Sesquiterpene metylenelactones in a palladium-catalyzed cross-coupling reaction

Full text of DOI:10.1134/S001250080906007X

ISSN 0012-5008, Doklady Chemistry, 2009, Vol. 426, Part 2, pp. 138–142. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.V. Belovodskii, E.E. Shul’ts, M.M. Shakirov, G.A. Tolstikov, 2009, published in Doklady Akademii Nauk, 2009, Vol. 426, No. 6, pp. 762–765.
CHEMISTRY
Sesquiterpene Metylenelactones
in a Palladium-Catalyzed Cross-Coupling Reaction
A. V. Belovodskii, E. E. Shul’ts,
M. M. Shakirov, and Academician G. A. Tolstikov
Received January 27, 2009
DOI: 10.1134/S001250080906007X
Compounds containing an α-methylene-γ-lactone have not been involved in reactions with organometalic
fragment, in particular sesquiterpene lactones, have
attracted attention for the past 50 years owing to their
diverse physiological activity, including antitumor
properties [1]. The biological activity of sesquiter-
pene lactones are known to result from their behavior
as alkylating agents. These compounds can form in
vivo adducts with nucleophilic regions of biomole-
cules (like products of the Michael reaction with free
sulfhydryl or amino groups) [2]. Eudesmane-type
sesquiterpene lactones show antiproliferative activ-
ity in vitro in tumor cells MK-1, HeLa, and B16F10
[3]. The capability to inhibit the growth of human
tumor cells (COLO-205, HT-29, HL-60, AGS) is
explained by the initiation of apoptosis, which is
considered to be associated with activation of a
caspase cascade in these cells [4–6].
reagents until now.
We established for the first time that isoalantolac-
tone 1 is a reactive alkene component in the palladium-
catalyzed cross-coupling reaction with aryl halides (the
Heck reaction [9]). The reaction of compound 1 with 4-
iodoanisole, 4-iodoveratrole, or 2-iodothioanisole in
DMF in the presence of catalytic amounts of palladium
acetate and tris(o-tolyl)phosphine and triethylamine as
a base (120°C, 8 h) leads to (E)-13-aryleudesm-11-en-
8α,12-olides (3, 4, 5) in 79–85% yield. The products of
double bond shift (6, 7, 8) also form in 9–17% yield
(Scheme 1). The cross-coupling of alantolactone 2 with
4-iodoveratrole under noted conditions results in lower
yield of aryl-substituted derivatives (9, 10) (20 and
36%, respectively). Thus, the yield of the products of
double bond shift in the reactions of alantolactone 2
(compound 10) is considerably higher than that for
isoalantolactone 1. This fact can be explained by the
tendency to form a system of conjugated double
bonds.
Antitumor drug Arglabin has been developed
on the basis of one of sesquiterpene methylenelac-
tones [7].
Sesquiterpene lactones isoalantolactone (1) and
alantolactone (2), available metabolites of elecampane
Inula helenium L. [8], have attracted our attention. In
this report, we describe the modification of these lac-
tones by introducing aromatic substituents via the Heck
reaction. It should be noted that exo methylenelactones
The structure of lactones 3–10 was established on
the basis of spectral data and elemental analysis. The
(E) configuration of C-11,13 bond in arylidenelac-
tones 3–5 and 9 follows from the presence in the 13C
NMR spectrum (monoresonance mode) of carbon–
3
proton J cis coupling constant between the olefin
Vorozhtsov Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, pr. Lavrent’eva 9,
Novosibirsk, 630090 Russia
proton (H13) and the carbonyl carbon of lactone 3J =
6.9–7.5 Hz.
138

SESQUITERPENE METYLENELACTONES
139
Scheme 1.
