Cycloaddition of 1-aryl-3-trimethylsiloxy-1,3-butadienes in the synthesis of natural quinone analogs

Article abstract of DOI:10.1023/A:1013127520476

7-Hydroxy-5-(2-methoxyphenyl)-2-methyl-6-R-1,4-naphthoquinones, 8-hydroxy-1-(2-methoxyphenyl)-3-oxo-1,2,3,4-tetrahydro-9,10-anthraquinone, and 2-ethoxycarbonyl-8-hydroxy-1-(2-methoxyphenyl)-3-trimethylsiloxy-1,1a,4,4a-tetrahydro-9,10-anthraquinone were sy

Full text of DOI:10.1023/A:1013127520476

Russian Journal of Organic Chemistry, Vol. 37, No. 9, 2001, pp. 1276 1283. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 9, 2001,
pp. 1344 1350.
Original Russian Text Copyright
2001 by Nechepurenko, Shul’ts, Tolstikov.
Cycloaddition of 1-Aryl-3-trimethylsiloxy-1,3-butadienes
in the Synthesis of Natural Quinone Analogs*
I. V. Nechepurenko, E. E. Shul’ts, and G. A. Tolstikov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: niv@nioch.nsc.ru
Received October 13, 2000
Abstract 7-Hydroxy-5-(2-methoxyphenyl)-2-methyl-6-R-1,4-naphthoquinones, 8-hydroxy-1-(2-methoxy-
phenyl)-3-oxo-1,2,3,4-tetrahydro-9,10-anthraquinone, and 2-ethoxycarbonyl-8-hydroxy-1-(2-methoxyphenyl)-
3-trimethylsiloxy-1,1a,4,4a-tetrahydro-9,10-anthraquinone were synthesized by reactions of 1-(2-methoxy-
phenyl)-2-R-3-trimethylsiloxy-1,3-butadienes with 2-bromo-5-methyl-1,4-benzoquinone and juglone. 1-Aryl-
2-ethoxycarbonyl-3-trimethylsiloxy-1,3-butadienes reacted with 1,4-naphthoquinone to afford 1-aryl-2-ethoxy-
carbonyl-3-hydroxy-9,10-anthraquinones and their 4,4a-dihydro derivatives.
Diversity of structures and accessibility of siloxy-
butadienes in combination with their high reactivity
and regioselectivity toward various dienophiles in the
Diels Alder reaction make them important synthons
[1, 2]. Of particular interest is the use of siloxybuta-
dienes in the synthesis of natural quinones and their
analogs exhibiting important biological activity
[1, 3, 4].
1-aryl-3-trimethylsiloxy-1,3-butadienes IV VI in 55,
50, and 28% yield, respectively. Dienes IV VI are
high-boiling liquids which are stable under argon but
undergo fast hydrolysis on exposure to atmospheric
1
moisture. Table 1 contains the H and 13C NMR
spectra of compounds I VI.
Scheme 1.
The present communication is an extension of our
studies on the synthesis of quinoid compounds which
are potential antiviral and cytostatic agents. As pre-
viously [5, 6], the synthesis of such compounds is
based on the Diels Alder reaction of 1-substituted
3-trimethylsiloxy-1,3-butadienes with quinones. The
structure of the diene component allowed us to
introduce into the target products 2-MeOC6H4 and
2,3-(MeO)2C6H3 fragments which are intrinsic to
a number of naturally occurring compounds of the
phenol and quinone series [3]. The initial siloxydienes
were obtained by the known procedure [5, 6]. Croto-
nization of acetone and ethyl acetoacetate with benz-
aldehydes [7] gave 74 78% of , -unsaturated
ketones I III (Scheme 1). Ketones II and III were
isolated as mixtures of Z and E isomers at a ratio of
1.6 : 1. Ketones I III were treated with chlorotri-
methylsilane in the presence of anhydrous zinc(II)
chloride and triethylamine under argon to obtain
____________
I, IV, Ar = 2-MeOC6H4, X = H; II, V, Ar = 2-MeOC6H4,
X = CO2Et; III, VI, Ar = 2,3-(MeO)2C6H3, X = CO2Et.
In the reactions of siloxybutadienes IV and V with
2-bromo-5-methyl-1,4-benzoquinone in boiling ben-
zene the only products were naphthoquinones VII
and VIII which were isolated in 35 40% yield
(Scheme 2). Under similar conditions diene IV reacted
with juglone IX with formation of tetrahydroanthra-
quinone X in 47% yield (Scheme 3). In contrast to
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 00-03-32882).
