Study of plant coumarins: XIV. Catalytic amination of 7-hydroxycoumarin derivatives

Article abstract of DOI:10.1134/S107042801405008X

Catalytic amination of 7-hydroxy-6-cyanocoumarin or 7-hydroxy-6- methoxycarbonylcoumarin triflates with substituted anilines, isoquinolin-5-amine, 1H-pyrazol-3-amine, or amino acids of penicillin series affords the corresponding 7-(N-substituted) aminocou

Full text of DOI:10.1134/S107042801405008X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 5, pp. 662–669. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © E.A. Makhneva, A.V. Lipeeva, E.E. Shul’ts, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 5, pp. 676–683.
Study of Plant Coumarins:
XIV.* Catalytic Amination of 7-Hydroxycoumarin Derivatives
E. A. Makhneva, A. V. Lipeeva, and E. E. Shul’ts
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: schultz@nioch.nsc.ru
Received July 31, 2013
Abstract—Catalytic amination of 7-hydroxy-6-cyanocoumarin or 7-hydroxy-6-methoxycarbonylcoumarin tri-
flates with substituted anilines, isoquinolin-5-amine, 1Н-pyrazol-3-amine, or amino acids of penicillin series
affords the corresponding 7-(N-substituted) aminocoumarins. In the amination of the mentioned triflates and also
of peuruthenicine tosilate with 2-(piperidin-1-yl)aniline the catalytic system Pd(OAc)2–BINAP has been efficient.
DOI: 10.1134/S107042801405008X
Natural and synthetic coumarins are an important
group of biologically active compounds whose range
of therapeutical action depends essentially on the
presence and the position of substituents. 7-
Methoxycoumarins are inhibitors of macrophage NO-
synthase [2, 3], the antiphlogistic action is found in 7-
hydroxycoumarins [4], 7-aryl-substituted coumarins
are considered as a new group of selective nonsteroid
inhibitors of 17-β-hydroxy-steroid dehydrogenase type 1
(17β-HSD1) [5], and 7-amino-6-aryl-substituted
coumarins are characterized as progesterone
antagonists [6]. Coumarins with heterocyclic
substituents in the aromatic ring may be utilized in the
synthesis of antihypertensive [7], antimicrobial [8],
and antitumor agents [9]. The derivatives of blue
fluorescent dye, (N,N-dimethyl-7-aminocoumarin-4-
yl)acetic acid, are used as fluorescent tags in
biomedical visualization and the other branches of
modern technology [10].
significant application [13], the catalytic approach with
respect to 7-substituted coumarins was utilized only in
the synthesis of 7-aminocoumarin from 7-trifluoro-
methanesulfonyloxycoumarins [14, 15].
We recently developed a procedure for the syn-
thesis of coumarins with aromatic, heterocyclic, or
styryl substituents in the position С7 by means of Pd-
catalyzed cross-coupling of 6-methoxycarbonyl-7-
(trifluoromethanesulfonyloxy)coumarin (I) [16].
Triflate
I
was prepared by the reaction of
peuruthenicine (II) with trifluoromethanesulfonic
anhydride in pyridine. In this study we carried out the
catalytic synthesis of coumarins containing nitrogen
functions in the position С7 underlain by triflate I and
7-trifluoromethanesulfonyloxy-6-cyanocoumarin (III).
Compound III was synthesized from available furo-
coumarin oreoselone (IV) along Scheme 1 including
the Beckmann rearrangement of oreoselone (E)- and
(Z)-oximes (V) followed by the reaction of the
obtained 7-hydroxy-6-cyanocoumarin (VI) with
trifluoromethane-sulfonic anhydride (Scheme 1).
The preparation methods of 7-(N-substituted)-
aminocoumarins are based on the aminophenols
reaction with β-ketoesters in the presence of various
condensation agents [11] or on the condensation of 4-
R-amino-2-hydroxybenzaldehydes with ethyl nitro-
acetate [12]. Although recently the catalytic methods
of building up the coumarin scaffold with the use of
Compounds I and III were brought into the cross-
coupling reactions with substituted anilines, 1Н-
pyrazol-3-amine, or isoquinolin-5-amine catalyzed with
palladium phosphine complexes (amination by
Buchwald–Hartwig reaction) [17]. The reactions of
coumarins I and III with 2-(piperidin-1-yl)aniline
(VIIа), 2-(morpholin-4-yl)-5-(trifluoromethyl)aniline
(VIIb), or 4-(methylsulfanyl)-3-(trifluoromethyl)ani-
metal complex and organic catalysis found
a
* For communication XIII, see [1].
662

STUDY OF PLANT COUMARINS
663
Scheme 1.
O
O
Tf2O_Py
MeO
MeO
TfO
O
O
HO
O
O
II
I
O
HON
NC
NC
HO
Tf2O_Py
O
.
PCl5
NH2OH HCl
O
TfO
O
O
O
O
O
O
O
O
III
V
IV
VI
line (VIIc) were carried out under the conditions that
we had developed for the catalytic amination of 2-
isopropyl-3-(trifluoromethanesulfonyloxy)psoralen with
aniline derivatives [solvent DMF, catalytic system Pd
(OAc)2–BINAP, 4 : 8 mol %, base triethylamine] [18].
To achieve a complete conversion of initial compounds
I and III the temperature was raised to 135–140°С and
the reaction time prolonged to 16 h. As a result we
obtained 7-(arylamino)-6-methoxycarbonylcoumarins
VIIIa–VIIIc (yield 63–71%) or 7-arylamino-6-
cyanocoumarins IXa–IXc (yield 54–65%) isolated by
column chromatography on silica gel (Scheme 2).
