Synthetic transformations of higher terpenoids: XXIX.* gold catalyzed cycloisomerization of propargylaminomethyl substituted and propargyloxymethyl substituted furanolabdanoids

Article abstract of DOI:10.1134/S1070428012080088

16-Propargylaminomethyl substituted and 16-propargyloxymethyl substituted furanolabdanoids were synthesized, which under the action of AuC_l3 in acetonitrile underwent cycloisomerization forming 7-hydroxyisoindolines or 7-hydroxydihydroisobenzof

Full text of DOI:10.1134/S1070428012080088

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 8, pp. 1081−1089. © Pleiades Publishing, Ltd., 2012.
Original English Text © Yu.V. Kharitonov, E.E. Shults, M.M. Shakirov, I.Yu. Bagryanskaya, G.A. Tolstikov, 2012, published in Zhurnal Organicheskoi Khimii,
2012, Vol. 48, No. 8, pp. 1085−1092.
Synthetic Transformations of Higher Terpenoids: XXIX.*
Gold Catalyzed Cycloisomerization of Propargylaminomethyl
Substituted and Propargyloxymethyl
Substituted Furanolabdanoids
Yu. V. Kharitonov, E. E. Shults, M. M. Shakirov, I. Yu. Bagryanskaya, and G. A. Tolstikov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, Novosibirsk, 630090 Russia
e-mail: schultz@nioch.nsc.ru
Received February 22, 2012
Abstract—16-Propargylaminomethyl substituted and 16-propargyloxymethyl substituted furanolabdanoids
were synthesized, which under the action of AuCl3 in acetonitrile underwent cycloisomerization forming
7-hydroxyisoindolines or 7-hydroxydihydroisobenzofurans substituted by a terpenoid fragment.
DOI: 10.1134/S1070428012080088
Vegetable furanolabdanoids are natural compounds
possessing versatile pharmacologic activity [2].
Lambertianic acid (I) and its methyl ester II produced
by the Siberian pine Pinus sibirica R. Mayr. belong
to available compounds of this type [3]. Synthetic
transformations of methyl lambertianate led to the
preparation of a number of natural substances [4–6] and
pharmacologically promising agents [7, 8].
p-toluenesulfonyl chloride in dichloromethane in the
presence of triethylamine furnishes the corresponding
sulfamide V (Scheme 1). The alkylation of compound V
with propargyl bromide led to the formation of methyl
N-tosyl-16-(propargylaminomethyl)lambertianate (VI).
After the treatment of compound VI withAuCl3 (5 mol%)
in acetonitrile 7-hydroxyisoindoline substituted in the
position 4 with terpenoid fragment, compound III, was
obtained.
Aiming at the preparation of heterocyclic derivatives
of the methyl lambertianate with 7-hydroxyisoisoindoli-
none or 7-hydroxydihydroisobenzofuran substituents we
studied the method of gold-catalyzed synthesis of benza-
renes fused with five- and six-membered rings [9]. The
method of enyne cycloisomerization of ω-alkynylfurans
catalyzed with Au(III) was successfully used in the
synthesis of number of biologically active compounds,
of some natural substances among them [9, 10], but
the application of this method to the transformations of
polyfunctional furan compounds of diterpene type was
not described.
Methyl 16-(formyl)lambertianate (VII) [11] was
utilized as the initial compound in the synthesis of dihy-
droisobenzofurans with a terpene substituent VIII, IXa,
IXb (Scheme 2). The reduction of methyl 16-(formyl)
lambertianate (VII) with sodium borohydride in methanol
gave rise to the corresponding 16-hydroxymethyl de-
rivative X whose reaction with propargyl bromide in the
presence of sodium hydride in DMF provided propargyl
furyl ether XI. The catalyzed by AuCl3 cycloisomer-
ization of compound XI gave cleanly 7-hydroxy-1,3-
dihydroisobenzofuran VIII with a terpenoid fragment
in the position 4.
In the reaction of methyl 16-(formyl)lambertianate
(VII) with propargyl bromide in the presence of acti-
vated zinc powder in the mixture THF–aqueous NH4Cl
homopropargyl alcohols XIIa, XIIb were obtained as
mixtures of 1’(R)- and 1’(S)-diastereomers in a ratio
The key compound in the synthesis of 7-hydroxy-
isoindoline-substituted labdanoid III is methyl 16-(ami-
nomethyl)lambertianate (IV) [8], whose reaction with
_______________
* For Communication XXVIII, see [1]
1081

KHARITONOV et al.
1082
Scheme 1.
NHTs
NH2
16
15
13
12
11
8
20
O
14
O
O
17
9
6
1
2
3
10
5
TsCl, Et3N
7
4
H
RO2C
19
H
H
18
MeO2C
MeO2C
I, II
V
IV
Ts
Ts
N
N
3
3a
2
3''
4''
1''
1
10'
7a
9'
4
14'
Br
K2CO3
5''
O
,
7
5
AuCl3
11'
6
5'
4'
3'
OH
4a'
6'
7'
8a'
2'
1'
8'
12'
H
13'
H
MeO2C
MeO2C
VI, 73%
III, 79%
R = H (I), CH3 (II).
Scheme 2.
CHO
O
3
1
OH
Br
O
O
4
2'
3'
4'
1'
,
7
AuCl3
NaBH4
NaH, DMF
OH
4'
O
O
6'
5'
2'
8a'
1'
H
MeO2C
H
MeO2C
VII
X
VIII, 78%
XI, 55%
3''
H
2''
1''
2''
OH
H
2'
1'
3'
4'
2'
3''
O
H
O
1
3'
4'
3
3a
1'
4''
Br
,
O
4
7a
Br
AuCl3
l
H C
, N
Zn
4
O
7
5
VII
5'
NaH
OH
4'
4'a
8а'
6'
7'
3'
2'
1'
8'
H
MeO2C
H
H
MeO2C
MeO2C
XIIIa, XIIIb
XIIa, XIIb, 66%
IXa, IXb
diterpene alcohols XIIa, XIIb with propargyl bromide
in DMF in the presence of sodium hydride we obtained
the corresponding diacetylene derivatives of methyl
~1 : 1. Compounds XIIa, XIIb were also obtained
from diterpene aldehyde VII and propargylmagnesium
bromide (ratio ~1 : 1, yield 74%). In the reaction of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

SYNTHETIC TRANSFORMATIONS OF HIGHER TERPENOIDS: XXIX.