1070-4280/01/3709-1276$25.00 2001 MAIK Nauka/Interperiodica

CYCLOADDITION OF 1-ARYL-3-TRIMETHYLSILOXY-1,3-BUTADIENES
1277
Scheme 2.
is formed in 19% yield. Treatment of siloxy ester
XII with methanol leads to formation of enol XV
1
which was detected by H NMR spectroscopy. The
reaction of XII with potassium carbonate in methanol
(reaction time 2 h) results in dehydrogenation with
formation of 85% of dihydroanthraquinone XIII. We
also failed to isolate primary adduct of diene V and
naphthoquinone XVI (in benzene under reflux); by
column chromatography on silica gel we isolated
compounds XVII and XVIII in 18 and 25% yield,
respectively. By addition of diene VI to naphtho-
quinone XVI we succeeded in isolating anthraquinone
derivatives XIX and XX in 32 and 8% yield, respec-
tively. Previously [6], we detected neither primary
siloxy adduct nor tetrahydroanthraquinone in the reac-
tions of 2-ethoxycarbonyl-1-(4-methoxyphenyl)-3-tri-
methylsiloxy-1,3-butadiene with 1,4-quinones. The
yields, IR and UV spectra, and elemental analyses of
naphthoquinones VII and VIII and anthraquinones
X XIV and XVII XX are given in Table 2.
VII, X = H; VIII, X = CO2Et.
our previous data [5], we failed to isolate the primary
adduct. Dehydrogenation is possible both by the
action of atmospheric oxygen and by the action of
juglone. The reaction of 2-bromonaphthoquinone with
diene IV is accompanied by dehydrobromination and
yields 36% of the expected arylanthraquinone XI.
When the reaction was performed at room temperature
in the presence of 0.5 equiv of Zn(OTf)2 (Tf = tri-
fluoromethylsulfonyl) [8], anthraquinone XI was
isolated in 44% yield by column chromatography.
The structure of the newly synthesized naphtho-
and anthraquinone derivatives was deduced from
1
the H and 13C NMR spectra (Tables 3, 4). Mutual
arrangement of the aryl substituent and methyl group
(in compounds VII and VIII) or hydroxy group
(in XIV) was determined on the basis of multiplicities
of signals from the carbonyl carbon atoms in the 13C
NMR spectra. The following data were obtained for
Diene V reacted with juglone (IX) in benzene
under reflux (Scheme 4). The reaction was regioselec-
tive; unlike preceding experiment, we succeeded in
isolating primary adduct XII in 66% yield. By column
chromatography of the residue on silica gel we
isolated anthraquinone derivatives XIII and XIV in
10 and 7% yield, respectively. In boiling benzene in
the presence of Eu(fod)3 (fod = 1,1,1,2,2,3,3-hepta-
fluoro-7,7-dimethyl-4,6-octadionate) as catalyst
anthraquinone XIV becomes the predominant product
(yield 51%). In this case dihydroanthraquinone XIII
naphthoquinone VIII: C1,
183.5 ppm, d.d,
C
3J(C1 3-H) = 5.4, 3J(C1 8-H) = 3.5 Hz; C4,
183.9 ppm, d, J(C4 3-H) = 4.4 Hz. It is known
2
C
that the constant J(C1 3-H) in naphthoquinone frag-
3
3
ment is the greatest, as compared to J(C1 8-H) and
2J(C4 3-H); it ranges from 6 to 7.5 Hz [9]. These
Scheme 3.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1278
NECHEPURENKO et al.
Scheme 4.
V, XII, XIII, XIV, XV, Ar = 2-MeOC6H4; VI, XIX, XX, Ar = 2,3-(MeO)2C6H3; IX, XII, XIII, XIV, XV, R = OH;
XVI, XVII, XVIII, XIX, XX, R = H; XII, R = SiMe3; XV, R = H.
findings indicate that the methyl group in naphtho- a good accuracy the experimental chemical shifts of
C9 and C10 in compounds XIII and XIV. In keeping
quinone VIII occupies position 2 rather than 3.
In the 13C NMR spectrum of anthraquinone XIV
with the monoresonance spectrum of XI, the down-
the carbonyl carbon signal (C9) is displaced downfield
field signal belongs to the carbonyl carbon atom
C10, and the upfield signal, to C9. The signal at
(
187.5 ppm), and the C10 atom gives a signal at
C182.1 ppm. The downfield shift of the C9 signal is
183.8 ppm is a triplet with the coupling constants
C
C
3
3J(C10 4-H) = 3.7 and J(C10 5-H) = 3.7 Hz; it corre-
caused by the effect of the hydroxy group in position
8 (
5.4 ppm for C9 and 0.7 ppm for C10) [10].
