spectrum (CDCl3), δ, ppm: 0.87 s (3H, C14H3),
1.12 d.d (1H, H9, J 11.9, 11.7 Hz), 1.30 d.d.d (1H, H1,
J 13.2, 13.2, 4.9 Hz), 1.55–1.64 m (3H, H1,2,2), 1.79 d.m
(1H, H5, J 13.0 Hz), 1.95 d.d.d (1H, H3, J 12.8, 12.6,
5.7 Hz), 2.28–2.33 m (2H, H6,9), 2.35 d.m (1H, H3,
J 13.2 Hz), 2.73 d.d (1H, H6, J 13.8, 5.7 Hz), 3.50 d
(1H, H13, J 15.0 Hz), 3.56 d (1H, H13, J 15.0 Hz), 4.54 d
(4aS,8aR,9aS)-8a-Methyl-5-methylidene-3-(4-
chlorobenzyl)-4a,5,6,7,8,8a,9,9a-octahydronaphtho-
[2,3-b]furan-2(4H)-one (IVj). Yield 20%, mp 126–
20
128°C (chloroform), [α]D +165° (c 0.7, CHCl3). IR
spectrum, ν, cm–1: 2979, 2934, 2841, 1745, 1680, 1645,
1490, 1440, 1170, 1090, 1060, 1049, 1014, 889, 803.
UV spectrum, λmax, nm (lgε): 201 (4.31), 222 (4.22), 288
(3.57), 311 (3.32). 1H NMR spectrum (CDCl3), δ, ppm:
0.86 s (3H, C14H3), 1.12 d.d (1H, H9, J 12.1, 11.8 Hz),
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SYNTHETIC TRANSFORMATIONS OF METHYLENELACTONES
1731
(1H, H15, J 0.8 Hz), 4.83–4.86 m (1H, H8), 4.85 d
(1H, H15, J 0.8 Hz), 7.09 d.d.d (2H, H2',6', J 8.4, 2.6,
1.9 Hz), 7.38 d.d.d (2H, H3',5', J 8.4, 2.6, 1.9 Hz).
13C NMR spectrum, δ, ppm: 16.35 q (C14), 22.19 t (C2),
25.77 t (C6), 28.64 t (C13), 36.15 t (C3), 36.85 s (C10),
40.67 t (C1), 47.51 t (C9), 49.99 d (C5), 77.93 d (C8),
106.93 t (C15), 120.27 s (C11), 123.09 s (C4'), 130.07 d
(C2',6'), 131.60 d (C3',5'), 137.29 s (C1'), 148.13 s (C4),
163.90 s (C7), 173.73 s (C12). Found, %: C 64.69; H 5.72;
Br 20.12. C21H23BrO2. Calculated, %: C 65.12; H 5.99;
Br 20.63.
H5, J 12.5 Hz), 1.95 d.d.d (1H, H6, J 14.2, 6.6, 2.4 Hz),
2.02 d.d.d (1H, H3, J 12.7, 11.7, 5.6 Hz), 2.23 s (3H,
COCH3), 2.25 m (1H, H9), 2.34 d.d.d (1H, H3, J 13.4,
1.8, 1.5 Hz), 3.40 d.d.d (1H, H7, J 11.7, 6.0, 5.9 Hz),
3.92 s (3H, OCH3), 4.39 d (1H, H15, J 1.2 Hz), 4.49 d.d.d
(1H, H8, J 4.6, 4.5, 1.5 Hz), 4.75 d (1H, H15, J 1.2 Hz),
7.36 s (1H, H13), 7.71 d.d (1H, H6', J 8.8, 2.2 Hz), 8.16 d
(1H, H2', J 2.2 Hz), 8.76 d (1H, H5', J 8.8 Hz), 11.10 s
(1H, NH). 13C NMR spectrum, δ, ppm: 17.56 q (C14),
22.64 t (C2), 24.68 t (C6), 25.42 q (CH3CO), 34.42 s
(C10), 36.79 t (C3), 39.47 d (C7), 41.31 t (C9), 42.15 t
(C1), 46.30 d (C5), 52.57 q (OCH3), 76.86 d (C8), 106.61 t
(C15), 114.95 s (C4'), 120.65 d (C5'), 128.38 s (C3'),
132.25 s (C11), 133.11 d (C2'), 133.33 d (C13), 134.26 d
(C6'), 142.32 s (C1'), 148.82 C (C4), 168.04 s (COOCH3),
169.07 s (COCH3), 172.09 s (C12). Mass spectrum, m/z
(Irel, %): 424 (22), 423 [M]+ (83), 391 (26), 382 (26), 381
(100), 258 (21), 255 (62), 245 (21), 188 (19), 156 (22),
123 (23), 79 (23), 44 (46), 43 (36). Found, %: C 70.33;
H 6.34; N 3.11. C25H29NO5. Calculated, %: C 70.90;
H 6.90; N 3.31. M 423.2040.