1083
lambertianate XIIIa, XIIIb as a mixture of 1’(R)- and
1’(S)-diastereomers (oily substance); during keeping in
air 1’(R)-diastereomer XIIIa slowly crystallized from
the mixture. A single crystal of compound XIIIa was
subjected to XRD analysis (see the figure). The cycloi-
somerization of the mixture of stereomers XIIIa, XIIIb
catalyzed by AuCl3 occurred selectively involving the
acetylene bond activated with oxygen and resulted in the
formation of a mixture of 3(R)- and 3(S)-7-hydroxy-3-
(prop-2-yn-1-yl)-1,3-dihydroisobenzofurans IXа, IXb
substituted in the position 4 with a terpenoid fragment.
The structure of XIIIa was elucidated by an X-ray
crystal structure determination (see the figure). The
six-membered rings in the molecule exist in the chair
conformation, the furan ring is flat (root-mean-square
deviation of atoms from the plane is 0.008 Å). The bond
lengths and bond angles in molecule XIIIa are close to
the average statistical values [12] and in the main part of
the skeleton coincide in the 3σ limits with the parameters
of the nearest analog, the methyl 16-cyanolambertianate
[13]. The crystal packing contains no shortened compared
to the sum of van der Waals radii nonvalent contacts.
Molecular structure of methyl (1S,4aR,5S,8aR)-1,4a-dimethyl-
6-methylidene-5-(2-{2-[(R)-1-(prop-2-yn-1-yloxy)but-3-yn-
1-yl]furan-3-yl}ethyl)decahydronaphthalene-1-carboxylate
(XIIIa) from X-ray data.
IXb results in the nonequivalence of protons H1 and in
the appearance in the 1Н NMR spectra of two one-proton
doublets in a weak field [e.g., δ 5.05, 5.10 ppm, J 10.2 Hz
(VIII)]. Similar changes were observed in the spectra of
N-substituted 7-hydroxyisoindolines [14].
The structure of all compounds is confirmed by the 1
Н
and 13С NMR spectra. The formation of compounds ХIIа,
XIIb, ХIIIа, XIIIb in the form of diastereomers mixture
(owing to the introduction of the propargyl substituent)
is seen from the doubling of some proton and carbon
signals in the 1Н and 13С NMR spectra. The difference in
the chemical shifts of protons H2’ of diastereomers ХIIа,
The appearance a substituent in the position 3 of
terpenoid dihydroisobenzofurans IXa, IXb led to the
increase in the difference in the chemical shifts of
the doublet signals of protons Н1 (δ 5.25, 5.09 ppm,
J 10.2 Hz). 13С NMR spectra of compounds III, VIII,
IXa, IXb contain characteristic signals of atoms С3a
(136.40–139.52 ppm), С4 (127.96–129.44 ppm), C5
(128.54–128.77 ppm), С6 (114.16–114.61 ppm), C7
(147.44–147.81 ppm), C7a (122.42–125.53 ppm). The
position of the hydroxy group at the atom С7 is confirmed
XIIb equals 0.01 ppm, of diastereomers ХIIIа, XIIIb
,
0.03–0.04 ppm.
The formation of heterocyclic systems of isoindoline
III and of dihydroisobenzofuran VIII, IXa, IXb was
confirmed by the 1Н and 13С NMR data. In the 13С NMR
spectrumofthediastereomersIXa, IXbmixtureadoubling
of signals of some carbon atoms of the terpene skeleton
and dihydroisobenzofuran was observed originating
from the introduction of the propargyl substituent into
the position С3. The formation of dihydroisobenzofurans
IXa, IXb as a mixture of diastereomers follows from the
1
by the data of 2D spectra of Н−13С correlation. In
1
1
the spectra Н−13С COLOC and Н−13С HMBC of
compound VIII cross-peaks were observed between the
signals of the protons Н10’ of the terpene skeleton and
the signal of the atom С5 (δ 128.61 ppm). Besides in the
monoresonance spectra the signals of atoms C1 and С3
appear as broadened singlets (J 1.7–2.0 Hz) confirming
the presence of substituents at the atoms С4 and С7 of the
dihydroisobenzofuran fragment.
1
presence in their Н NMR spectra of double signals of
protons H1’ and H3 (∆δ 0.03–0.06 ppm). A characteristic
feature of the 1Н NMR spectra of compounds III, VIII,
IXa, IXb is the appearance of doublet signals of protons
Н6 and Н5 at 6.59–6.67 and 6.88–6.95 ppm respectively,
J 7.8–8.0 Hz. The introduction of a hydroxy group in
the position С7 of 4-terpenyl substituted derivatives of
isoindoline III and dihydroisobenzofuran VIII and IXa,
Thus new derivatives of lambertianic acid were
obtained containing the 16-propargylaminomethyl or
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

KHARITONOV et al.
1084
Synthesis of methyl 16-aminomethyl lambertianate
(IV) was described in [8]. Methyl 16-formyllambertianate
(VII) and methyl 16-(hydroxymethyl )lambertianate (X)
were obtained by procedure [11].
16-propargyloxymethyl substituents in the position
С16. The new acetylene derivatives of furanolabdanoids
exhibited a high activity and regioselectivity in the cy-
cloisomerization catalyzed by gold(III) chloride. Hybride
structures were synthesized combining the fragments of
7-hydroxy-1,3-dihydroisobenzofurans or 7-hydroxyisoin-
dolines and labdane diterpenoids.
Methyl (1S,4аR,5S,8аR)-1,4а-dimethyl-6-
methylidene-5-(2-{2-[(4-methylphenylsulfonamido)
methyl ]furan-3-yl}ethyl)decahydronaphthalene-1-
carboxylate (V). To a solution of 1.00 g (2.2 mmol) of
methyl 16-(aminomethyl )lambertianate (IV) in 20 ml of
dichloromethane was added at stirring 0.77 ml (5.6 mmol)
of triethylamine and 0.42 g (2.2 mmol) of tosyl chloride.