The signal at
at
sponds to C10. The signal at
182.2 ppm (C9) is
C
C
3
a doublet with J(C9 8-H) = 3.4 Hz.
187.5 ppm (C9) is a singlet, and that
182.1 ppCm (C10) is a triplet with the coupling
C
constants J(C10 4-H) = 3.4 Hz and J(C10 5-H) =
3
3
EXPERIMENTAL
3
3.4 Hz. The J values coincide with the known data
(3 4.5 Hz [9]), and the signal multiplicities indicate
The IR spectra were recorded on a Specord M-80
spectrometer in KBr. The UV spectra were measured
that the OH and Ar substituents occupy positions 1
4
from solution in ethanol (c = 10 M) using a Specord
and 8. Likewise, the carbonyl carbon (C9) signal in
the spectrum of tetrahydroanthraquinone X is dis-
placed downfield ( 190.1 ppm), the C10 signal is
UV-Vis spectrophotometer. The 1H NMR spectra
were obtained on a Bruker WP-200SY instrument at
200.2 MHz. The 13C NMR spectra were recorded on
a Bruker AC-200 spectrometer (50.323 MHz) in the
JMOD and monoresonance modes; samples were
prepared as 5 10% solutions in CDCl3 or (CD3)2CO.
The solvent signal was used as reference. The prog-
ress of reactions was monitored by TLC on Silufol
UV-254 plates in the system chloroform methanol
(20:1); spots were visualized in UV light or with
ammonia vapor. Column chromatography was per-
formed on KSK silica gel (0 140) using chloroform
and chloroform methanol (100:1, 50:1, and 20:1)
as eluent. Zinc(II) trifluoromethanesulfonate was syn-
thesized by the procedure described in [11].
observed at
group (C3) isCcharacterized by a chemical shift
204.8 ppm. In the monoresonance spectrum of XCthe
signal at
184.0 ppm (C10) is split due to coupling
with 5-H, 4 -H, and 4 -H; it appears as a broadened
multiplet with a more complex structure than that of
184.0Cppm, and unconjugated carbonyl
of
C
the multiplet signal at
190.1 ppm (C9). These data
allowed us to locate thCe OH and Ar substituents at
positions 1 and 8, respectively.
The 13C NMR spectra of dihydroanthraquinones
XVII and XIX should be characterized by more
upfield signal from the conjugated carbonyl group
(C9,
182.4 182.9 ppm), as compared to the C10
4-Aryl-3-buten-2-ones I III. Ketone I was syn-
thesized from acetone and 2-methoxybenzaldehyde
under conditions corresponding to aldol condensation
signal C( 184.0 185.2 ppm). Using the increments
for hydrCoxy group (see above), we obtained with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

CYCLOADDITION OF 1-ARYL-3-TRIMETHYLSILOXY-1,3-BUTADIENES
1279
Table 1. 1H and 13C NMR spectra of ketones I III and siloxydienes IV VI in CDCl3
Comp. no.