We have established that the reaction of 7-
tosyloxycoumarin (Х) with 2-(piperidin-1-yl)aniline
(VIIa) proceeds with the formation of amination
product VIIIa, but the complete conversion of initial
coumarin Х requires a considerable prolongation of the
reaction time (in 16 h the conversion has reached
50%).
The catalytic amination of compounds I and III with
isoquinoline-5-amine (XI) provided 7-[(isoquinolin-5-yl)-
amino]coumarins XII and XIII (yield 63–64%)
(Scheme 3). 7-(Trifluoromethanesul-fonyloxy)coumarins
I and III with 3-amino-1Н-pyrazole (XIV) afforded the
corresponding 6-substituted 7-(1H-pyrazol-3-ylamino)
coumarins XV and XVI (yield 44 and 72% respectively).
Only few instances of Pd-catalyzed amination of
aryl tosylates and benzyl sulfonates are published [19].
Scheme 2.
O
NH2
MeO
R1
R2
Pd(OAc)2_BINAP,
O
O
HN
+
I
R1
R2
Et3N, DMF, 135_140oC
R4
R3
R4
VIIa_VIIc
R3
VIIIa_VIIIc
NC
HN
Pd(OAc)2_BINAP,
O
O
VIIa_VIIc
III
+
R1
R2
Et3N, DMF, 135_140oC
R4
R3
O
IXa_IXc
VIIa
TsCl, K2CO3, THF
MeO
TsO
II
VIIIa
Pd(OAc)2_BINAP,
Et3N, DMF, 135_140oC
O
O
X
R1 = (CH2)5N, R2 = R3 = R4 = Н (a); R1 = morpholin-4-yl, R2 = R3 = Н, R4 = CF3 (b); R1 = R4 = H, R2 = CF3, R3 = SCH3 (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 5 2014

MAKHNIOVA et al.
664
Scheme 3.
NH2
NH2
R
R
N
N
H
N
O
O
HN
O
O
HN
XI
XIV
I, III
4'
1'
3'
8'
Pd(OAc)2_BINAP,
Et3N, DMF, 135_140oC
Pd(OAc)2_BINAP,
Et3N, DMF, 135_140oC
6'
7'
3'
N 2'
N
NH
XII, XIII
XV, XVI
R
NH2
H
O
O
O
HN
H
R
H
Pd(OAc)2_BINAP,
Et3N, DMF, 135_140oC
N
S
+
H
6'
7'
O
5'
O
H
O
TfO
S
2' N
3'
OMe
O
4''
H
3''
OMe
O
XVII
XVIII, XIX
I, III
R = CO2Me (XII, XV, XVIII), CN (XIII, XVI, XIX).
Aiming at the synthesis of lactam antibiotics with a
coumarin fragment we examined the reaction of
compounds I and III with methyl 6-aminopenicillanate
(XVII). We thus obtained coumarinоpenicillins XVIII
and XIX (yield 65%). The combination in the same
molecule of a coumarin and a β-lactam fragments
seems promising in the light of modern trends in
penicillins improvement by conjugation with peptides,
catechols, and isochromans [20].
Thus the catalytic amination of 7-hydroxycoumarin
derivatives with diverse amines affords N-substituted
7-aminocoumarins that may be of interest like
bioactive compounds.
EXPERIMENTAL**
NMR spectra were registered on spectrometers
Bruker AV-300 [300.13 (1Н), 282.38 (19F), 75.47 MHz
(13С)], AV-400 [400.13 (1Н), 100.78 MHz (13С)], and
AV-600 [600.30 (1Н), 150.96 MHz (13С)]. Chemical
The composition and structure of compounds
synthesized were established from spectral data and
elemental analysis. IR spectra of 6-cyanocoumarins
III, IXa–IXc, XIII, XVI, and XIX contain
characteristic bands of stretching vibrations of cyano
group (2226–2241 cm–1). In the IR spectra of lactam
derivative coumarins XVIII and XIX characteristic
absorption bands of the carbonyl groups are observed
at 1785, 1748–1740 (β-lactam), 1680–1726 (C=O of
coumarin and COOMe) and of amino groups, at 3465–
3478, 3412–3431 cm–1.
1
shifts in the Н and 13С spectra were measured with
respect to the residual signals of solvent СHСl3 (δH
7.24, δС 76.90 ppm); in 19F spectra an internal
reference С6F6 (δF 0.00 ppm) was used. The
multiplicity of signals in 13С NMR spectra was
established by common procedures in the single
resonance mode. IR spectra were recorded on a
spectrophotometer Vector-22 from pellets with KВr.
UV spectra were taken on a spectrophotometer HР
8453 UV Vis. Melting points were measured on a
heating block Stuart SMF-38.
1Н and 13С NMR spectra of obtained compounds
correspond to their assumed structure and contain a
single set of the characteristic signals from the coumarin
scaffold and the respective substituent. The special
feature of compounds XVIII and XIX is the presence of
the penicillin fragment. The protons of the lactam ring
Elemental analysis was carried out on a СНN-
analyzer Carlo Erba 1106.
Reaction products were isolated by column
chromatography on silica gel Acros (0.035–0.070 mm)
1
H2',5',6' in the Н NMR spectra give rise to signals at δ,
** Analytic and spectral measurements were performed at the
Chemical Services Center for general use of the Siberian
Branch of the Russian Academy of Sciences.
ppm: 4.26 s (1Н, Н2'), 4.60–4.68 d (1Н, Н5'), and 5.26–
5.48 d.d (Н6', J5',6' 4.3–4.4 Hz).