The reaction mixture was stirred for 24 h at room tem-
perature, diluted with 50 ml of chloroform, washed with
water (3 × 50 ml), dried with MgSO4, and evaporated.
Yield 1.06 g (93%), oily substance, [α]D +29.12° (c 0.57,
CHCl3). UV spectrum, λmax, nm (log ε): 225 (4.07). IR
spectrum, cm–1: 3277, 3022, 2945, 2876, 2847, 1722,
1645, 1447, 1331, 1229, 1161, 1094, 1051, 984, 891,
EXPERIMENTAL
1Н and 13С NMR spectra were registered on spec-
trometers Bruker AV-300 [operating frequencies 300.13
(1Н), 75.47 MHz (13С)] and Bruker AV-400 [operating
frequencies 400.13 (1Н), 100.78 MHz (13С)] from solu-
tions of compounds in CDCl3, the signals of the solvent
served as internal references (δH 7.24, δС 76.9 ppm).
The multiplicity of signals in the 13С NMR spectra was
determined by standard procedures at registering spectra
in the mode of J-modulation (JMOD). The assignment
of signals in NMR spectra was performed taking into ac-
count the data of [8, 13]; for compound VIII were taken
2D correlation proton-proton and carbon-proton spectra
COSY, НХСО, COLOC, HMBC. In the description of
1
814, 756, 663. Н NMR spectrum, δ, ppm: 0.45 s (3Н,
С20Н3), 0.92 d.t (1H, H1, J 13.5, 4.2 Hz), 0.99 d.t (1H,
H3, J 13.6, 4.2 Hz), 1.15 s (3Н, С19Н3), 1.22 d.d (1Н, H5,
J 12.1, 3.1 Hz), 1.45 m (1Н, Н2), 1.47 m (1Н, Н9), 1.58 m
(1Н, Н11), 1.70–1.81 m (4H, H1,2,6,11), 1.85 m (1Н, Н7),
1.96 m (1Н, Н6), 2.13 m (2Н, Н3,12), 2.34 m (1Н, Н12),
2.37 m (1Н, Н7), 2.41 s (3Н, СН3), 3.60 s (3Н, OCH3),
4.03 d, 4.06 d (2Н, СН2, J 11.6 Hz), 4.48 s, 4.85 s (2Н,
Н17), 4.72 m (1Н, NH), 6.11 d (1Н, Н14, J14,15 2.0 Hz),
7.16 d (1Н, Н15, J14,15 2.0 Hz), 7.23 d (2Н, Н3',5', J 7.8 Hz),
7.67 d (2Н, Н2',6', J 7.8 Hz). 13C NMR spectrum, δ, ppm:
12.52 q (C20), 19.81 t (С2), 21.43 q (СН3), 22.79 t (С12),
24.10 t (С11), 26.15 t (C6), 28.67 q (C19), 37.95 t (СН2),
38.04 t (C3), 38.60 t (C7), 38.91 t (C1), 40.03 s (C10),
44.16 s (С4), 51.06 q (ОСН3), 54.71 d (С9), 56.05 d (С5),
106.52 t (С17), 111.31 d (С14), 122.96 s (С13), 126.97 d
(C2',6'), 129.46 d (C3',5'), 136.71 s (C4'), 141.77 d (С15),
143.18 s (C1'), 144.40 s (С16), 147.64 s (С8), 177.64 s
(С18). Mass spectrum, m/z (Irel, %): 513 (0.19), 429 (11),
358 (29), 342 (29), 283 (12), 263 (12), 249 (18), 235 (12),
194 (11), 189 (34), 184 (12), 181 (90), 171 (18), 161 (16),
155 (33), 149 (17), 133 (14), 122 (19), 121 (100), 119
(17), 110 (12), 109 (49), 107 (26), 105 (17), 95 (13), 94
(11), 93 (56), 91 (56), 85 (35), 83 (52), 81 (23), 79 (16),
55 (13). Found [M]+ 513.2537. C29H39NO5S. Calculated
M 513.2543.
1
the Н and 13С NMR spectra the used numeration of
atoms of diterpene framework was indicated in Scheme
1 in formula I for compounds V, VI, X, XII, XIII and
formula III for compounds VIII, IX. The recording of
mass spectra, determination of molecular masses and el-
emental composition of compounds was performed on a
high resolution mass spectrometer DFS Thermo Scientific
(ionizing electrons energy 70 eV, vaporizer temperature
230–280°С). The specific rotation was measured on a po-
larimeter PoLAAr 3005 at room temperature (20–23°С).
IR spectra were taken on a spectrophotometer Vector-22
from mulls in mineral oil. UV spectra were recorded on a
spectrophotometer HР 8453 UVVis in ethanol. The XRD
analysis of compound XIIIa was carried out on a dif-
fractometer KарраAрех II Bruker with a two-coordinate
CCD detector (MoKα-radiation, graphite monochromator,
ω-φ scanning in the range up to 2θ<51°). Melting points
were measured on a heating block Stuart SMF-38.
The monitoring of reaction progress and checking
of homogeneity of compounds obtained was performed
by TLC on Silufol UV-254 plates, eluents chloroform–
ethanol, 3 : 1, petroleum ether–ethyl acetate, 10 : 1. The
spots were visualized by spraying the plates with 10%
water solution of H2SO4 followed by heating at 100°C
or by UV irradiation.
Methyl (1S,4аR,5S,8аR)-1,4а-dimethyl-5-[2-(2-
{[4-methyl-N-(prop-2-yn-1-yl)phenylsulfonamido]
methyl}furan-3-yl)ethyl]-6-methylidenedecahydro-
naphthalene-1-carboxylate (VI). To the stirred solution
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

SYNTHETIC TRANSFORMATIONS OF HIGHER TERPENOIDS: XXIX.
1085
(1Н, H1, J 10.4 Hz), 4.53 d (1Н, H1, J 10.4 Hz), 4.56 m
(2Н, H3), 4.58 s (1Н, Н11'), 4.91 s (1Н, Н11'), 5.50 br.s(1Н,
ОН), 6.59 d (1Н, Н6, J 7.6 Hz), 6.88 d (1Н, Н5, J 7.6 Hz),
7.29 d (2Н, Н3'',5'', J 7.8 Hz), 7.75 d (2Н, Н2'',6'', J 7.8 Hz).