(3aR,4aS,8aR,9aR,E)-3-(2-Aminobenzylidene)-
8a-methyl-5-methylidenedecahydronaphtho[2,3-b]-
furan-2(3H)-one (IIIm). Conversion of lactone 85%.
Yield 62%, mp 155–157°C (ethyl acetate), [α]D20 +417°
(c 1.2, CHCl3). IR spectrum, ν, cm–1: 3463, 3383, 3090,
1726, 1662, 1603, 1564, 1490, 1457, 1414, 1250, 1220,
1204, 1175, 1159, 1089, 1033, 1001, 900, 858, 764, 746.
UV spectrum, λmax, nm (lgε): 202 (4.29), 236 (4.03),
1
287 (3.88), 329 (3.41), 370 (3.63). H NMR spectrum
(CDCl3), δ, ppm: 0.85 s (3H, C14H3), 1.25 m (1H, H1),
1.39 d.d.d (1H, H6, J 13.0, 12.8, 11.8 Hz), 1.48–1.59 m
(4H, H1,2,2,9), 1.85–1.89 m (2H, H5,6), 1.99 d.d.d (1H,
H3, J 12.8, 11.6, 5.8 Hz), 2.20 d (1H, H9, J 15.5 Hz),
2.33 br.d (1H, H3, J 13.3 Hz), 3.31 d.d.d (1H, H7, J 11.6,
6.0, 5.3 Hz), 4.05 br.s (2H, NH2), 4.41 br.s (1H, H15),
4.48 d.d (1H, H8, J 4.2, 4.1 Hz), 4.75 br.s (1H, H15,
J 1.5 Hz), 6.70 d (1H, H3', J 8.0 Hz), 6.73 d.d (1H, H5',
J 7.8, 7.5 Hz), 7.14 d.d (1H, H4', J 8.0, 7.8 Hz), 7.31 d
(1H, H6', J 7.5 Hz), 7.48 C (1H, H13). 13C NMR spectrum,
δ, ppm: 17.66 q (C14), 22.67 t (C2), 25.56 t (C6), 34.36 s
(C3), 36.77 t (C10), 39.24 d (C7), 41.31 t (C9), 42.09 t
(C1), 46.29 d (C5), 77.16 d (C8), 106.60 t (C15), 116.36 d
(C3'), 118.39 d (C5'), 119.30 s (C1'), 128.18 d (C6'),
129.96 d (C4'), 130.75 d (C13), 132.95 s (C11), 145.91 s
(C2'), 149.03 s (C4), 172.39 s (C12). Found, %: C 78.21;
H 7.67; N 4.59. C21H25NO2. Calculated, %: C 77.98;
H 7.79; N 4.33.