14CH3
CH3
CH3
H
H
H
H
H
I
O
O
O
1
9
O
O
12
O +
+
3
5
7
11
R3
R1
H
H
H
H
C
C
R2
CH2
CH2
CH2
CH2
H
H
13
15
1
R3
R3
R1=OCH3, R2=R3=H (3, 6)
R1=R2=OCH3, R3=H (4, 7)
R1=R2=H, R3=SCH3 (5, 8)
R1
3, 4, 5
R1
6, 7, 8
R2
R2
CH3
CH3
CH3
H
H
H
H
I
O
O
O
+
+
O
O
O
OCH3
H
H
CH2
C
C
OCH3
CH
CH2
CH3
CH3
H
H
3
2
H3CO
H3CO
OCH3
OCH3
9
10
Thus, in this work we accomplished for the first time lowed by isolation via morpholine adducts as described
the arylation of sesquiterpene methylenelactones via
cross-coupling reaction catalyzed by palladium phos-
phine complexes.
in [11].
The Heck reaction. General procedure. A two-
necked glass ampoule was purged with argon. The
ampoule was charged sequentially in an argon flow
with 2.15 mmol (500 mg) of lactone 1 or 2, 2.58 mmol
of aryl iodide, 0.086 mmol (4 mol %) of palladium ace-
tate, 0.34 mmol (16 mol %) of tris(o-tolyl)phosphine,
7 mL of DMF, 3.87 mmol of triethylamine, and molec-
EXPERIMENTAL
NMR spectra of the compounds as solutions in
CDCl3 were recorded on Bruker AV-300 (operating at
300.13 (1ç) and 75.47 MHz (13C)), Bruker AM-400 ular sieves 3 Å. The ampoule was sealed (small excess
(operating at 400.13 (1ç) and 100.78 MHz (13C)), and
Bruker DRX-500 (operating at 500.13 (1ç) and
125.76 MHz (13C)) spectrometers. Signal assignment
in NMR spectra was performed using different types of
proton–proton and carbon–proton shift correlation
spectroscopy (COSY, COLOC). Mass spectra, molecu-
lar weights, and elemental composition were measured
pressure of argon), and the reaction mixture was heated
for 8–10 h at 120°C. After completion of the reaction,
the ampoule was allowed to cool and opened, and the
reaction mixture was poured into a Petri dish. The solid
residue was dissolved in a minimal amount of chloro-
form and chromatographed on silica gel (chloroform–
ethanol, 100 : 0 to 10 : 1 as an eluent). The following
with a Finnigan MAT-8200 high-resolution mass spec- products were eluted sequentially: tris(o-tolyl)phos-
trometer at an ionizing voltage of 70 eV (injector tem-
perature of 270–300°ë). IR spectra were obtained on a
Vector-22 spectrometer as KBr pellets. UV absorption
spectra were recorded on a HP 8453 UV Vis spectro-
photometer as solutions in ethanol or chloroform.
phine, the initial lactone, a mixture of the lactone with
reaction product, and a mixture of two reaction prod-
ucts (chloroform as an eluent). Repeated chromatogra-
phy and recrystallization from appropriate solvent was
used to isolate pure arylation product.
Reaction products were isolated by column chroma-
tography on silica gel (Acros, 0.035–0.070 mm, pore
size 6 nm) (elution with benzene–ethyl acetate, chloro-
form–ethanol).
(3aR,4aS,8aR,9aR,E)-3-(4-Methoxybenzylide-
ne)-8a-methyl-5-methylenedecahydronaphtho[2,3-
b]furan-2(3H)-one (3). Yield 85%, mp 199–201°ë
(from ethyl acetate), [α]589 + 561 (c 1.445, CHCl3).
IR (ν, cm–1): 787, 908, 1001, 1032, 1073, 1089, 1169,
1186, 1201, 1225, 1247, 1281, 1299, 1334, 1368, 1417,
1440, 1518, 1586, 1649, 1689, 1709, 1745 (C=O).
UV (chloroform, λmax, nm (logε)): 241 (3.66), 314
Solvents used were freshly distilled, chemicals were
of pure grade. Palladium(II) acetate was obtained
according to the procedure in [10]. Lactones 1 and 2
were obtained by extraction of herbal raw material fol-
DOKLADY CHEMISTRY Vol. 426 Part 2 2009

140
BELOVODSKII et al.