13C NMR spectrum, δ, ppm: 12.49 q (C14'), 19.84 t (С3'),
21.40 q (СН3), 24.44 t (С9'), 26.17 t (C8'), 30.91 t (С10'),
28.67 q (C13'), 38.01 t (C2'), 38.59 t (C7'), 38.92 t (C4'),
40.15 s (C4a'), 44.20 s (С1'), 51.09 q (ОСН3), 51.79 t (С3),
53.24 t (С1), 55.29 d (С8a'), 56.09 d (С5'), 106.38 t (С11'),
114.40 d (С6), 122.42 s (С7a), 127.47 d (C2'',6''), 128.73 d
(C5), 129.44 s (С4), 129.70 d (C3'',5''), 133.56 s (C4''),
136.40 s (C3a), 143.57 s (C1''), 147.74 s (С6'), 147.78 s
(C7), 178.07 s (С12'). Mass spectrum, m/z (Irel, %): 551
(6), 399 (18), 398 (66), 397 (37), 396 (88), 338 (15), 336
(12), 302 (10), 301 (38), 273 (10), 189 (11), 160 (16),
155 (15), 149 (13), 148 (19), 147 (34), 146 (100), 133
(11), 123 (12), 121 (39), 119 (12), 109 (18), 107 (19), 105
(14), 95 (18), 93 (17), 92 (10), 91 (48), 81 (22), 79 (13),
77 (11), 69 (12), 67 (12), 57 (13), 55 (18). Found [M]+
551.2684. C32H41NO5S. Calculated M 551.2700.
of 1.00 g (1.9 mmol) of compound V in 20 ml of acetone
at room temperature was added in succession 0.54 g
(3.9 mmol) of K2CO3 and 0.32 ml (2.9 mmol) of 80%
solution of propargyl bromide in toluene. The reaction
mixture was stirred for 24 h, diluted with 50 ml of water,
the reaction product was extracted into chloroform (3 ×
30 ml), the extract was washed with water (3 × 50 ml),
dried with MgSO4, and evaporated. The residue was
chromatographed on a column packed with silica gel
(eluent chloroform). Yield 0.78 g (73%), oily substance.
1Н NMR spectrum, δ, ppm: 0.48 s (3Н, С20Н3), 0.96 m
(1H, H1), 1.00 d.t (1H, H3, J 13.4, 4.3 Hz), 1.15 s (3Н,
С19Н3), 1.24 m (1Н, H5), 1.46 m (1Н, Н2), 1.54 m (1Н,
Н9), 1.64 m (1Н, Н11), 1.72–1.82 m (4H, H1,2,6,11), 1.86 m
(1Н, Н7), 1.94 m (1Н, Н6), 2.13 m (1Н, Н3), 2.28 m (1Н,
Н12), 2.38 m (1Н, Н7), 2.41 s (3Н, СН3), 2.49 m (1Н, Н12),
2.55 m (1Н, Н5''), 3.58, 3.60 s (3Н, OCH3), 3.93 d, 3.95 d
(2Н, Н3'', J 9.3 Hz), 4.31 d, 4.36 d (2Н, Н1'', J 10.1 Hz),
4.56 s, 4.87 s (2Н, Н17), 6.19 d, 6.20 d (1Н, Н14, J 2.0 Hz),
7.27 s (1Н, Н15), 7.27 d (2Н, Н3',5', J 8.0 Hz), 7.71 d (2Н,
Н2',6', J 8.0 Hz). 13C NMR spectrum, δ, ppm: 12.52 q
(C20), 19.82 t (С2), 21.43 q (СН3), 22.56 t, 22.87 t (С12),
24.34 t (С11), 26.16 t (C6), 28.67 q (C19), 35.92 t (С3''),
38.05 t (C3), 38.63 t (C7), 38.95 t (C1), 40.06 с (C10),
40.62 t (С1''), 44.17 s (С4), 51.01 q (ОСН3), 54.93 d (С9),
56.13 d (С5), 73.68 s (С4''), 77.65 d (С5''), 106.53 t (С17),
111.40 d (С14), 124.79 s (С13), 126.90 d, 127.68 d (C2',6'),
129.29 d (C3',5'), 135.93 s (C4'), 142.17 d (С15), 143.38 s
(C1'), 143.62 s (С16), 147.56 s (С8), 177.60 s (С18).
Methyl (1S,4аR,5S,8аR)-1,4а-dimethyl-6-
methylidene-5-(2-{2-[(prop-2-yn-1-yloxy)methyl ]fu-
ran-3-yl}ethyl)decahydronaphthalene-1-carboxylate
(XI). To a stirred solution of 1.00 g (2.8 mmol) of com-
pound X in 10 ml of DMF was added at 0°С by portions
0.33 g (8.3 mmol) of 60% dispersion of sodium hydride
in mineral oil, the mixture was stirred for 30 min, and
0.61 ml (5.5 mmol) of 80% solution of propargyl bromide
in toluene was added. The reaction mixture was warmed
to room temperature and the stirring continued for 4 h.
The reaction mixture was poured on 50 g of ice, the reac-
tion product was extracted into chloroform (3 × 50 ml).