(3aR,4aR,8aR,9aR,3E,5E)-3,5-bis(3,4-dimethoxy-
benzylidene)-8a-methyldecahydronaphtho[2,3-b]-
furan-2(3H)-one (Vf). Yield 6%. Oily substance, [α]D20
+534° (c 1.0, CHCl3). IR spectrum, ν, cm–1: 3092, 1749,
1649, 1599, 1583, 1515, 1463, 1418, 1377, 1333, 1253,
1248, 1185, 1161, 1144, 1101,1084, 1026, 995, 954,
900, 872, 809, 757, 667, 630. UV spectrum, λmax, nm
(log ε) (ethanol): 204 (4.45), 248 (4.20), 296 (4.04),
327 (4.09). 1H NMR spectrum (CDCl3), δ, ppm: 0.93 s
(3H, C14H3), 1.33 d.d.d (1H, H1, J 13.8, 13.0, 4.9 Hz),
1.51 d.d.d (1H, H6, J 13.7, 12.7, 12.2 Hz), 1.56–1.65 m
(4H, H1,2,2,9), 1.78 d.d.d (1H, H3, J 13.2, 12.7, 4.4 Hz),
2.06 br.d (1H, H6, J 12.7 Hz), 2.10 d.d.d (1H, H5, J 14.2,
6.8, 2.0 Hz), 2.28 d.d (1H, H9, J 15.5, 1.8 Hz), 3.0 br.d
(1H, H3, J 14.2 Hz), 3.45 d.d.d (1H, H7, J 11.7, 5.9,
5.4 Hz), 3.82 s (3H, OCH3), 3.83 s (3H, OCH3), 3.88 s
(3H, OCH3), 3.89 s (3H, OCH3), 4.50 d.d.d (1H, H8,
J 4.8, 4.5, 1.7 Hz), 5.93 br.s (1H, H15), 6.65 d (1H, H2'',
J 2.0 Hz), 6.70 d.d (1H, H6'', J 8.2, 2.0 Hz), 6.78 d (1H,
H5'', J 8.2 Hz),6.91 d (1H, H5', J 8.4 Hz), 7.03 C (1H, H2',
J 2.0 Hz), 7.19 d.d (1H, H6', J 8.4, 2.0 Hz), 7.38 s (1H,
H13). 13C NMR spectrum, δ, ppm: 17.85 q (C14), 22.57 t
(C2), 24.75 t (C6), 30.52 t (C3), 35.26 s (C10), 39.65 d
(C7), 41.59 t (C9), 42.46 t (C1), 47.24 d (C5), 55.94 q
(4×OCH3), 76.56 d (C8), 110.89 d (C5''), 111.41 d (C5'),
112.29 d (C2''), 113.17 d (C2'), 121.00 d (C6''), 121.27 d
(C15), 122.82 d (C6'), 127.11 s (C1'), 130.14 C (C11),
(3aR,4aS,8aR,9aR,E)-3-(3'-Acetamido-4'-methoxy-
carbonylbenzylidene)-8a-methyl-5-methylidene-
decahydronaphtho[2,3-b]furan-2(3H)-one (IIIn). Yield
20
54%, mp 201–203°C, [α]D +293° (c 1.3, CHCl3). IR
spectrum, ν, cm–1: 3465, 3090, 1739, 1655, 1601, 1572,
1513, 1442, 1302, 1264, 1224, 1166, 1073, 1032, 999,
890, 840, 810, 539, 527. UV spectrum, λmax, nm (log ε):
198 (4.24), 231 (4.22), 245 (4.25), 309 (4.42). 1H NMR
spectrum (CDCl3), δ, ppm: 0.86 s (3H, C14H3), 1.26 d.d.d
(1H, H1, J 12.5, 12.5, 4.9 Hz), 1.39 d.d.d (1H, H6, J 13.9,
12.5, 12.2 Hz), 1.51–1.63 m (4H, H1,2,2,9), 1.91 d (1H,
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BELOVODSKII et al.