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STUDY OF PLANT COUMARINS
665
or on aluminum oxide, eluents chloroform, chloro-
form–ethanol, 25 : 1.
Methyl 2-oxo-7-(tosyloxy)-2H-chromene-6-car-
boxylate (X). To a solution of 200 mg (0.91 mmol) of
6-methoxycarbonyl-7-hydroxycoumarin (II) in 3 mL of
THF was added at stirring in succession 345 mg
(1.82 mmol) of p-tolyenesulfonyl chloride and 579 mg
(2.73 mmol) of K2CO3. The reaction mixture was
heated to 60°С and kept at this temperature for 30 h.
On the completion of the reaction (TLC monitoring by
disappearance of the spot of initial coumarin II) the
reaction mixture was evaporated to 1 mL, the residue
was diluted with 5 mL of water, the reaction product
was extracted into dichloromethane (4 × 5 mL). Yield
250 mg (73%), mp 145–146°С (chloroform). IR
spectrum, cm–1: 3053, 2937, 2739, 2677, 2492, 1722,
1624, 1599, 1441, 1379, 1320, 1286, 1219, 1178,
1132, 1105, 1040, 1013, 966, 926, 908, 818, 779, 750,
690, 667. UV spectrum (EtOH), λmax, nm (log ε): 213
Reaction progress was monitored by TLC on
Silufol UV-254 plates, eluent chloroform–ethanol,
25 : 1, spots visualized with iodine vapor or under UV
irradiation.
Solvents (DMF, THF, chloroform), and also Et3N
were purified by standard procedures.
Used in the study BINAP, tosyl chloride, 6-amino-
penicillanic acid, and trifluoromethanesulfonic anhyd-
ride were purchased from Alfa Aesar.
Methyl 6-aminopenicillanate (XVII) was obtained
by procedure [21], peuruthenicine triflate (I), by
procedure [16], Pd(OAc)2, by procedure [22], 7-hyd-
roxy-6-cyanocoumarin (VI) was prepared by oreselone
(IV) oximation [23] with subsequent rearrangement of
oximes V by Beckmann reaction [24]. Spectral
characteristics of compound VI were consistent with
the published data [24].
1
(3.89), 239 (4.13), 334 (4.09). Н NMR spectrum
(CDCl3), δ, ppm: 2.45 s (3H, СН3), 3.84 s (3H, OСН3),
6.43 d (1Н, Н3, J 9.6 Hz), 6.90 s (1Н, Н8), 7.37 d (2Н,
Н3',5', J 8.2 Hz), 7.70 d (1Н, Н4, J 9.6 Hz), 7.78 d (1Н,
Н2', J 8.2 Hz), 7.88 d (1Н, Н6', J 8.2 Hz), 8.09 s (1Н,
Н5). 13С NMR spectrum (CDCl3), δ, ppm: 21.68 (СН3),
52.04 (OСН3), 112.19 (С8), 117.27 (C6), 117.46 (C4a),
125.78 (C3), 128.37 (С2',6'), 128.70 (C5), 129.94 (C3',5'),
132.03 (C1'), 142.21 (C4'), 146.06 d (C4), 149.90 (C7),
156.15 (C8a), 159.01 (C2), 163.72 s (C=O при С6).
Found, %: C 57.30; H 3.63; S 8.86. С18Н14O7S.
Calculated, %: С 57.75; H 3.77; S 8.57.
2-Oxo-7-(trifluoromethanesulfonyloxy)-2H-
chromene-6-carbonitrile (III). A solution of 500 mg
(2.67 mmol) of 7-hydroxy-6-cyanocoumarin (VI) in 5 mL
of pyridine was cooled to 0°С and at stirring under an
argon atmosphere was added thereto within 15 min
1.35 mL (8.02 mmol) of trifluoromethanesulfonic
anhydride. The mixture was warmed to room
temperature and left standing for 2 days with
intermittent stirring. It was quenched with 10 mL of
water. The reaction product was extracted into
dichloromethane (4 × 5 mL), the combined organic
solutions were dried with MgSO4 and evaporated,
pyridine traces were removed by azeotropic distillation
with benzene, the residue was crystallized from
ethanol. Yield 510 mg (60%), mp 124–125°С
(ethanol). IR spectrum, cm–1: 3127, 3087, 3059, 2960,
2226, 1725, 1703, 1630, 1331, 1226, 1135, 1100, 960,
870, 750, 658, 601. UV spectrum (EtOH), λmax, nm
Methyl 2-oxo-7-[2-(piperidin-1-yl)phenylamino]-
2Н-chromene-6-carboxylate (VIIIа). а. To a solution
of 100 mg (0.3 mmol) of peuruthenicine triflate (I) in
3 mL of DMF under an argon atmosphere was added
in succession 106 mg (0.6 mmol) of 2-(piperidin-1-yl)
aniline (VIIa), 4 mg (4 mo l%) of Pd(OAc)2, 22 mg
(8 mol %) of BINAP, 0.062 mL (0.3 mmol) of Et3N.
The reaction mixture was stirred for 8 h at 135–140°С
[23], then it was poured in a Petri dish for evaporation
in air. The residue was chromatographed on a column
packed with silica gel (eluent chloroform), trace
amount of reaction product and 90 mg of initial
compound VIIa were isolated.