1
12.0, 6.2), 2.18 (br d, 1H, 9-H, J = 15.5), 2.29 (br d, 1H,
3-H, J = 13.0), 2.43 (s, 3H, SCH3), 3.22 (ddd, 1H, 7-H,
J = 11.8, 6.0, 5.3), 4.39 (br d, 1H, 15-H), 4.46 (dd, 1H,
8-H, J = 4.6, 4.5), 4.73 (br s, 1H, 15-H), 7.15 (br dd, 1H,
4'-H, J = 7.5, 7.0), 7.27 (br d, 1H, 6'-H, J = 7.8), 7.31
(br dd, 1H, 5'-H, J = 8.0, 6.9), 7.39 (br d, 1H, 3'-H, J =
7.6), 7.76 (s, 1H, 13-H). 13C NMR (δ, ppm): 16.15 (q,
SCH3), 17.66 (q, C-14), 22.64 (t, C-2), 25.73 (t, C-6),
34.33 (s, C-10), 36.74 (t, C-3), 39.10 (d, C-7), 41.24 (t,
C-9), 42.05 (t, C-1), 46.27 (d, C-5), 77.03 (d, C-8),
106.54 (t, C-15), 125.11 (d, C-5'), 126.49 (d, C-6'),
127.88 (d, C-3'), 129.63 (d, C-4'), 132.08 (d, C-13),
133.12 (s, C-1'), 134.53 (s, C-11), 139.67 (s, C-2'),
149.04 (s, C-4), 171.69 (s, C-12).
(4.40). H NMR (CDCl3, δ, ppm, J, Hz): 0.86 (s, 3H,
14-H3), 1.26 (m, 1H, 1-H), 1.39 (ddd, 1H, 6-H, J = 13.9,
12.6, 12.2), 1.47–1.68 (m, 4H, 1,2,2,9-H), 1.90–2.06
(m, 3H, 3,5,6-H), 2.24 (dd, 1H, 9-H, J = 13.3, 1.2), 2.34
(ddd, 1H, 3-H, J = 13.4, 1.8, 1.5), 3.40 (ddd, 1H, 7-H,
J = 11.7, 5.6, 5.3), 3.83 (s, 3H, OCH3), 4.41 (br s, 1H,
15-H), 4.48 (dd, 1H, 8-H, J = 4.7, 3.5), 4.75 (br s, 1H,
15-H), 6.93 (d, 2H, 3',5'-H, J = 8.8), 7.37 (s, 1H, 13-H),
7.48 (d, 2H, 2',6'-H, J = 8.8). 13C NMR (δ, ppm): 17.66
(q, C-14), 22.72 (t, C-2), 24.54 (t, C-6), 34.50 (s, C-10),
36.85 (t, C-3), 39.46 (d, C-7), 41.38 (t, C-9), 42.19 (t,
C-1), 46.37 (d, C-5), 55.32 (q, OCH3), 76.84 (d, C-8),
106.67 (t, C-15), 114.48 (d, C-3',5'), 126.84 (s, C-1'),
129.67 (s, C-11), 131.45 (d, C-2',6'), 134.72 (d, C-13),
149.13 (s, C-4), 168.80 (s, C-4'), 172.77 (s, C-12).
For C22H26O2S anal. calcd. (%): C, 74.54; H, 7.39;
S, 9.05. Found (%): C, 74.42; H, 7.35; S, 9.02.
For C22H26O3 anal. calcd. (%): C, 78.07; H, 7.74.
Found (%): C, 78.01; H, 7.95.