The combined extracts were washed with water (7 ×
50 ml) and dried with MgSO4. The solvent was distilled
off, the residue was chromatographed on silica gel (eluent
petroleum ether–ether, 4 : 1). Yield 0.61 g (55%), oily
substance, [α]D +37.29° (c 3.10, CHCl3). UV spectrum,
λmax, nm (log ε): 221 (3.83). IR spectrum, cm–1: 741, 891,
1074, 1153, 1229, 1382, 1449, 1466, 1643, 1724, 2849,
Methyl (1S,4аR,5S,8аR)-5-[2-(7-hydroxy-2-
tosylisoindolin-4-yl)ethyl]-1,4а-dimethyl-6-
methylidenedecahydronaphthalene-1-carboxylate
(III). To a solution of 0.300 g (0.544 mmol) of compound
VI in 10 ml of acetonitrile was added at room tempera-
ture 0.008 g (0.027 mmol) of AuCl3, and the mixture
was stirred for 24 h (TLC monitoring). The solvent
was distilled off, the residue was chromatographed on a
column packed with silica gel (eluent petroleum ether–
ether, 1 : 1). Yield 0.230 g (73%), oily substance, [α]D
+17.26° (c 0.34, CHCl3). UV spectrum, λmax, nm (log ε):
226 (4.11), 275 (3.25). IR spectrum, cm–1: 3423, 2925,
2851, 1722, 1620, 1609, 1580, 1503, 1456, 1346, 1315,
1290, 1231, 1163, 1097, 1065, 816, 757, 662. 1Н NMR
spectrum, δ, ppm: 0.46 s (3Н, С14'Н3), 0.96 m (1H, H4'),
1.00 m (1H, H2'), 1.16 с (3Н, С13'Н3), 1.24 m (1Н, H8'),
1.49 m (1Н, Н3'), 1.53 br.s(1Н, Н5'), 1.66 m (1Н, Н9'),
1.70–1.78 m (4H, H3',4',8',9'), 1.85 m (1Н, Н7'), 1.97 m
(1Н, Н8'), 2.14 m (2Н, Н2',10'), 2.38 s (3Н, СН3), 2.40 m
(1Н, Н7'), 2.42 m (1Н, Н10'), 3.60 s (3Н, OCH3), 4.50 d
1
2934, 2943, 3306. Н NMR spectrum, δ, ppm: 0.42 s
(3Н, С20Н3), 0.89 d.t (1H, H1, J 13.4, 3.2 Hz), 0.93 d.t
(1H, H3, J 13.3, 3.5 Hz), 1.08 s (3Н, С19Н3), 1.19 m (1Н,
H5), 1.40 m (1Н, Н2), 1.51 m (1Н, Н9), 1.62 m (1Н, Н11),
1.68–1.83 m (5H, H1,2,6,7α,11), 1.89 m (1Н, Н6), 2.06 d.m
(1Н, Н3, Jгеm 13.2 Hz), 2.23 m (1Н, Н12), 2.33 m (1Н, Н7),
2.48 m (1Н, Н12), 2.50 m (1Н, Н5'), 3.51 s (3Н, OCH3),
4.01 d (1Н, Н3', J 2.3 Hz), 4.02 d (1Н, Н3', J 2.3 Hz),
4.38 s (2Н, Н1'), 4.52 s, 4.82 s (2Н, Н17), 6.16 d (1Н,
Н14, J 1.5 Hz), 7.24 d (1Н, Н15, J 1.5 Hz). 13C NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

KHARITONOV et al.
1086
spectrum, δ, ppm: 12.32 q (C20), 19.62 t (С2), 22.87 t
(С12), 24.38 t (С11), 25.94 t (C6), 28.43 q (C19), 37.83 t
(C3), 38.37 t (C7), 38.68 t (C1), 39.80 s (C10), 43.91 s (С4),
50.74 q (ОСН3), 54.51 d (С9), 55.85 d (С5), 56.25 t (С3'),
60.70 t (С1'), 74.38 d (С5'), 79.25 s (С4'), 106.18 t (С17),
111.17 d (С14), 124.63 s (С13), 141.90 d (С15), 146.11 s
(С16), 147.47 s (С8), 177.21 с (С18). Mass spectrum, m/z
(Irel, %): 398 (1.58), 342 (13), 283 (13), 189 (28), 188
(12), 161 (12), 133 (14), 121 (100), 120 (15), 119 (21),
110 (15), 109 (16), 107 (27), 105 (23), 95 (29), 94 (38),
93 (22), 91 (33), 85 (16), 83 (14), 81 (36), 79 (23), 77
(18), 71 (20), 69 (16), 67 (19), 57 (34), 55 (37), 53 (14),
43 (33), 41 (39), 39 (16), 29 (14). Found [M]+ 398.2455.
C25H34O4. Calculated M 398.2452.
(17), 149 (50), 148 (100), 135 (11), 133 (10), 121 (66),
120 (15), 119 (11), 109 (12), 107 (20), 105 (12), 95 (10),
93 (14), 91 (20), 81 (21), 79 (10). Found [M]+ 398.2450.
C25H34O4. Calculated M 398.2452.
Methyl (1S,4aR,5S,8aR)-5-(2-{2-[(R)-1-hydroxy-
but-3-yn-1-yl]furan-3-yl}ethyl)- and 5-(2-{2-[(S)-1-hy-
droxybut-3-yn-1-yl]furan-3-yl}ethyl)-1,4а-dimethyl-
6-methylidenedecahydronaphthalene-1-carboxylates
(XIIa, XIIb). а. To a stirred solution of 0.40 g (2.8 mmol)
of propargylmagnesium bromide in 20 ml of anhydrous
ether at –40°С in an argon flow was added dropwise a
solution of 1.00 g (2.8 mmol) of methyl 16-formyllam-
bertianate (VII) in 10 ml of ether. The temperature of the
reaction mixture was raised to 10°С, and the stirring was
continued for 10 min. The formation of a white dispersion
with large grains was observed. To the reaction mixture
was cautiously added 100 ml of water solution of am-
monium chloride (17 g of NH4Cl per 100 g of H2O), and
the mixture was vigorously stirred till phase separation.
The organic layer was separated, the reaction product
was extracted from the water layer into ether (3 × 30 ml).
Combined organic solutions were dried with MgSO4. The
solvent was removed to give in the residue 0.83 g (74%)
of oily mixture of diastereomers XIIa, XIIb.
Methyl (1S,4аR,5S,8аR)-5-[2-(7-hydroxy-1,3-
dihydroisobenzofuran-4-yl)ethyl]-1,4а-dimethyl-6-
methylidenedecahydronaphthalene-1-carboxylate
(VIII). To a solution of 0.300 g (0.753 mmol) of com-
pound XI in 10 ml of acetonitrile was added at room
temperature 0.011 g (0.038 mmol) of AuCl3, and the
stirring was continued for 24 h. The solvent was distilled
off, the residue was chromatographed on a column packed
with silica gel (eluent petroleum ether–ether, 1 : 1).