1
(log ε): 220 (3.99), 238 (4.20), 335 (4.11). Н NMR
spectrum (CDCl3), δ, ppm: 6.59 d (1Н, Н3, J 9.8 Hz),
7.45 s (1Н, Н8), 7.71 d (1Н, Н4, J 9.8 Hz), 7.92 s (1Н,
Н5). 13С NMR spectrum (CDCl3), δ, ppm: 103.58 (С6),
112.11 (C3), 112.41 (C4a), 116.43 (C8), 118.9 (CN),
117.94, 118.47, 119.51, 120.04 (CF3, J 146.3 Hz),
133.71 (С5), 140.62 (C4), 150.72 (C7), 160.01 (C2),
163.91 (C8a). 19F NMR spectrum (CDCl3), δ, ppm:
89.70 (СF3). Found, %: C 40.84; H 1.40; F 17.56; N
4.25; S 9.79. С11Н4F3NO5S. Calculated, %: C 41.39; H
1.26; F 17.85; N 4.39; S 10.05.
b. To a solution of 100 mg (0.3 mmol) of
peuruthenicine triflate (I) in 3 mL of DMF under an
argon atmosphere was added in succession 106 mg
(0.6 mmol) of compound VIIa, 4 mg (4 mol %) of Pd
(OAc)2, 22 mg (8 mol %) BINAP, and 0.062 mL
(0.3 mmol) of Et3N. The reaction mixture was stirred
for 16 h at 135–140°С (TLC monitoring), cooled, and
poured in a Petri dish for evaporation in air. The
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MAKHNIOVA et al.
666
column chromatography on slica gel (eluent
chloroform) afforded 80 mg (71%) of compound
VIIIа.
NMR spectrum (CDCl3), δ, ppm: 50.96 (C3",5"), 52.93
(OСН3), 67.36 (C2",6"), 93.22 (С8), 97.36 (С4а), 110.60
(C6), 111.67 (С3), 114.67 (C3'), 115.49 (C6'), 116.47
(C4'), 117.49 (С5'), 119.49 q (CF3, J 147.9 Hz), 132.67
(С5), 141.74 (С1'), 145.91 (С4), 149.57 (C2'), 156.72
(С7), 158.37 (С8а), 161.78 (С2), 162.94 (C=O). Found,
%: C 59.22; H 4.03; F 12.28; N 6.69. С22Н19F3N2O5.
Calculated, %: С 58.93; H 4.27; F 12.71; N 6.25.
c. To a solution of 150 mg (0.4 mmol) of
peuruthenicine tosylate (Х) in 3 mL of DMF under an
argon atmosphere was added 141 mg (0.8 mmol) of
compound VIIа, 5 mg (4 mol %) of Pd(OAc)2, 28 mg
(8 mol %) of BINAP, and 0.081 mL (0.4 mmol) of
Et3N. The mixture was stirred for 16 h at 135–140°С.
After the workup as described above we isolated
85 mg (56%) of compound VIIIa and 70 mg of initial
compound X. Conversion 48%.
Methyl 7-{[4-methylsulfanyl-3-(trifluoromethyl)-
phenyl]amino}-2-oxo-2Н-chromene-6-carboxylate
(VIIIc) was prepared by method b from 100 mg
(0.3 mmol) of peuruthenicine triflate (I) and 124 mg
(0.6 mmol) of 4-methylsulfanyl-3-(trifluoromethyl)-
aniline (VIIc). Yield 90 mg (69%), mp 132–133°С
(ethanol). IR spectrum, cm–1: 3393, 3222, 3061, 2964,
1735, 1676, 1626, 1579, 1491, 1446, 1393, 1342,
1299, 1278, 1234, 1214, 1195, 1145, 1109, 1076,
1064, 948, 915, 903, 826, 797, 735. UV spectrum
(EtOH), λmax, nm (log ε): 226 (4.10), 245 (3.84), 288
Compound VIIIa, mp 70–71°С (ethanol). IR
spectrum, cm–1: 3435, 3065, 2959, 1723, 1678, 1630,
1612, 1600, 1576, 1491, 1431, 1377, 1331, 1292,
1221, 1178, 1140, 1099, 1059, 1030, 962, 905, 878,
835, 785, 752. UV spectrum (EtOH), λmax, nm (log ε):
222 (4.27), 240 (4.24), 275 (3.75), 285 (3.87), 311
1
(3.46). Н NMR spectrum (CDCl3–CD3OD), δ, ppm:
1
1.59 m (2H, H3",5"), 1.71 m (2H, H3",5" and 2H, H4"),
2.87 m (4H, H2",6"), 3.99 s (3H, OСН3), 6.52 d (1Н, Н3,
J 9.7 Hz), 6.71 d (1Н, Н3', J 7.7 Hz), 6.74 d.d (1Н, Н5',
J 7.2, 7.7 Hz), 6.92 d.d (1Н, Н4', J 7.2, 8.0 Hz), 6.99 d
(1Н, Н6', J 8.0 Hz), 7.33 s (1Н, Н8), 7.73 d (1Н, Н4, J
9.7 Hz), 8.28 s (1Н, Н5). 13С NMR spectrum (CDCl3–
CD3OD), δ, ppm: 24.13 (C4"), 26.58 (C3",5"), 52.82
(C2",6"), 52.14 (OСН3), 93.16 (С8), 100.46, 100.51
(С4а,3'), 108.39 (C6), 111.83 (C4'), 115.26 (С3), 118.49
(C6'), 119.69 (С5'), 132.59 (С5), 139.72 (С1'), 141.41
(С2'), 142.86 (C4), 156.71 (С7), 158.65 (С8а), 161.33
(С2), 162.92 (C=O). Found, %: C 70.09; H 5.67; N
6.99. С22Н22N2O4. Calculated, %: С 69.83; H 5.86; N
7.40.