(4aS,8aR,9aR)-3-(4-Methoxybenzyl)-8a-methyl-
5-methylene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-
b]furan-2(4H)-one (6). Yield 9%, mp 136–139°C
(from ethyl acetate), [α]589 +125 (c 0.733, CHCl3). IR
(3aR,4aS,8aR,9aR,E)-3-(4-Dimethoxybenzylide-
ne)-8a-methyl-5-methylenedecahydronaphtho[2,3-
b]furan-2(3H)-one (4). Yield 81%, mp 160–162°C
(from ethanol), [α]589 +534 (c 1.047, CHCl3). IR (ν,
(ν, cm–1): 895, 1017, 1045, 1055, 1177, 1247, 1512,
cm–1): 808, 890, 1001, 1033, 1139, 1172, 1214, 1248,
1272, 1327, 1337, 1464, 1520, 1594, 1651, 1743
(C=O). UV (chloroform, λmax, nm (logε)): 246 (4.13),
1
1678, 1746 (C=O). H NMR (CDCl3, δ, ppm, J, Hz):
0.86 (s, 3H, 14-H3), 1.12 (dd, 1H, 9-H, J = 12.2, 11.7),
1.29 (ddd, 1H, 1-H, J = 13.7, 13.2, 4.9), 1.54–1.62 (m,
3H, 1,2,2-H), 1.70 (br d, 1H, 5-H, J = 10.8), 1.94 (ddd,
1H, 3-H, J = 12.7, 12.7, 5.4), 2.26–2.36 (m, 3H, 3,6,9-
H), 2.74 (dd, 1H, 6-H, J = 13.7, 3.9), 3.48 (d, 1H, 13-H,
J = 14.7), 3.55 (d, 1H, 13-H, J = 14.7), 3.75 (s, 3H,
OCH3), 4.54 (br s, 1H, 15-H), 4.81 (m, 1H, 8-H), 4.84
(br s, 1H, 15-H), 6.79 (ddd, 2H, 3',5'-H, J = 8.3, 2.9,
2.2), 7.13 (ddd, 2H, 2',6'-H, J = 8.3, 3.2, 2.2). 13C NMR
(δ, ppm): 16.01 (q, C-14), 21.87 (t, C-2), 25.33 (t, C-6),
27.98 (t, C-13), 35.82 (t, C-3), 36.48 (s, C-10), 40.33 (t,
C-1), 47.14 (t, C-9), 49.58 (d, C-5), 54.81 (q, OCH3),
77.47 (d, C-8), 106.53 (t, C-15), 113.58 (d, C-3',5'),
123.51 (s, C-1'), 128.96 (d, C-2',6'), 130.04 (s, C-11),
147.88 (s, C-4), 157.77 (s, C-4'), 162.94 (s, C-7),
173.66 (s, C-12). MS (m/z (Irel, %)): 340 (3), 339 (24),
338 (100), 293 (74), 215 (30), 171 (19), 123 (20),
121 (51).
1
326 (4.32). H NMR (CDCl3, δ, ppm, J, Hz): 0.81 (s,
3H, 14-H3), 1.22 (m, 1H, 1-H), 1.34 (ddd, 1H, 6-H, J =
13.0, 12.8, 12.6), 1.45–1.58 (m, 4H, 1,2,2,9-H), 1.87 (d,
1H, 5-H, J = 12.9), 1.91–2.04 (m, 2H, 3,6-H), 2.19 (d,
1H, 9-H, J = 15.5), 2.28 (d, 1H, 3-H, J = 13.2), 3.37
(ddd, 1H, 7-H, J = 11.4, 5.6, 5.5), 3.82 (s, 3H, OCH3),
3.85 (s, 3H, OCH3), 4.36 (br s, 1H, 15-H), 4.44 (dd, 1H,
8-H, J = 4.1, 3.6), 4.70 (br s, 1H, 15-H), 6.86 (d, 1H, 5'-
H, J = 8.5), 6.97 (s, 1H, 2'-H), 7.12 (d, 1H, 6'-H, J =
7.0), 7.30 (s, 1H, 13-H). 13C NMR (δ, ppm): 17.47 (q,
C-14), 22.53 (t, C-2), 24.56 (t, C-6), 34.34 (s, C-10),
36.68 (t, C-3), 39.40 (d, C-7), 41.21 (t, C-9), 42.02 (t,
C-1), 46.20 (d, C-5), 55.76 (q, two OCH3), 76.66 (d, C-
8), 106.48 (t, C-15), 111.22 (d, C-6'), 112.72 (d, C-2'),
122.92 (d, C-5'), 126.97 (s, C-1'), 129.93 (s, C-11),
134.84 (d, C-13), 148.88 (s, C-4,3'), 150.37 (s, C-4'),
172.44 (s, C-12).