Yield 0.23 g (78%), oily substance, [α]D +39.62° (c 1.81,
СHCl3). UV spectrum, λmax, nm (log ε): 214 (4.72), 278
(3.10). IR spectrum, cm–1: 3375, 3080, 3019, 2945, 2849,
1722, 1701, 1643, 1609, 1500, 1452, 1379, 1317, 1292,
1231, 1186, 1155, 1132, 1092, 1055, 1032, 1005, 984,
b. To a stirred dispersion of 1.00 g (2.8 mmol) of
methyl 16-formyllambertianateа (VII), 0.91 g (5.6 mmol)
of activated zinc powder, and 0.62 ml of 80% solution
of propargyl bromide in toluene in 20 ml of THF at 0°С
was added dropwise within 1 h 5 ml of saturated solution
of ammonium chloride. The temperature of the reaction
mixture was raised to ambient, and the stirring was con-
tinued for 24 h more. The organic layer was separated, the
reaction product was extracted from the water layer into
ethyl ether (3 × 30 ml). The combined organic solutions
were washed with saturated water solution of ammonium
chloride (2 × 20 ml), with brine (2 × 20 ml), and dried
with MgSO4. The solvent was distilled off, the residue
was chromatographed on a column packed with silica gel
(eluent petroleum ether–ether, 4 : 1). Yield of the mixture
of diastereomers XIIa, XIIb 0.74 g (66%), oily substance.
UV spectrum, λmax, nm (log ε) 220 (3.85), 279 (3.09). IR
spectrum, cm–1: 3481, 3308, 3078, 2945, 2846, 2122,
1958, 1722, 1643, 1464, 1449, 1381, 1333, 1229, 1159,
1
891, 816, 756, 710. Н NMR spectrum, δ, ppm: 0.47 s
(3Н, С14'Н3), 0.96 d.t (1H, H4', J 13.8, 4.6 Hz), 1.01 d.t
(1H, H2', J 13.4, 4.4 Hz), 1.16 s (3Н, С13'Н3), 1.26 d.d (1Н,
H8а', J 12.5, 3.2 Hz), 1.48 m (1Н, Н3'), 1.57 br.s(1Н, Н5'),
1.70 m (1Н, Н9'), 1.76 m, 1.79 m, 1.81 m (4H, H9',8',4',3'),
1.88 m (1Н, Н7'), 1.98 m (1Н, Н8'), 2.14 d.m (1Н, Н2' ,
J 13.0 Hz), 2.22 m (1Н, Н10'), 2.41 d.d.d (1Н, Н7', J 11.9,
4.0, 2.3 Hz), 2.60 m (1Н, Н10'), 3.60 s (3Н, OCH3), 4.59
s, 4.89 s (2Н, Н11'), 5.05 d (1Н, Н1, J 10.2 Hz), 5.10 d
(1Н, Н1, J 10.2 Hz), 5.16 s (2Н, Н3), 5.40 br.s(1Н, ОН),
6.61 d (1Н, Н6, J 8.0 Hz), 6.90 d (1Н, Н5, J 8.0 Hz).
13C NMR spectrum, δ, ppm: 12.52 q (C14'), 19.82 t (С3'),
24.64 t (С9'), 26.18 t (C8'), 28.70 q (C13'), 31.35 t (С10'),
38.03 t (C2'), 38.62 t (C7'), 38.92 t (C4'), 40.16 s (C4'a),
44.24 s (С1'), 51.20 q (ОСН3), 55.28 d (С5'), 56.12 d (С8a'),
72.19 t (С3), 73.37 t (С1), 106.36 t (С11'), 114.16 d (С6),
124.59 s (С7a), 128.02 s (С4), 128.61 d (C5), 139.30 s
(C3a), 147.80 s (C6'), 148.44 s (С7), 178.04 s (С12'). Mass
spectrum, m/z (Irel, %): 398 (7), 237 (12), 236 (53), 235
(25), 202 (13), 201 (19), 189 (34), 177 (10), 162 (49), 161
1
1090, 1034, 986, 891, 748, 640. Н NMR spectrum, δ,
ppm: 0.47 s (3Н, *С20Н3), 0.85 m (1H, *H1), 0.99 d.t (1H,
*H3, J 13.4, 4.0 Hz), 1.14 s, 1.23 s (3Н, С19Н3), 1.25 m
(1Н, *H5), 1.46 d.m (1Н, *Н2, Jгеm 13.9 Hz), 1.56 m (1Н,
*
*
*Н9), 1.59 m (1Н, Н11), 1.68–1.83 m (4H, H1,2,6,11),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

SYNTHETIC TRANSFORMATIONS OF HIGHER TERPENOIDS: XXIX.
1087
1.83 m (1Н, *Н7), 1.91 m (1Н, *Н6), 2.01 m (2Н, *Н4', 2H,
*OН), 2.12 d.m (1Н, *Н3, Jгеm 13.2 Hz), 2.25–2.34 m (1Н,
*Н12), 2.40 m (1Н, Н7), 2.50–2.55 m (1Н, *Н12), 2.62 d.d
(1Н, Н2', J 6.8, 2.6 Hz), 2.67 d.d (1Н, Н2', J 6.8, 2.6 Hz),
2.79 d.d (1Н, Н2', J 7.0, 2.6 Hz), 2.84 d.d (1Н, Н2', J 7.0,
2.6 Hz), 3.57 s (3Н, *CH3O), 4.58 s (1Н, *Н17), 4.79 m
(1Н, *Н1'), 4.89 s (1Н, *Н17), 6.20 d (1Н, *Н14, J 1.8 Hz),
7.28 d (1Н, *Н15, J 1.8 Hz). 13C NMR spectrum, δ, ppm:
12.53 q (C20), 19.82 t (С2), 22.94 t (С12), 24.55 t (С11),
26.03 t (C6), 26.17 t (С2'), 28.70 q (C19), 38.07 t (C3),
38.59 t (C7), 38.96 t (C1), 40.08 s (C10), 44.17 s (С4),
51.04 q (ОСН3), 54.91 d (С9), 56.16 d (С5), 64.27 d (С1'),
70.43 d (С4'), 80.41 s (С3'), 106.52 t (С17), 111.47 d (С14),
122.50 s (С13), 141.51 d (С15), 147.72 s, 147.88 s (С16),
148.70 s (С8), 177.61 s (С18). Mass spectrum, m/z (Irel,
%): 398 (3), 341 (18), 315 (29), 299 (25), 281 (23), 249
(13), 189 (37), 181 (16), 173 (13), 161 (15), 148 (25),
147 (17), 131 (28), 123 (29), 121 (100), 119 (17), 110
(36), 109 (18), 107 (25), 105 (18), 95 (14), 93 (20), 91
(21), 81 (30), 79 (16), 77 (15), 55 (14), 41 (14). Found [M]+
398.2453. C25H34O4. Calculated M 398.2452.
3296, 3078, 2930, 2851, 2120, 1722, 1771, 1643, 1600,
1510, 1466, 1449, 1383, 1333, 1229, 1155, 1078, 1040,
889, 770, 642. Н NMR spectrum, δ, ppm: 0.47 s (3Н,
1
*С20Н3), 0.96 d.t (1H, *H1, J 12.6, 3.6 Hz), 1.01 d.t (1H,
*H3, J 13.2, 4.6 Hz), 1.13 s (3Н, С19Н3), 1.14 s (3Н,
С19Н3), 1.26 m (1Н, *H5), 1.46 m (1Н, *Н2), 1.59 m (1Н,
*
Н9), 1.61 m (1Н, Н9), 1.65–1.71 m (1Н, Н11), 1.72–
1.82 m (5H, *H11,6,1,2,7), 1.96 m (1Н, *Н6), 2.13 m (1Н,
*Н3), 2.24–2.35 m (1Н, *Н12), 2.38 m (2Н, *Н4',4''), 2.40 m
*
*
(1Н, Н7), 2.51–2.63 m (1Н, Н12), 2.73–2.79 m (2Н,
*Н2'), 3.57 s (3Н, *CH3O), 3.81 d (1Н, Н2'', J 16.2 Hz),
3.82 d (1Н, Н2'', J 15.9 Hz), 4.05 d.d (1Н, Н2'', J 15.9,
2.6 Hz), 4.06 d.d (1Н, Н2'', J 16.2, 2.7 Hz), 4.59 s (1Н,
*Н17), 4.70 m (1Н, *Н1'), 4.89 с (1Н, *Н17), 6.21 d (1Н,
Н14, J14,15 1.5 Hz), 6.22 d (1Н, Н14, J14,15 2.0 Hz), 7.31 d
(1Н, *Н15). 13C NMR spectrum, δ, ppm: 12.38 q, 12.44 q
(C20), 19.75 t (*С2), 22.88 t, 22.99 t (С12), 23.88 t, 26.17 t
(С2'), 24.51 t, 24.78 t (С11), 26.08 t (*C6), 28.60 q (*C19),
38.01 t (*C3), 38.48 t, 38.55 t (C7), 38.89 t, 39.00 t (C1),
40.01 s, 40.06 s (C4), 44.06 s (*С10), 50.90 q (*ОСН3),
54.89 d, 55.27 d (С9), 55.02 t, 55.08 t (С2''), 56.06 d,
56.09 d (С5), 63.38 d, 69.60 d (С1'), 69.70 d (*С4'), 74.40 d
(*С4''), 79.29 с (*С3'), 79.85 s, 80.01 s (C3''), 106.44 t,
106.50 t (С17), 111.05 d (*С14), 125.52 s, 152.60 s (С13),
142.13 d, 142.15 d (С15), 145.31 s, 145.54 s (С16),
147.56 s (*С8), 177.39 s (*С18). Mass spectrum, m/z (Irel,
%): 436 (0.25), 341 (24), 316 (23), 315 (100), 281 (29),
255 (17), 189 (15), 181 (28), 173 (12), 161 (50), 147
(45), 132 (11), 131 (29), 121 (90), 119 (14), 109 (24),
107 (22), 105 (20), 95 (17), 93 (18), 91 (31), 85 (12), 81
(31), 79 (19), 77 (21), 71 (17), 69 (14), 67 (15), 57 (26),
55 (26), 43 (17), 41 (20), 39 (15). Found [M]+ 436.2604.
C28H36O4. Calculated M 436.2608.
Methyl (1S,4aR,5S,8aR)-1,4a-dimethyl-6-methy-
lidene-5-(2-{2-[(R)-1-(prop-2-yn-1-yloxy)- but-3-yn-
1-yl]furan-3-yl}ethyl)- and methyl (1S,4aR,5S,8aR)-
1,4a-dimethyl -6-methylene-5-(2-{2-[(S)-1-(prop-2-
yn-1-yloxy)but-3-yn-1-yl]furan-3-yl}ethyl)decahy-
dronaphthalene-1-carboxylates (XIIIa, XIIIb). To
a stirred solution of 0.52 g (1.3 mmol) of compound
XIIa, XIIb in 10 ml of DMF at 0°С was added by por-
tions 0.31 g (13.1 mmol) of 60% dispersion of sodium
hydride in mineral oil, the mixture was stirred for 30 min,
then 0.58 ml (6.56 mmol) of 80% solution of propargyl
bromide in toluene was added. The reaction mixture was
warmed to room temperature and the stirring continued
for 4 h. The reaction mixture was poured on 50 g of ice,
the reaction product was extracted into chloroform (3 ×
50 ml). The extract was washed with water (7 × 50 ml),
dried with MgSO4, and evaporated. The residue was chro-
matographed on silica gel (eluent petroleum ether–ether,
10 : 1). We obtained 0.32 g (57%) of oily mixture of
compounds XIIIa, XIIIb. The purification was performed
by column chromatography. At keeping in air from the
enriched fraction of stereoisomers individual compound
XIIIa was isolated, mp 55–58°С, which was subjected
to XRD analysis.