(3.66), 325 (3.84), 335 (3.75). Н NMR spectrum
(CDCl3), δ, ppm: 2.39 s (3H, SСН3), 3.99 s (3H,
OСН3), 4.58 br.s (1Н, NH), 6.53 d (1Н, Н3, J 9.6 Hz),
6.76 d.d (1Н, Н6', J 7.8, 2.2 Hz), 6.94 s (1Н, Н8), 6.96
d (1Н, Н2', J 2.2 Hz), 7.32 d (1Н, Н5', J 7.8 Hz), 7.74 d
(1Н, Н4, J 9.6 Hz), 8.27 s (1Н, Н5). 13С NMR spectrum
(CDCl3), δ, ppm: 19.52 (SCН3), 52.93 (OСН3), 104.84
(С8), 110.02 (С4а), 111.89 (С3), 112.08 (C6), 113.18
(C2'), 116.58 (C4'), 121.45 q (CF3, J 147.9 Hz), 125.54
(C6'), 127.21 (С5'), 132.67 (С5), 134.52 (C3'), 141.68
(С1'), 145.35 (С4), 156.79 (С7), 158.45 (С8а), 161.73
(С2), 162.98 (C=O). Found, %: C 56.08; H 3.65; F
13.26; N 3.69; S 8.02. С19Н14F3NO4S. Calculated, %:
С 55.74; H 3.42; F 13.92; N 3.42; S 7.83.
Methyl 7-{[2-(morpholin-4-yl)-5-(trifluoro-
methyl)phenyl]amino}-2-oxo-2Н-chromene-6-
carboxylate (VIIIb) was prepared by method b from
100 mg (0.3 mmol) of peuruthenicine triflate (I) and
152 mg (0.6 mmol) of 2-(morpholin-4-yl)-5-
(trifluoromethyl)aniline (VIIb). Yield 85 mg (63%),
mp 89–91°С (ethanol). IR spectrum, cm–1: 3435, 3065,
2959, 1735, 1678, 1630, 1611, 1576, 1491, 1431,
1377, 1331, 1292, 1221, 1178, 1140, 1099, 1059,
1030, 962, 905, 878, 835, 785, 752. UV spectrum
(EtOH), λmax, nm (log ε): 239 (4.41), 274 (3.95), 285
2-Oxo-7-[2-(piperidin-1-yl)phenylamino]-2Н-
chromene-6-carbonitrile (IХа) was prepared by
method b from 100 mg (0.3 mmol) of compound III
and 106 mg (0.6 mmol) of compound VIIa, 4 mg
(4 mol %) of Pd(OAc)2, 22 mg (8 mol %) of BINAP,
0.062 mL (0.3 mmol) of Et3N. Yield 60 mg (54%), mp
78–80°С (ethanol). IR spectrum, cm–1: 3437, 3344,
3057, 2932, 2853, 2804, 2239, 1753, 1665, 1626,
1609, 1572, 1501, 1439, 1425, 1379, 1319, 1273,
1238, 1229, 1177, 1136, 1101, 1072, 1034, 918, 907,
870, 833, 777, 748, 698. UV spectrum (EtOH), λmax
,
1
(3.92), 309 (3.79). Н NMR spectrum (CDCl3), δ,
nm (log ε): 220 (4.39), 240 (4.18), 286 (3.74), 335
ppm: 2.84 m (4H, H3",5"), 3.76 m (4H, H2",6"), 3.89 s
(3H, OСН3), 4.58 br.s (1Н, NH), 6.38 d (1Н, Н3, J
9.6 Hz), 6.46 d (1Н, Н3', J 7.6 Hz), 6.87 d.d (1Н, Н4', J
7.6, 2.2 Hz), 6.91 d (1Н, Н6', J 2.2 Hz), 7.16 s (1Н,
Н8), 7.67 d (1Н, Н4, J 9.6 Hz), 8.19 s (1Н, Н5). 13С
(2.76). Н NMR spectrum (CDCl3–CD3OD), δ, ppm:
1
1.53 m (2H, H3",5"), 1.63–1.74 m (2Н, H3",5" and 2Н,
H4"), 2.79 m (4H, H2",6"), 6.55 d (1Н, Н3, J 9.7 Hz),
6.70 d (1Н, Н3', J 7.7 Hz), 6.74 d.d (1Н, Н5', J 7.2,
7.7 Hz), 6.86 d.d (1Н, Н4', J 7.2, 8.0 Hz), 6.95 d (1Н,
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STUDY OF PLANT COUMARINS
667
Н6', J 8.0 Hz), 7.43 s (1Н, Н8), 7.71 d (1Н, Н4, J
9.7 Hz), 7.92 s (1Н, Н5). 13С NMR spectrum (CDCl3–
CD3OD), δ, ppm: 24.09 (C4"), 26.59 (C3",5"), 52.59,
53.02 (C2",6"), 103.41 (C6), 109.51 (С4а), 111.80 (С3),
112.35 (С8), 113.01 (С3'), 113.96 (C4'), 115.18 (C6'),
118.68 (CN), 118.90 (С5'), 123.98 (С1'), 132.59 (С5),
140.91 (С2'), 141.38 (C4), 156.86 (С7), 159.46 (С8а),
160.30 (С2). Found, %: C 73.30; H 5.67; N 11.79.
С21Н19N3O2. Calculated, %: С 73.03; H 5.54; N 12.17.