1H NMR spectrum, , ppm (J, Hz)
13C NMR spectrum, C, ppm
I
2.28 s (3H, MeCO), 3.89 s (3H, OMe),
6.57 d (1H, CH , 16.5), 6.84 d (1H,
3 -H, 8), 6.84 d (1H, 4 -H, 8), 7.26 t.d
(1H, 5 -H, 8, 1.5), 7.49 d.d (1H, 6 -H, 8,
1.5), 7.70 d (1H, CH , 16.5)
IIa
1.19 t (Z-Me), 1.33 t (E-Me), 2.17 s 13.9 q (Z-Me), 14.2 q (E-Me), 26.4 q (Z-C1), 30.6 q (E-C1),
(E-MeCO), 2.32 s (Z-MeCO), 3.86 s
(3H, OMe), 4.18 q (Z-CH2), 4.25 q
(E-CH2), 6.84 m (2H, Harom), 7.27 m
(2H, Harom), 7.75 br.s (1H, CH )
55.0 q (E-OMe), 55.2 q (Z-OMe), 60.7 t (CH2), 110.5 d
(C3 ), 120.4 d (Z-C6 ), 120.5 d (E-C6 ), 122.5 s (E-C3),
122.7 s (Z-C3), 129.2 d and 131.6 d (Z-C4 , C5 ), 130.2 d
and 131.4 d (E-C4 , C5 ), 134.1 s (E-C1 ), 134.6 s (Z-C1 ),
135.8 d (E-C4), 136.2 d (Z-C4), 157.5 s (E-C2 ), 157.8 s
(Z-C2 ), 164.0 s (E-CO2), 167.0 s (Z-CO2), 193.0 s (Z-C2),
200.0 s (E-C2)
IIIa
1.19 t (Z-Me), 1.32 t (E-Me), 2.33 s 13.8 q (Z-Me), 14.1 q (E-Me), 26.5 q (Z-C1), 30.8 q (E-C1),
(Z-MeCO), 2.18 s (E-MeCO), 3.79 s,
3.81 s, 3.82 s (2OMe), 4.16 q (Z-CH2),
4.24 q (E-CH2), 7.71 s (Z-CH ), 7.73 s
55.7 q and 60.9 q (2OMe), 61.1 t (CH2), 114.1 s (Z-C4 ),
114.6 s (E-C4 ), 120.7 d and 123.8 d (Z-C5‘,C6‘), 121.4 d
and 123.9 d (E-C5 , C6 ), 127.5 s (Z-C3), 127.8 s (E-C3),
135.0 s (E-C1 ), 135.6 s (Z-C1 ), 136.1 d (Z-C4), 136.7 d
(E-C4), 148.5 s and 152.6 s (C2 , C3 ), 164.2 s (Z-CO2),
167.2 s (E-CO2), 194.1 s (Z-C2), 200.1 s (E-C2)
(E-CH ), 6.88 m (3H, Harom
)
IV
V
0.27 s (9H, Me3SiO), 3.85 s (3H, OMe), 0.2 s (Me3SiO), 53.3 q (OMe), 96.4 t (C4), 110.8 d (C3 ),
4.35 s and 4.40 s (2H, CH2 ), 6.57 d
(1H, CH , 15.5), 6.84 m (2H, Harom),
7.08 d (1H, CH , 15.5), 7.17 m (1H,
120.8 d (C6 ), 124.8 s (C2), 126.0 s (C1 ), 126.8 d and
127.1 d (C4 , C5 ), 128.5 d (C1), 155.6 s (C3), 157.1 s (C2 )
Harom), 7.41 m (1H, Harom)
0.26 s (9H, Me3SiO), 1.08 t (3H, Me), 0.1 s (Me3SiO), 13.7 q (Me), 55.1 q (OMe), 60.5 t (CH2),
3.77 s (3H, OMe), 4.10 q (2H, CH2),
4.41 s and 4.50 s (2H, CH2 ), 6.81 m
(2H, Harom), 7.19 s (1H, CH ), 7.19 m
94.9 t (C4), 110.2 d (C3 ), 120.1 d (C6 ), 124.6 s (C2),
125.5 d (C1), 128.4 d and 129.3 d (C4 , C5 ), 132.6 s (C1 ),
152.6 s (C3), 157.1 s (C2 ), 168.3 s (CO2)
(2H, Harom
)
VI
0.24 s (9H, Me3SiO), 1.08 t (3H, Me),
3.65 s and 3.85 s (6H, 2OMe), 4.07 q
(2H, CH2), 4.41 s and 4.49 s (2H,
CH2 ), 6.84 m (3H, Harom), 7.14 s
(1H, CH )
a
Z/E ratio 1.6:1.
(crotonization); ketones II and III were obtained from
ethyl acetoacetate and 2-methoxy- or 2,3-dimethoxy-
benzaldehyde, respectively, according to Knoevenagel
(Cope modification) [7]. The products, E isomer of I
and Z/E isomeric mixtures of II and III, were isolated
in 74, 76, and 78% yield, respectively; bp 107 112
(1 mm), 145 146 (2 mm), and 161 163 C (3 mm).
1-Substituted 3-trimethylsiloxy-1,3-butadienes
IV VI. To a suspension of 5 mmol of anhydrous
ZnCl2 and 19 ml of triethylamine, heated to 80 C, we
added with stirring under argon a solution of 50 mmol
of ketone I III in 30 ml of anhydrous acetonitrile and
then 18.9 ml of chlorotrimethylsilane. The mixture
was stirred for 5 h at 50 C and cooled, 250 ml of
dry diethyl ether was added, and the precipitate was
filtered off. The filtrate was evaporated under reduced
pressure (water-jet pump), and the residue was treated
with 100 ml of dry diethyl ether (as above). The sol-
vent was removed, and the residue was distilled under
reduced pressure. Compound IV: yield 55%, bp 96
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1280
NECHEPURENKO et al.