For C22H26O3 calcd.: M = 338.1876. Found: m/z
338.1872 [M]+.
For C23H28O4 anal. calcd. (%): C, 74.97; H, 7.66.
Found (%): C, 74.90; H, 7.92.
(4aS,8aR,9aR)-3-(3,4-Dimethoxybenzyl)-8a-methyl-
(3aR,4aS,8aR,9aR,E)-3-(2-Methylthiobenzylide-
ne)-8a-methyl-5-methylenedecahydronaphtho[2,3-
b]furan-2(3H)-one (5). Yield 79%, mp 95–98°C,
[α]589 + 355 (c 1.126, CHCl3). IR (ν, cm–1): 748, 759,
898, 1103, 1171, 1218, 1440, 1647, 1746 (C=O). UV
(chloroform, λmax, nm (logε)): 257 (4.16), 283 (3.98),
5-methylene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-
1
b]furan-2(4H)-one (7). Yield 13%. Oily matter. H
NMR (CDCl3, δ, ppm, J, Hz): 0.87 (s, 3H, 14-H3),
1.12 (dd, 1H, 9-H, J = 11.8, 11.8), 1.29 (ddd, 1H, 1-H,
J = 13.3, 13.3, 5.3), 1.55–1.64 (m, 3H, 1,2,2-H), 1.80
(dddd, 1H, 5-H, J = 12.5, 3.3, 1.7, 1.3), 1.93 (ddd, 1H,
3-H, J = 12.8, 12.8, 5.8), 2.28 (m, 1H, 6-H), 2.30 (dd,
1H, 9-H, J = 12.3, 6.4), 2.36 (dddd, 1H, 3-H, J = 13.4,
3.8, 2.2, 1.8), 2.77 (dd, 1H, 6-H, J = 13.8, 3.8), 3.50 (d,
1H, 13-H, J = 15.5), 3.56 (d, 1H, 13-H, J = 14.8), 3.83
(s, 3H, OCH3), 3.84 (s, 3H, OCH3), 4.55 (dd, 1H, 15-H,
1
338 (3.46). H NMR (CDCl3, δ, ppm, J, Hz): 0.83 (s,
3H, 14-H3), 1.21 (ddd, 1H, H1, J = 12.7, 12.3, 5.8), 1.44
(ddd, 1H, 6-H, J = 13.4, 12.6, 12.3), 1.48–1.57 (m, 4H,
1,2,2,9-H), 1.80 (ddd, 1H, 6-H, J = 14.0, 6.7, 2.4), 1.83
(br d, 1H, 5-H, J = 14.0), 1.97 (ddd, 1H, 3-H, J = 12.6,
DOKLADY CHEMISTRY Vol. 426 Part 2 2009

SESQUITERPENE METYLENELACTONES
141
J = 3.0, 1.2), 4.84 (dd, 1H, 8-H, J = 11.5, 6.3), 4.85 (dd, (δ, ppm): 16.76 (t, C-2), 22.37 (q, C-15), 28.54 (q, C-14),
1H, 15-H, J = 2.8, 1.4), 6.73 (dd, 1H, 6'-H, J = 8.2, 2.0), 32.80 (s, C-10), 32.83 (t, C-3), 38.03 (d, C-4), 38.87 (d,
6.76 (d, 1H, 5'-H, J = 8.2), 6.81 (d, 1H, 2'-H, J = 2.0). C-7), 41.96 (t, C-1), 42.44 (t, C-9), 55.95 (q, OCH3),
13C NMR (δ, ppm): 16.35 (q, C-14), 22.18 (t, C-2), 76.17 (d, C-8), 111.33 (d, C-5'), 112.76 (d, C-2'),
25.70 (t, C-6), 28.77 (t, C-13), 36.14 (t, C-10), 36.83 (s, 114.53 (d, C-6), 123.71 (d, C-6'), 127.11 (s, C-11),
C-3), 40.68 (t, C-1), 47.55 (t, C-9), 49.97 (d, C-5), 128.23 (s, C-1'), 135.81 (d, C-13), 149.13 (s, C-4'),
55.72 (q, two OCH3), 77.82 (d, C-8), 106.89 (t, C-15), 150.30 (s, C-5), 150.60 (s, C-3'), 172.38 (s, C-12). MS
(m/z (Irel, %)): 370 (5), 369 (28), 368 (100), 337 (21),
111.15 (d, C-6'), 111.67 (d, C-2'), 120.04 (d, C-5'),
123.76 (s, C-1'), 130.97 (s, C-11), 147.53 (s, C-3'), 323 (42), 307 (35), 305 (43), 241 (18), 165 (20), 152
148.17 (s, C-4), 148.99 (s, C-4'), 163.41 (s, C-7), (25), 151 (69), 138 (20), 105 (21).