1732
130.95 s (C1''), 134.91 d (C13), 141.58 s (C4), 147.33 s
(C3''), 148.45 s (C4''), 149.08 s (C3'), 150.54 s (C4'),
172.46 s (C12). Found, %: C 73.45; H 6.96. C31H36O6.
Calculated, %: C 73.79; H 7.19.
148.37 s (C4), 162.41 s (C7), 174.70 s (C12).
(S)-3-[(2R,4aR,8aS)-4a-Methyl-8-methylene-3-
oxodecahydronaphthalen-2-yl]-3,4-dihydroquinolin-
2(1H)-one (VIIIa). Yield 2%, [α]D20 +7° (c 0.6, CHCl3).
IR spectrum, ν, cm–1: 3435, 3208, 3079, 2931, 1702,
1680, 1595, 1492, 1439, 1392, 1290, 1253, 1237, 1221,
888, 751. UV spectrum, λmax, nm (log ε): 205 (4.45), 252
(3.99). 1H NMR spectrum (CDCl3), δ, ppm: 0.74 s (3H,
CH3), 1.48–1.53 m (3H, H5',5',6'), 1.57–1.68 m (1H, H6'),
1.77 d.d. (1H, H1', J 12.3, 12.0 Hz), 1.98–2.08 m (2H,
H1',7'), 2.24 d (1H, H4', J 13.6 Hz), 2.32–2.37 m (2H,
H4',7'), 2.44 br.d (1H, H8a', J 8.5 Hz), 2.91 m (2H, H4),
3.22 d.d.d (1H, H3, J 10.2, 2.7, 2.0 Hz), 3.34 m (1H, H2',
J2',3 10.2 Hz), 4.43 br.s, 4.78 br.s (2H, CH2), 6.71 d (1H,
H8, J 8.5 Hz), 6.96 d.d (1H, H6, J 8.2, 8.4 Hz), 7.14 d.d
(1H, H7, J 8.5, 8.4 Hz), 7.15 d (1H, H5, J 8.2 Hz), 8.04 br.s
(1H, NH). 13C NMR spectrum, δ, ppm: 17.28 q (CH3),
22.88 t (C6'), 27.27 t (C1',4), 36.45 t (C7'), 38.27 d (C3),
40.46 s (C4'a), 41.28 t (C5'), 48.13 d (C8a'), 48.61 d (C2'),
55.82 t (C4'), 107.08 t (CH2=), 114.73 d (C8), 122.96 d
(C6), 124.13 C (C4a), 127.27 d and 127.95 d (C5,7),
136.55 s (C8a), 148.34 s (C8'), 172.37 s (C2), 209.78 s
(C3'). Mass spectrum, m/z (Irel, %): 325 (3), 324 (4), 323
[M]+ (3), 319 (5), 308 (7), 306 (7), 305 (13), 288 (5), 266
(8), 232 (10), 184 (100), 167 (66), 146 (25), 100 (40),
93 (28). Found [M]+ 323.1877. C21H25NO2. Calculated
M 323.1880.