Methyl (1S,4аR,5S,8аR)-5-{2-[(R)- and (S)-7-hy-
droxy-3-(prop-2-yn-1-yl)-1,3-dihydroisobenzo-furan-
4-yl]ethyl}-1,4а-dimethyl -6-methylidenedecahydro-
naphthalene-1-carboxylate (IXa, IXb). To a solution of
0.300 g (0.687 mmol) of a mixture of compounds XIIIa,
XIIIb in 10 ml of acetonitrile was added at room tempera-
ture 0.010 g (0.034 mmol) ofAuCl3 , and the mixture was
stirred for 24 h. The solvent was distilled off, the residue
was chromatographed on silica gel (eluent – petroleum
ether–ether, 1 : 1). Yield 0.21 g (70%). Oily mixture of
diastereomers, 1 : 1. UV spectrum, λmax, nm (log ε):
224 (3.93), 282 (3.32). IR spectrum, cm–1: 3381, 3308,
3308, 3080, 3017, 2945, 2874, 2849, 2122, 1722, 1643,
1607, 1501, 1464, 1450, 1381, 1367, 1335, 1292, 1248,
1231, 1211, 1155, 1092, 1053, 1030, 984, 962, 891, 819,
Mixture of compounds XIIIa, XIIIb. UV spectrum,
λ
, nm (log ε): 220 (3.74). IR spectrum, cm–1: 3422,
_m_a_x___________
1
*
756, 667, 640. Н NMR spectrum, δ, ppm: 0.49 s (3Н,
Doubling of the signal.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

KHARITONOV et al.
1088
*С14'Н3), 1.01 m (2H, *H2',4'), 1.16 s (3Н, *С13'Н3), 1.27 m
(1Н, *H8а'), 1.49 m (1Н, Н3'), 1.60 m (1Н, *Н5'), 1.52 m
CIF file containing full information on the studied
structure has been deposited into CСDC, no. 862589 and
can be obtained freely by the address www.ccdc.cam.
ac.uk/data_request/cif.
*
(1Н, Н9'), 1.78–1.91 m (5H, H4',3',7',8',9'), 1.98 m (1Н,
Н8'), 2.14 d.m (1Н, *Н2', J 13.9 Hz), 2.24 m (1Н, *Н10'),
2.41 m (1Н, *Н7'), 2.51 m (1Н, Н1''), 2.57 m (1Н, Н1''),
2.60–2.68 m (2Н, *Н10', *Н3''), 2.73 m, 2.79 m (2Н, Н1''),
3.60 s (3Н, *CH3O), 4.60 s (1H, *Н11'), 4.91 s (1Н, *Н11'),
ACKNOWLEDGMENTS
*
*
5.09 d (1Н, Н1, J 10.2 Hz), 5.25 d.t (1Н, Н1, J 10.2,
The study was carried out under the financial sup-
port of the Russian Foundation for Basic Research
(grant no. 11-03-00242) and of the Program of the
President of the Russian Federation for the support of
the leading scientific schools (grant NSh-3986.2012.3).
2.0 Hz), 5.40 m, 5.44 m (1Н, Н3), 5.95 br.s(1Н, НО),
*
*
*
6.67 d (1Н, Н6, J 7.9 Hz), 6.95 d (1Н, Н5, J 7.9 Hz).
13C NMR spectrum, δ, ppm: 12.20 q (*C14'), 19.49 t,
19.52 t (С3'), 24.33 t, 24.57 t (С1''), 25.41 t, 25.51 t (С9'),
25.87 t (*C8'), 28.73 q, 28.40 q (C13'), 30.01 t, 30.09 t
(С10'), 37.72 t (*C2'), 38.24 t, 38.29 t (C7'), 38.63 t (*C4'),
39.86 s, 39.91 s (C4а'), 43.92 s (*С1'), 50.88 q (*ОСН3),
55.03 d (*С8а'), 55.81 d (*С5'), 69.45 d, 69.50 d (С3),
70.99 t, 71.10 t (С1), 80.38 s (*С2''), 82.18 d, 82.26 d (С3''),
106.06 t, 106.11 t (С11'), 114.59 d, 114.61 d (С6), 125.08 s,
125.53 s (С7a), 127.96 s (*С4), 128.54 d, 128.77 d (C5),
139.52 s (*C3a), 147.56 s, 147.63 с (*С7), 147.81 s (C6'),
177.70 s (*С12'). Mass spectrum, m/z (Irel, %): 436 (4),
398 (27), 397 (100), 379 (28), 337 (14), 319 (28), 249
(13), 201 (15), 199 (26), 189 (34), 187 (24), 186 (48), 185
(27), 173 (15), 161 (42), 159 (15), 157 (14), 148 (33), 145
(12), 133 (12), 121 (89), 120 (20), 119 (16), 109 (18), 107
(29), 105 (18), 95 (17), 93 (22), 91 (32), 81 (38), 79 (17),
77 (13), 67 (14), 55 (21), 41 (18). Found [M]+ 436.2605.
C28H36O4. Calculated M 436.2608.
REFERENCES
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X-ray crystallographic data for compound XIIIa.
For the experiment a needle crystal of compound XIIIa
was selected of the size 0.80 × 0.40 × 0.04 mm. Crys-
tals monoclinic, a 11.533(2), b 7.169(1), c 15.427(3)
Å, β 99.139(6)°, V 1259.4(4) Å3, space group P21, Z 2.
C28H36O4. dcalc 1.151 g/cm3, μ 0.075 mm–1. The intensi-
ties of 4539 independent reflections were measured. The
corrections for extinction were introduced with the help
of SADABS program [15]. The structure was solved by
the direct method and was refined by the full-matrix
least-squares method in the anisotropic approximation
(except for H atoms) using SHELX-97 software [16].
The positions of the hydrogen atoms wer calculated geo-
metrically and refined in the rider model (parameters of
hydrogen atoms were calculated in each refinement cycle
from the coordinates of the corresponding carbon atoms).
The final refinement of the structure was performed with
respect to all F2 to wR2 0.2032, S 1.04, 292 parameters
were refined (R 0.0669 for 3237 F > 4σ).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

SYNTHETIC TRANSFORMATIONS OF HIGHER TERPENOIDS: XXIX.
1089
pen, A.G., and Taylor, R., J. Chem. Soc., Perkin Trans. II,
1987, p. 1.
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anskaya, I.Yu., and Tolstikov, G.A., Russ. J. Org. Chem.,
2010, vol. 46, p. 1347.
14. Dalence-Guzmán, M.F., Berglund, M., Skogvall, S., and
Sterner, O., Bioorg. Med. Chem., 2008, vol. 16, p. 2499.
15. Sheldrick, G.M., SADABS. Version 2.01, BrukerAXS, Inc.
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