174.05 (s, C-12).
For C23H28O4 calcd.: M = 368.1982. Found: m/z
368.1978 [M]+.
For C23H28O4 anal. calcd. (%): C, 74.97; H, 7.66.
Found (%): C, 74.90; H, 7.92.
(8aR,9aR)-3-(3,4-Dimethoxybenzyl)-5,8a-dime-
thyl-6,7,8,8a,9,9a-hexahydronaphtho[2,3-b]furan-
2(5H)-one (10). Yield 36%. Oily matter. [ [α]589 –123
(4aS,8aR,9aR)-3-(2-Methylthiobenzyl)-8a-methyl-
5-methylene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-
b]furan-2(4H)-one (8). Yield 17%, mp 112–113°C
(from ethanol). IR (ν, cm–1): 755, 906, 1015, 1058,
1099, 1128, 1223, 1265, 1584, 1543, 1680, 1748
(C=O). UV (ethanol, λmax, nm (logε)): 210 (4.07), 251
(c 0.780, CHCl3). IR (ν, cm–1): 732, 756, 1029, 1059,
1107, 1140, 1237, 1262, 1341, 1419, 1464, 1515, 1590,
1658, 1746 (C=O). UV (λmax, nm (logε)): 234 (4.00),
1
280 (4.19). H NMR (CDCl3, δ, ppm, J, Hz): 1.15 (d,
1
(3.15), 292 (1.36). H NMR (CDCl3, δ, ppm, J, Hz):
3H, 15-H3, J = 6.3), 1.27 (m, 1H, 1-H), 1.29 (s, 3H, 4-
H3), 1.41–1.45 (m, 2H, 2,9-H), 1.56–1.61 (m, 3H,
1,3,3-H), 1.81 (ddddd, 1H, 2-H, J = 13.7, 13.3, 13.2,
3.9, 3.4), 2.04 (dd, 1H, 9-H, J = 11.7, 4.9), 2.57 (ddd,
1H, 4-H, J = 12.7, 7.3, 5.8), 3.47 (d, 1H, 13-H, J =
14.7), 3.55 (d, 1H, 13-H, J = 15.1), 3.79 (s, 3H, OCH3),
3.80 (s, 3H, OCH3), 4.95 (dd, 1H, 8-H, J = 13.2, 4.9),
6.09 (s, 1H, 6-H), 6.72 (dd, 1H, 6'-H, J = 8.1, 1.7), 6.73
0.85 (s, 3H, 14-H3), 1.16 (dd, 1H, 9-H, J = 11.8, 11.8),
1.30 (m, 1H, 1-H), 1.53–1.61 (m, 3H, 1,2,2-H), 1.79 (br
d, 1H, 5-H, J = 11.1), 1.91 (ddd, 1H, 3-H, J = 13.0,
13.0, 5.8), 2.18 (dd, 1H, 3-H, J = 13.7, 13.1), 2.28–2.34
(m, 2H, 6,9-H), 2.44 (s, 3H, SCH3), 2.67 (dd, 1H, 6-H,
J = 14.0, 3.5), 3.66 (d, 1H, 13-H, J = 15.8), 3.71 (d, 1H,
13-H, J = 16.0), 4.44 (d, 1H, 15-H, J = 1.3), 4.78 (d, 1H,
15-H, J = 1.3), 4.85 (dd, 1H, 8-H, J = 11.3, 6.3), 7.09
(m, 1H, 4'-H), 7.18–7.23 (m, 3H, 3',5',6'-H). 13C NMR
(δ, ppm): 15.97 (q, C-14), 16.37 (q, SCH3), 22.20 (t, C-
2), 25.76 (t, C-6), 27.41 (t, C-13), 36.13 (t, C-3), 36.67
(s, C-10), 40.70 (t, C-1), 47.57 (t, C-9), 49.83 (d, C-5),