(С4а), 113.24 (C4'), 113.88 (С3), 115.72 (C2'), 117.47
(CN), 125.88 q (CF3, J 147.9 Hz), 129.66 (C6’), 130.95
(С5'), 134.00 (С5), 134.47 (C3'), 136.06 (С1'), 143.17
(С4), 158.17 (С7), 160.83 (С8а), 162.98 (С2). Found, %:
C 57.12; H 3.03; F 14.95; N 7.89; S 8.43.
С18Н11F3N2O2S. Calculated, %: С 57.44; H 2.95; F
15.14; N 7.44; S 8.52.
Methyl 7-(isoquinolin-5-ylamino)-2-oxo-2Н-
chromene-6-carboxylate (XII). To a solution of
100 mg (0.3 mmol) of peuruthenicine triflate (I) in 3
mL of DMF under an argon atmosphere was added in
succession 83 mg (0.6 mmol) of isoquinolin-5-amine
(XI), 4 mg (4 mol %) of Pd(OAc)2, 22 mg (8 mol %)
of BINAP, 0.062 mL (0.3 mmol) of Et3N. The reaction
mixture was stirred for 16 h at 135–140°С (TLC
monitoring), cooled, and poured in a Petri dish for
evaporation in air. By column chromatography on
silica gel (eluent chloroform) we isolated 70 mg (63%)
of compound XII, mp 113–114°С (ethanol). IR
spectrum, cm–1: 3435, 3065, 3143, 1740, 1678, 1630,
1611, 1576, 1491, 1431, 1377, 1331, 1292, 1221,
1178, 1140, 1099, 1059, 1030, 962, 905, 878, 835,
780, 752. UV spectrum (EtOH), λmax, nm (log ε): 225
(4.17), 240 (4.30), 275 (3.83), 285 (3.79), 311 (3.64).
1Н NMR spectrum (CDCl3–CD3OD), δ, ppm: 3.92 s
(3H, OСН3), 6.46 d (1Н, Н3, J 9.7 Hz), 6.90 d.d (1Н,
Н6', J 8.2, 1.6 Hz), 7.18 s (1Н, Н8), 7.32 d.d (1Н, Н7', J
8.2, 7.6 Hz), 7.52 d (1Н, Н4', J 7.2 Hz), 7.60 d.d (1Н,
Н8', J 7.6, 1.6 Hz), 7.71 d (1Н, Н4, J 9.7 Hz), 8.20 с
(1Н, Н5), 8.32 d (1Н, Н3', J 7.2 Hz), 9.04 d (1Н, Н1').
13С NMR spectrum (CDCl3–CD3OD), δ, ppm: 52.78
(OСН3), 104.12 (C6), 111.69 (C8), 113.32 (C4а), 114.76
(C3), 117.54 (C8'), 118.35 (C6'), 120.56 (С4'), 125.92
(С8a), 128.11 (С7'), 130.63 (C5), 132.54 (C4a'), 141.66
(C5'), 142.35 (C4), 144.74 (С3'), 150.05 (C1'), 151.95
(C7), 158.45 (C8a), 160.87 (C2), 162.88 (C=O). Found,
%: C 69.65; H 4.32; N 7.78. С20Н14N2O4. Calculated,
%: С 69.36; H 4.07; N 8.09.
7-{[2-(Morpholin-4-yl)-5-(trifluoromethyl)phenyl]-
amino}-2-oxo-2Н-chromene-6-carbonitrile (IХb)
was prepared by method b from 100 mg (0.3 mmol) of
compound III and 152 mg (0.6 mmol) of compound
VIIb. Yield 80 mg (65%), mp 138–139°С (ethanol).
IR spectrum, cm–1: 3433, 3344, 3078, 3059, 2239,
1753, 1655, 1628, 1605, 1570, 1485, 1452, 1425,
1379, 1337, 1275, 1240, 1219, 1177, 1136, 1101,
1072, 995, 939, 916, 907, 870, 833, 777, 750, 698. UV
spectrum (EtOH), λmax, nm (log ε): 233 (4.54), 203
1
(4.47), 274 (3.96), 285 (3.93), 312 (3.86). Н NMR
spectrum (CDCl3–CD3OD), δ, ppm: 2.86 m (4H,
H3",5"), 3.78 m (4H, H2",6"), 6.48 d (1Н, Н3, J 9.6 Hz),
6.54 d (1Н, Н3', J 7.8 Hz), 6.91 d.d (1Н, Н4', J 7.8,
2.0 Hz), 6.94 d (1Н, Н6', J 2.0 Hz), 7.41 s (1Н, Н8),
7.73 d (1Н, Н4, J 9.6 Hz), 7.94 s (1Н, Н5). 13С NMR
spectrum (CDCl3–CD3OD), δ, ppm: 50.53, 50.66
(C3",5"), 67.11, 67.14 (C2",6"), 93.98 (С8), 103.05 (C6),
104.54 (С4а), 111.66 (С3), 105.84 (C3'), 108.15 (C6'),
118.77 (CN), 119.29 (C4'), 125.12 q (CF3, J 147.9 Hz),
129.65 (С5'), 131.82 (С5), 134.01 (С1'), 141.08 (С4),
142.54 (C2'), 156.71 (С7), 158.37 (С8а), 160.04 (С2).
Found, %: C 60.20; H 4.03; F 13.63; N 9.98.
С21Н16F3N3O3. Calculated, %: С 60.72; H 3.88; F
13.72; N 10.12.