(3aR,4aS,8aR,9aR,Z)-8a-Methyl-5-methylidene-
3-(4-fluorobenzylidene)decahydronaphtho[2,3-b]
furan-2(3H)-one (VI). Yield 4%, mp 99–115°C, [α]D20
+55° (c 1.4, CHCl3). IR spectrum, ν, cm–1: 3085, 1739,
1646, 1599, 1508, 1375, 1230, 1160, 1124, 1103, 1089,
1036, 1000, 961, 938, 895, 882, 838, 780, 555, 528. UV
spectrum, λmax, nm (lgε): 202 (4.19), 221 (3.94), 292
(4.01). 1H NMR spectrum (CDCl3), δ, ppm: 0.86 s (3H,
C14H3), 1.24 d.d.d (1H, H1, J 13.2, 12.9, 5.0 Hz), 1.49 m
(1H, H6), 1.53–1.56 m (4H, H1,2,2,9), 1.76 d.d.d (1H, H6,
J 14.5, 7.0, 2.6 Hz), 1.85 d.d (1H, H5, J 12.6, 1.5 Hz),
2.00 d.d.d (1H, H3, J 12.6, 12.6, 5.8 Hz), 2.17 d.d (1H, H9,
J 15.5, 1.5 Hz), 2.33 d.d.d (1H, H3, J 12.9, 2.0, 1.5 Hz),
2.93 d.d.d (1H, H7, J 11.7, 5.6, 5.3 Hz), 4.46 d (1H, H15,
J 1.5 Hz), 4.58 d.d.d (1H, H8, J 4.7, 4.7, 1.5 Hz), 4.77 d
(1H, H15, J 1.5 Hz), 6.82 s (1H, H13), 7.03 d.d.d.d (2H,
H3',5', J 8.8, 8.5, 2.9, 2.0 Hz), 7.91 d.d.d.d (2H, H2',6', J 8.8,
8.6, 2.9, 2.3 Hz). 13C NMR spectrum, δ, ppm: 17.71 q
(C14), 22.59 t (C2), 27.88 t (C6), 34.28 C (C10), 36.73 t
(C3), 41.35 t (C9), 42.15 t (C1), 44.38 d (C7), 46.20 d (C5),
76.32 d (C8), 106.54 t (C15), 115.15 d (C3',5', J 22.2 Hz),
129.80 s (C1'), 131.97 s (C11), 132.83 d (C2',6', J 8.5 Hz),
136.56 d (C13), 148.98 s (C4), 163.17 d (C4', J 251.1 Hz),
168.93 s (C12). Mass spectrum, m/z (Irel, %): 328 (2), 327
(15), 326 [M]+ (61), 305 (13), 284 (12), 214 (44), 213
(37), 191 (15), 190 (100), 185 (25) 183 (26), 170 (18),
165 (20), 133 (30), 123 (18), 109 (19), 91 (16). Found
[M]+ 326.1675. C21H23O2F. Calculated M 326.1677.
(R)-3-[(2R,4aR,8aS)-4a-Methyl-8-methylidene-3-
oxodecahydronaphthalen-2-yl]-3,4-dihydro-quinolin-
2(1H)-one (VIIIb). Yield 4%, [α]D20 +13° (c 0.3, CHCl3).
IR spectrum, ν, cm–1: 3436, 3206, 3078, 2928, 1701,
1679, 1649, 1596, 1493, 1439, 1393, 1294, 1274, 1256,
891, 752. UV spectrum, λmax, nm (lgε): 203 (4.55), 251
(4.03). 1H NMR spectrum (CDCl3), δ, ppm: 0.75 s (3H,
CH3), 1.46–1.51 m (3H, H5',5',6'), 1.56 m (1H, H6'), 1.88–
2.06 m (3H, H1',1',7'), 1.98–2.21 m (1H, H4'), 2.30 m (1H,
H4'), 2.35 m (1H, H7'), 2.48 m (1H, H8a'), 2.85 m (1H, H4),
2.90 m (1H, H3, J 3.0, 1.8, 1.6 Hz), 3.04 m (1H, H2', J 3.0,
2.7, 2.5, 1.8 Hz), 3.17 m (2H, H4), 4.52 br.s, 4.80 br.s
(2H, CH2=), 6.71 d (1H, H8, J 8.6 Hz), 6.94 d.d (1H, H6,
J 8.2, 8.3 Hz), 7.10 d (1H, H5, J 8.2 Hz), 7.14 d.d (1H, H7,
J 8.3, 8.6 Hz), 8.20 br.s (1H, NH). 13C NMR spectrum,
δ, ppm: 16.83 q (CH3), 22.55 t (C6'), 27.57 t (C4), 28.45
(C1'), 36.16 t (C7'), 39.66 d (C3), 40.01 s (C4'a), 40.94 t
(C5'), 47.95 d (C8a'), 47.95 d (C2'), 55.58 t (C4'), 106.89 t
(CH2=), 114.73 d (C8), 122.49 d (C6), 122.93 s (C4a),
127.00 d (C7), 127.80 d (C5), 136.46 s (C8a), 148.06 s
(C8'), 171.48 s (C2), 208.45 s (C3'). Mass spectrum, m/z