Table 2. Yields, melting points, IR and UV spectra, and elemental analyses of naphthoquinones VII and VIII and
anthraquinones X XIV and XVII XX
Found, %
Calculated, %
Comp. Yield,
IR spectrum,
UV spectrum,
nm (log )
,
max
mp,
C
Formula
1
no.
%
, cm
C
H
C
H
VII
40
35
47
134 136 3400, 1650, 1595, 267 (4.34), 374 (3.41)
(decomp.) 1560, 1345, 1250
73.0
4.5 C18H14O4
5.0 C21H18O6
4.8 C21H16O5
73.4
4.8
VIII
X
155 157 3425, 1650, 1560, 269 (4.44), 381 (3.32)
1350, 1240, 1220
68.1
68.8
72.4
4.9
4.6
213 215 3450, 1715, 1640, 275 (4.11), 420 (3.57), 72.0
1615, 1485, 1450,
1275, 1240
517 (3.16), 719 (2.71)
XI
36
66
264 266 3365, 1669, 1591, 245 (4.50), 372 (3.51)
1558, 1361, 1293
76.5
65.4
4.2 C21H14O4
76.4
65.6
4.3
6.1
XII
155 159 3400, 1680, 1645, 233 (4.32), 352 (3.61)
6.1 C27H30O7Si
1450, 1365, 1245,
840
XIII
10
198 200 3425, 1650, 1610, 251 (4.30), 422 (3.64),
68.5
4.7 C24H20O7
68.6
4.8
1450, 1310, 1275,
1245, 1210
661 (2.30)
XIV
7
230 235 3400, 1640, 1560, 272 (4.30), 409 (3.69)
1455, 1455, 1225
68.6
71.0
4.7 C24H18O7
4.9 C24H20O6
68.9
71.3
4.3
5.0
XVII
18
168 172 3430, 1660, 1610, 250 (4.30), 340 (3.48),
1325, 1290, 1275,
1245, 1210
530 (2.70)
XVIII
XIX
25
34
205 208 3425, 1660, 1590, 270 (4.30), 390 (3.65)
1460, 1340, 1250
71.3
69.0
4.2 C24H18O6
5.0 C25H22O7
71.6
69.1
4.5
5.1
152 155 3440, 1675, 1660, 250 (4.48), 334 (3.52),
1300, 1280, 1250,
1225
523 (2.72)
XX
17
184 188 3425, 1670, 1660, 272 (4.04), 370 (3.38)
69.1
4.8 C25H20O7
69.4
4.6
1590, 1460, 1340,
1250
100 C (1 mm); V: yield 50%, bp 133 134 C (3 mm);
VI: yield 28%, bp 158 164 C (2 mm). According
to the H NMR data, diene VI contained 20% of
primary adduct XII or unchanged quinone XVI. The
products were isolated from the filtrate by column
chromatography. Compounds VII XI and XVII XIX
were recrystallized from diethyl ether, and XII XIV,
from diethyl ether hexane (1:2).
b. A suspension of 2 mmol of 2-bromo-1,4-naph-
thoquinone, 3 mmol of diene IV, and 1 mmol of
zinc(II) trifluoromethanesulfonate in 15 ml of CH2Cl2
was stirred for 3 days at room temperature. The mix-
ture was treated with 10 ml of 1 N HCl in THF and
with chloroform (3 10 ml), washed with a saturated
aqueous solution of NaCl (3 10 ml), and evaporated
under reduced pressure. Column chromatography of
the residue gave anthraquinone XI in 44% yield.
1
ketone III.
Reactions of siloxydienes IV VI with 2-bromo-
5-methyl-1,4-benzoquinone, 2-bromo-1,4-naphtho-
quinone, juglone (IX), and 1,4-naphthoquinone
(XVI). a. A solution of 2 3.5 mmol of 2-bromo-
5-methyl-1,4-benzoquinone, 2-bromo-1,4-naphtho-
quinone, juglone (IX), or 1,4-naphthoquinone (XVI)
and 1.1 1.5 equiv of diene IV VI in 20 ml of
benzene was refluxed for 14 26 h under argon. The
solvent was distilled off on a rotary evaporator, and
the residue was ground with diethyl ether to isolate
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

CYCLOADDITION OF 1-ARYL-3-TRIMETHYLSILOXY-1,3-BUTADIENES
1281
Table 3. 1H NMR spectra of naphthoquinones VII and VIII and anthraquinones X XV and XVII XX in CDCl3
Comp.
no.