7-{[4-Methylsulfanyl-3-(trifluoromethyl)phenyl]-
amino}-2-oxo-2Н-chromene-6-carbonitrile (IХc)
was prepared by method b from 100 mg (0.3 mmol) of
compound III and 124 mg (0.6 mmol) of compound
VIIc. Yield 70 mg (57%), mp 139–140°С (ethanol). IR
spectrum, cm–1: 3431, 3061, 2230, 1760, 1705, 1624,
1504, 1483, 1439, 1394, 1327, 1286, 1263, 1240,
1223, 1157, 1130, 1030, 997, 908, 851, 826, 748, 725,
692. UV spectrum (EtOH), λmax, nm (log ε): 225
7-(Isoquinolin-5-ylamino)-2-oxo-2Н-chromene-
6-carbonitrile (XIII) was similarly obtained from
100 mg (0.3 mmol) of compound III and 83 mg
(0.6 mmol) of isoquinolin-5-amine (XI). Yield 60 mg
(64%), mp 102–103°С (ethanol). IR spectrum, cm–1:
3449, 3375, 3256, 2233, 1735, 1630, 1605, 1572,
1495, 1487, 1425, 1391, 1277, 1250, 1227, 1177,
1136, 1101, 1074, 1030, 916, 907, 870, 833, 800, 777,
750, 700. UV spectrum (EtOH), λmax, nm (log ε): 220
(4.12), 239 (4.22), 274 (3.34), 285 (3.45), 324 (3.72).
1Н NMR spectrum (CDCl3–CD3OD), δ, ppm: 6.53 d
(1Н, Н3, J 9.7 Hz), 7.13 d.d (1Н, Н6', J 8.0, 1.6 Hz),
1
(4.57), 236 (4.54), 325 (4.11). Н NMR spectrum
(CDCl3–CD3OD), δ, ppm: 2.08 s (3H, SСН3), 6.43 d
(1Н, Н3, J 9.6 Hz), 6.62 d.d (1Н, Н6', J 7.6, 1.8 Hz),
6.88 d (1Н, Н2', J 1.8 Hz), 6.94 s (1Н, Н8), 7.26 d
(1Н, Н5', J 7.6 Hz), 7.81 d (1Н, Н4, J 9.6 Hz), 8.19 s
(1Н, Н5). 13С NMR spectrum (CDCl3–CD3OD), δ,
ppm: 20.12 (SCН3), 98.22 (C6), 103.69 (С8), 112.39
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MAKHNIOVA et al.
668
7.14 s (1Н, Н8), 7.37 d.d (1Н, Н7', J 8.0, 7.6 Hz), 7.48
d (1Н, Н4', J 7.0 Hz), 7.56 d.d (1Н, Н8', J 7.6, 1.6 Hz),
7.87 d (1Н, Н4, J 9.7 Hz), 8.12 с (1Н, Н5), 8.23 d.d
(1Н, Н3', J 7.0, 1.8 Hz), 8.77 d (1Н, Н1', J 1.8 Hz). 13С
NMR spectrum (CDCl3–CD3OD), δ, ppm: 102.78 (C6),
111.47 (C8), 112.13 (C4а), 115.71 (C3), 117.15 (C8'),
118.20 (C6'), 118.41 (С4'), 118.99 (CN), 126.47 (С8a’),
128.56 (С7'), 130.38 (C5), 132.61 (C4a'), 140.30 (C5'),
141.16 (C4), 143.38 (С3'), 148.11 (C1'), 150.15 (C7),
157.96 (C8a), 160.88 (C2). Found, %: C 73.14; H 3.26;
N 13.59. С19Н11N3O2. Calculated, %: С 72.84; H 3.54;
N 13.41.
spectrum (EtOH), λmax, nm (log ε): 205 (4.08), 211
(4.07), 227 (4.05), 236 (4.07), 301 (3.45), 325 (3.61). 1Н
NMR spectrum (CDCl3), δ, ppm: 6.11 br.s (2H, NH and
1H, H4'), 6.46 d (1Н, Н3, J 9.7 Hz), 7.11 s (1Н, Н8), 7.32
d (1Н, H5', J 1.9 Hz), 7.81 d (1Н, Н4, J 9.7 Hz), 8.28 s
(1Н, Н5). 13С NMR spectrum (CDCl3), δ, ppm: 102.48
(C6), 104.51 (C4'), 109.37 (С4а), 113.25 (С8), 113.84
(С3), 118.99 (CN), 131.56 (С5), 140.99 (С5'), 142.51
(С4), 143.97 (С7), 155.16 (C1'), 159.18 (С8а), 161.54
(С2). Found, %: C 61.93; H 3.70; N 22.66. С13Н8N4O2.
Calculated, %: С 61.90; H 3.20; N 22.21.