(Irel, %): 323 [M]+ (2), 305 (2), 172 (1), 159 (1), 147 (11),
(4aS,8aR,9aS)-3,8a-Dimethyl-5-methylidene-
4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-
2(4H)-one (VII). Yield 4%, mp 150–152°C (ethyl
ether), [α]D20 +238° (c 1.1, CHCl3). UV spectrum, λmax
,
nm (log ε): 192 (3.80), 199 (4.00), 220 (4.18). 1H NMR
spectrum (CDCl3), δ, ppm: 0.87 s (3H, C14H3), 1.12 d.d
(1H, H9, J 11.8, 11.7 Hz), 1.30 d.d.d (1H, H1, J 13.3,
13.0, 4.3 Hz), 1.55–1.64 m (3H, H1,2,2), 1.80 s (3H, H13),
1.81–1.86 m (1H, H5), 1.96 d.d.d (1H, H3, J 13.0, 12.3,
6.5 Hz), 2.26–2.33 m (2H, H6,9), 2.36 d.d.d.d (1H, H3,
J 13.0, 3.8, 2.0, 1.8 Hz), 2.72 d.d (1H, H6, J 13.8, 3.8 Hz),
4.59 d (1H, H15, J 1.5 Hz), 4.82 d.d (1H, H8, J 11.5,
6.3 Hz), 4.86 d (1H, H15, J 1.5 Hz). 13C NMR spectrum,
δ, ppm: 8.14 q (C13),16.33 q (C14), 22.22 t (C2), 25.60 t
(C6), 36.16 t (C3), 36.89 s (C10), 40.74 t (C1), 47.41 t (C9),
49.83 d (C5), 77.90 d (C8), 106.81 t (C15), 120.06 C (C11),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SYNTHETIC TRANSFORMATIONS OF METHYLENELACTONES
1733
146 (100), 145 (2), 130 (3), 117 (3), 106 (3), 91 (4). Found
[M]+ 323.1869. C21H25NO2. Calculated M 323.1880.
ACKNOWLEDGMENTS
The study was carried out under a financial sup-
port from the Russian Foundation for Basic Research
(grant no.08-03-00340).
XRD investigation of compound IIIf. For the experi-
ment a colorless needle crystal was selected of dimen-
sions 0.06×0.20×0.90 mm. The analysis of geometry and
intermolecular interactions was performed with the use of
PLATON program [10]. Crystals rhombic: a 6.2067(4),
b 15.298(1), c 21.059(2) Å, V 1999.5(2) Å3, space group
P212121, Z 4, dcalc 1.221 g/cm3.At –100°C in the range up
to 2θ 55° the intensity of 8736 reflections were measured,
among them 4517 independent (Rint 0.047). The correc-
tion for extinction was done using SADABS program
[22] that used multiple measurements of the same reflec-
tions at different orientations of the crystal (transmission
0.62–0.75). The structure was solved by the direct method
and refined in the anisotropic approximation of the
thermal oscillations of the nonhydrogen atoms applying
SHELXL software [23]. The hydrogen atoms positions
were geometrically calculated and refined in the rider
model (the parameters of hydrogen atoms were calculated
in every refinement cycle from the coordinates of the cor-
responding C atoms). The final refinement of the structure
was performed for all F2 till wR2 0.1345, S 1.04, 245
parameters were refined (R 0.0510 for 3740 F > 4σ). CIF
file containing complete information on the investigated
structure is deposited to the Cambridge Crystallographic
Database Center under the number CCDC 729045, and
the data are available by the address: www.ccdc.cam.
ac.uk/data_request/cif.
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