Chemical shifts , ppm (J, Hz)
VII
VIII
Xa
2.03 s (3H, Me), 3.67 s (3H, OMe), 6.73 s (1H, 3-H), 6.90 d (1H, 6-H), 6.91 d (1H, 3 -H), 7.00 t (1H, 4 -H),
7.08 d.d (1H, 6 -H), 7.34 t (1H, 5 -H), 7.54 d (1H, 8-H), 11.04 s (1H, OH)
0.75 t (3H, MeCH2), 2.00 s (3H, Me), 3.68 s (3H, OMe), 3.93 q (3H, MeCH2), 6.75 s (1H, 3-H), 6.90 m
(3H, 3 -H, 4 -H, 6 -H), 7.35 m (1H, 5 -H), 7.67 s (1H, 8-H), 11.04 s (1H, OH)
2.65 d.t (1H, 2 -H, J2 , 1 = 1.5, J2 , 2 = 14.5, J2 , 4 = 1.5), 3.05 d.d (1H, 2 -H, J2 , 2 = 14.5, J2 , 1 = 7),
3.35 d.t (1H, 4 -H, J4 , 2 = 1.5, J4 , 1 = 1.5, J4 , 4 = 23), 3.60 d (1H, 4 -H, J4 , 4 = 23), 3.85 s (3H,
OMe), 5.18 d.t (1H, 1-H, J1, 2 = 1.5, J1, 2 = 7, J1, 4 = 1.5), 6.82 m (1H, Harom), 7.01 m (1H, Harom),
7.23 m (2H, Harom), 7.23 (2H), 7.28 (1H), 11.96 s (1H, OH)
XIa
XII
3.66 s (3H, OMe), 7.01 m (2H, Harom), 7.01 m (1H, 2-H), 7.14 m (1H, Harom), 7.38 m (1H, Harom), 7.68 m
(2H, 6-H, 7-H), 7.79 m (1H, 4-H), 8.10m and 8.22 m (2H, 5-H, 8-H), 11.96 s (1H, OH)
0.36 s (9H, Me3SiO), 0.99 t (3H, MeCH2), 2.40 d.d (1H, 4 -H, 18, 8), 3.21 d.d (1H, 4 -H, 18, 8), 3.56 m
(2H, 9a-H, 4a-H), 3.78 s (3H, OMe), 3.96 q (3H, MeCH2), 5.00 d (1H, 1-H, 5), 6.12 m (1H, 3 -H), 6.52 m
(1H, 4 -H), 6.80 m (2H, 5 -H, 6 -H), 7.00 m (2H), 7.28 m (1H), 11.88 s (1H, 8-OH)
XIII
1.22 t (3H, MeCH2), 3.60 d.d (2H, 4-H, 9, 4), 3.71 s (3H, OMe), 4.12 k (3H, MeCH2), 5.30 d.d (1H, 4a-H,
4, 5), 6.80 m (2H, Harom), 7.17 m (1H, Harom), 7.17 m (1H), 7.53 m (1H, Harom), 7.53 m (2H), 11.96 s
(1H, 3-OH), 12.48 s (1H, 8-OH)
XIV
XV
0.90 t (3H, MeCH2), 3.65 s (3H, OMe), 3.91 q (3H, MeCH2), 6.96 m (2H, Harom), 7.25 m (2H, Harom),
7.34 m (1H), 7.73 m (1H), 7.83 m (1H), 7.94 s (1H, 4-H), 12.54 s (1H, 3-OH), 13.67 s (1H, 8-OH)
1.09 t (3H, MeCH2), 2.68 d.d (1H, 4 -H, 18, 8), 2.71 d.d (1H, 4 -H, 18, 8), 3.49 s (3H, OMe), 3.60 m (2H,
9a-H, 4a-H), 3.99 q (3H, MeCH2), 4.81 d (1H, 1-H, 5), 6.25 m (1H, Harom), 6.50 m (1H, Harom), 6.86 m
(2H, Harom), 7.02 m (2H), 7.49 m (1H), 11.95 s (1H, 3-OH), 12.52 s (1H, 8-OH)
XVII
1.21 t (3H, MeCH2), 3.61 d.d (2H, 4-H, 10, 4), 3.70 s (3H, OMe), 4.11 q (3H, MeCH2), 5.32 d.d (1H, 4a-H,
5, 3.5), 6.74 m and 6.90 m (2H, Harom), 7.13 m (1H, Harom), 7.46 m (1H, Harom), 7.65 m (2H), 8.00 m
(2H), 12.47 s (1H, 3-OH)
XVIII
XIX
0.90 t (3H, MeCH2), 3.64 s (3H, OMe), 3.90 q (3H, MeCH2), 6.64 m (2H, Harom), 7.05 m (2H, Harom),
7.10 m (1H), 7.83 m (1H), 8.00 s (1H, 4-H), 8.10 m (1H), 11.40 s (1H, 3-OH)