77.89 (d, C-8), 106.76 (t, C-15), 121.91 (s, C-1'),
125.01 (d, C-3'), 125.77 (d, C-5'), 127.24 (d, C-6'),
129.27 (d, C-4'), 135.70 (s, C-11), 137.16 (s, C-2'),
148.15 (s, C-4), 164.42 (s, C-7), 173.91 (s, C-12). MS
(m/z (Irel, %)): 356 (8), 355 (25), 354 (100), 339 (14),
307 (40), 293 (21), 137 (50), 121 (51). For C22H26O2S
13
(d, 1H, 5'-H, J = 8.1), 6.79 (d, 1H, 2'-H, J = 1.4). C
NMR (δ, ppm): 16.40 (t, C-2), 22.18 (q, C-15), 26.01
(q, C-14), 28.96 (t, C-13), 32.46 (t, C-3), 38.04 (s, C-
10), 38.18 (d, C-4), 41.77 (t, C-1), 46.67 (t, C-9), 55.72
(q, OCH3), 75.95 (d, C-8), 111.15 (d, C-5'), 111.93 (d,
C-2'), 113.97 (d, C-6), 119.60 (s, C-11), 120.29 (d, C-
6'), 130.98 (s, C-1'), 147.50 (s, C-3'), 148.82 (s, C-4'),
157.70 (s, C-7), 162.25 (s, C-5), 174.76 (s, C-12). MS
(m/z (Irel, %)): 370 (4), 369 (27), 368 (100), 323 (73),
324 (19), 246 (30), 215 (18), 201 (21), 171 (12),
151 (38).
calcd.: M = 354.1648. Found: m/z 354.1647 [M]+.
For C23H28O4 calcd.: M = 368.1982. Found: m/z
(3aR,8aR,9aR,E)-3-(3,4-Dimethoxybenzylidene)-
5,8a-dimethyl-3,3a,6,7,8,8a,9,9a-octahydronaphtho[2,3-
b]furan-2(5H)-one (9). Yield 20%. Oily matter. IR (ν,
cm–1): 759, 1024, 1140, 1182, 1232, 1250, 1275, 1331,
368.1985 [M]+.
ACKNOWLEDGMENTS
1420, 1464, 1516, 1597, 1645, 1745 (C=O). UV (λmax
,
nm (logε)): 240 (4.05), 328 (4.19). 1H NMR (CDCl3, δ,
ppm, J, Hz): 1.04 (d, 3H, 15-H3, J = 7.6), 1.14 (ddd, 1H,
1-H, J = 13.5, 13.2, 3.5), 1.25 (s, 3H, 14-H3), 1.38–1.60
(m, 5H, 1,2,3,3,9-H), 1.82 (m, 1H, 2-H), 2.13 (dd, 1H,
9-H, J = 14.7, 2.9), 2.40 (ddd, 1H, 3-H, J = 7.9, 4.4,
3.0), 3.90 (s, 3H, OCH3), 3.92 (s, 3H, OCH3), 4.07
(ddd, 1H, 7-H, J = 6.5, 2.5, 1.8), 4.79 (ddd, 1H, 8-H,
J = 6.4, 3.0, 2.6), 5.39 (d, 1H, 6-H, J = 3.5), 6.91 (d, 1H,
5'-H, J = 8.5), 7.09 (d, 1H, 2'-H, J = 2.0), 7.21 (dd, 1H,
6'-H, J = 8.2, 2.0), 7.39 (d, 1H, 13-H, J = 1.8). 13C NMR
This work was supported by the Russian Foundation
for Basic Research (project no. 08–03–00340).
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