1.22 t (3H, MeCH2), 3.60 d.d (2H, 4-H, 7, 4), 3.66 s and 3.75 s (6H, 2OMe), 4.13 q (3H, MeCH2), 5.24 d.d
(1H, 4a-H, 4, 5.5), 6.76 m (1H, 4 -H), 6.96 m (1H, 5 -H), 7.13 m (1H, 6 -H), 7.60 m (2H, 6-H, 7-H),
7.95 m (2H, 5-H, 8-H), 12.48 s (1H, 3-OH)
XXa
0.94 t (3H, MeCH2), 3.60 s and 3.91 s (6H, 2OMe), 4.00 q (3H, MeCH2), 7.09 m (3H, Harom), 7.83 m (2H),
8.00 s (1H, 4-H), 8.18 m (2H), 11.38 s (1H, 3-OH)
a
In acetone-d6.
Table 4. 13C NMR spectra of naphthoquinones VII and VIII and anthraquinones X XIV and XVII XX in CDCl3
a
Chemical shifts C, ppm
Atom
no.
VII
VIII
X
XI
XII
XIII
XVII
XIX
XIV
XVIII
XX
C1
C9a
C2
184.3
130.4
150.3
183.5
129.7
151
36.3 143.3
127.8 125.9
44.5 125.4 117.7
43.9
51.8
142.6
128.5
97.9
142.8
128.8
98.1
143.0
133.9
98.4
148.8
143.5
143.5
123.7b
120.2b
123.5b
122.0b
123.5b
122.0b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1282
NECHEPURENKO et al.
Table 4. (Contd.)
Chemical shifts C, ppm
Atom
no.
VII
VIII
X
XI
XII
XIII
XVII
XIX
XIV
XVIII
XX
C3
133.6
185.7
123.8
142.7
133.5
183.9
123
204.8
38.0
162.1
113.0
132.3b
129.3
158.9
28.2
168.6
29.5
168.7
29.3
168.7
29.3
38.9
126.0b 124.7
131.7c
132.7
133.4d 135.6
133.3d 118.8
126.4b 162.2c
132.0c
182.9
184.0
171.2
60.6
164.2c
116.3
130.1
157.3
118.5
133.4
126.9c
157.3
118.5
133.4c
126.9d
C4
C4a
C5
145.5
124.8
134.3
137.4
119.5
162.3
116.9
190.1
184.0
54.3
38.1
38.4
143.6
122.1
133.8b 133.3
124.2
131.7
135.8
118.7
161.3
114.9
188.4
183.3
171.2
60.4
128.0b
131.7c
133.2d
133.2d
128.1b
132.1c
182.8
184.0
171.2
60.5
C10a
C6
134.9d 134.9e
124
120.4
163.7
115.1
134.0c
135.0c
129.6
135.7
116.6
160.3
135.5e
134.8e
127.4c
135.5f
134.8f
127.4d
C7
159.6
112.3
C8
C8a
135.8b 111.4
117.1
187.5
182.1
169.8
62.0
135.3d 135.3e
C9
182.2
183.8
204.4
194.0
165.5
59.7
182.4
185.2
167.2
62.1
182.4
185.2
167.2
62.1
C10
CO2Et
MeCH2
MeCH2
OMe
169.8
62.0
12.9
55.4
13.9
13.6
13.8
13.9
12.9
13.9
13.9
55.3
55.6
55.7
54.3
55.5
55.5
55.4
56.0
55.5
55.5
56.1
60.0
C1
C2
C3
C4
C5
C6
135.2
156
138.6
156.8
109.9
127.9b
128.6b
120.4
146.7
157.7
112.1
129.0b
129.5b
121.4
137.52 126.0
140.8
157.8
111.1
128.3b 129.5e
133.3b 126.5e
139.4
157.8
111.1
139.4
148.1d
152.4d
111.2
125.5
122.7
138.6
156.8
109.9
127.9d 129.5e
128.6d 126.5e
139.4
157.8
111.1
133.9c
153.3g
149.1g
113.5
126.6h
124.1h
157.4
111.5
127.0d
127.4d
156.8
108.2
128.5b
130.6b
110.4
128.7b
128.9b
120.7
121.29 119.3
120.1
120.1
120.4
120.1
a
The spectra of compounds X, XI, and XX were recorded in acetone-d6; C(2-Me), ppm: 16.8 (VII), 17.0 (VIII);
C(Me3SiO) 0 ppm.
Alternative assignment is possible (within a single column).
b
h
1
c. By reaction of 2.21 mmol of juglone (IX) and
(84%). According to the H NMR data, the filtrate
contained a mixture of compounds XIII and XV at
a ratio of 3:2.
2.44 mmol of diene V in 20 ml of benzene containing
0.12 mmol of Eu(fod)3 as catalyst (reaction time 26 h)
we obtained compounds XIII (yield 19%) and XIV
(yield 51%).
REFERENCES
2-Ethoxycarbonyl-3,8-dihydroxy-1-(2-methoxy-
phenyl)-1,4,4a,9a-tetrahydro-9,10-anthraquinone
(XV). A 50-mg portion of compound XII was dis-
solved in 5 ml of methanol, and the solution was
1. Brownbridge, P., Synthesis, 1983, no. 2, pp. 85 104.
2. Danishefsky, S.J., de Minno, T.P., and Chen, S.,
J. Am. Chem. Soc., 1988, vol. 110, no. 12, pp. 3929
3940; Olsen, K.R., Feng, X., Campbele, M., Shao, R.,
and Math, S.K., J. Org. Chem., 1995, vol. 60, no. 19,
pp. 6025 6031; Krohn, K., Angew. Chem., 1986,
vol. 98, no. 9, pp. 788 805; Adeva, M., Cabal-
lero, E., Garsia, F., Medarde, M., Sahagun, H., and
Tome, F., Tetrahedron Lett., 1997, vol. 38, no. 39,
pp. 6893 6896; Smith, E.M., Tetrahedron Lett.,
1999, vol. 40, no. 17, pp. 3228 3288.
1
evaporated. According to the H NMR data, the
residue was a mixture of compounds XV and XII at
a ratio of 9:1.
Alkaline treatment of compound XII. To 102 mg
of compound XII we added 10 ml of methanol and
5 mg of K2CO3, and the mixture (which turned green)
was stirred for 2 h. The finely crystalline precipitate
was filtered off. Yield of compound XIII 73 mg
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

CYCLOADDITION OF 1-ARYL-3-TRIMETHYLSILOXY-1,3-BUTADIENES
1283
3. Thompson, R.H., Naturally Occuring Quinones. III.
Recent Advances, New York: Chapman and Hall,
1987.
7. Organikum. Organisch-Chemisches Grundpraktikum,
Berlin: Wissenschaften, 1976, 15th ed. Translated
under the title Organikum, Moscow: Mir, 1979,
vol. 2, pp. 138 150.
4. Human Medicinal Agents from Plants, King-
horn, A.D. and Balendrin, M.F., Eds., Washington:
ACS Symposium Series 534, 1993, pp. 181 189.
8. Huang, P., Isayan, K., Sarkissian, A., and Oh, T.,
J. Org. Chem., 1998, vol. 63, no. 13, pp. 4500 4502.
9. Hofle, G., Tetrahedron, 1977, vol. 33, no. 15,
5. Tolstikov, G.A., Shul’ts, E.E., Safarova, G.M.,
Spirikhin, L.V., and Panasenko, A.A., Zh. Org.
Khim., 1990, vol. 26, no. 6, pp. 1283 1295.
pp. 1963 1970.
10. Kobayashi, M., Teriu, Y., Tori, K., and Tsuji, N.,
Tetrahedron Lett., 1976, no. 8, pp. 619 620.
6. Shul’ts, E.E., Petrova, T.N., Rybalova, T.V., Gati-
lov, Yu.V., and Tolstikov, G.A., Russ. J. Org. Chem.,
1998, vol. 34, no. 6, pp. 845 855.
11. Corey, E.J. and Shimoji, K., Tetrahedron Lett., 1983,
vol. 24, no. 2, pp. 169 172.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001