Methyl (2R,5S,6S)-3,3-dimethyl-6-[(6-
Methyl 2-oxo-7-[(1H-pyrazol-3-yl)amino]-2Н-chro- methoxycarbonyl-2-oxo-2H-chromen-7-yl)amino]-
mene-6-carboxylate (XV). To a solution of 100 mg
(0.3 mmol) of peuruthenicine triflate (I) in 3 mL of
DMF under an argon atmosphere was added in
succession 50 mg (0.6 mmol) of 1Н-pyrazol-3-amine
(XIV), 4 mg (4 mol %) of Pd(OAc)2, 22 mg
(8 mol %) of BINAP, and 0.062 mL (0.3 mmol) of
triethylamine. The reaction mixture was stirred for 16 h
at 135–140°С (TLC monitoring), cooled, and poured
in a Petri dish for evaporation in air. By column
chromatography on silica gel (eluent chloroform) we
isolated 50 mg (44%) of compound XV, mp 124–125°С
(ethanol). IR spectrum, cm–1: 3325, 3088, 3060, 2959,
2855, 1744, 1725, 1680, 1630, 1609, 1576, 1550,
1493, 1430, 1376, 1297, 1238, 1228, 1222, 1205,
1181, 1135, 1101, 1060, 1031, 961, 904, 885, 870,
844, 785, 772, 750, 658, 601. UV spectrum (EtOH),
7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate
(XVIII). To a solution of 100 mg (0.3 mmol) of
peuruthenicine triflate (I) in 3 mL of DMF under an
argon atmosphere was added in succession 259 mg
(0.6 mmol) of methyl 6-aminopenicillanate (XVII),
4 mg (4 mol %) of Pd(OAc)2, 22 mg (8 mol %) of
BINAP, and 0.062 mL (0.3 mmol) of triethylamine.
The reaction mixture was stirred for 16 h at 135–140°С
(TLC monitoring), cooled, and poured in a Petri dish
for evaporation in air. By column chromatography on
silica gel (eluent chloroform) we isolated 84 mg (65%)
of viscous light-yellow oily compound XVIII. IR
spectrum, cm–1: 3465, 3412, 3143, 3065, 1785, 1740,
1678, 1630, 1611, 1526, 1495, 1431, 1375, 1331,
1292, 1221, 1178, 1140, 1099, 1059, 1030, 962, 930,
905, 878, 850, 780, 752, 728. UV spectrum (EtOH),
λ
max, nm (log ε): 232 (4.16), 274 (3.55), 285 (3.48),
λmax, nm (log ε): 210 (4.21), 224 (4.17), 240 (4.30),
1
1
311 (3.30). Н NMR spectrum (CDCl3–CD3OD), δ,
ppm: 3.90 s (3Н, ОСН3), 4.52 br.s (2Н, NH), 6.05 d
(1H, H4', J 1.9 Hz), 6.46 d (1Н, Н3, J 9.7 Hz), 7.18 s
(1Н, Н8), 7.22 d (1Н, H5', J 1.9 Hz), 7.72 d (1Н, Н4, J
9.7 Hz), 8.21 s (1Н, Н5). 13С NMR spectrum (CDCl3–
CD3OD), δ, ppm: 52.77 (OСН3), 104.49 (C4'), 111.68
(С4а), 113.66 (С8), 113.94 (С3), 116.23 (C6), 133.59
(С5), 141.87 (С5'), 142.90 (С4), 149.38 (С7), 156.52
(C1'), 158.58 (С8а), 160.76 (С2), 162.93 (C=O). Found,
%: C 58.86; H 3.95; N 14.56. С14Н11N3O4. Calculated,
%: С 58.95; H 3.89; N 14.73.
278 (3.83), 285 (3.79), 321 (3.64), 365 (3.02). Н
NMR spectrum (CDCl3–CD3OD), δ, ppm: 1.33 s (3H,
С3"Н3), 1.52 s (3H, C4"Н3), 3.71 s (3H, OСН3), 3.92 s
(3H, OСН3), 4.26 s (1Н, Н2'), 4.40 d (1Н, NН, J
6.2 Hz), 4.60 d (1Н, Н5', J 4.4 Hz), 5.26 d.d (1Н, Н6', J
6.2, 4.4 Hz), 6.48 d (1Н, Н3, J 9.7 Hz), 7.22 s (1Н, Н8),
7.78 d (1Н, Н4, J 9.7 Hz), 8.10 s (1Н, Н5). 13С NMR
spectrum (CDCl3–CD3OD), δ, ppm: 27.24 (СН3),
29.16 (СН3), 51.75 (OСН3), 52.36 (OСН3), 63.54 (С6'),
67.02 (С5'), 68.08 (С3'), 73.86 (С2'), 111.69 (C8),
113.65 (C4а), 114.08 (C3), 117.02 (C6), 130.38 (C5),
143.06 (C4), 146.15 (C7), 156.88 (C8a), 160.91(C2),
162.88 (C=O), 165.39 (С7'), 170.12 (C=O при С2').
Found, %: C 55.98; H 4.39; N 6.56. С20Н20N2O7S.
Calculated, %: С 55.55; H 4.66; N 6.48.
2-Oxo-7-[(1H-pyrazol-3-yl)amino]-2Н-chromene-
6-carbonitrile (XVI) was similarly obtained from
100 mg (0.3 mmol) of compound III and 50 mg
(0.6 mmol) of 1Н-pyrazol-3-amine (XIV). Yield 80
mg (72%), mp 124–125°С (ethanol). IR spectrum, cm–1:
3339, 3245, 3148, 2233, 2220, 2855, 1725, 1702,
1690, 1627, 1630, 1598, 1552, 1492, 1430, 1416,
1398, 1323, 1270, 1254, 1231, 1173, 1138, 1118,
1030, 992, 856, 826, 819, 770, 763, 686, 638. UV
Methyl (2R,5S,6S)-3,3-dimethyl-6-[(6-cyano-2-
oxo-2H-chromen-7-yl)amino]-7-oxo-4-thia-1-aza-
bicyclo[3.2.0]heptane-2-carboxylate (XIX) was
similarly obtained from 100 mg (0.3 mmol) of
compound III and 259 mg (0.6 mmol) of compound
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 5 2014

STUDY OF PLANT COUMARINS
669
8. Ronad, P.M., Noolvi, M.N., Sapkal, S., Dharbhamulla, S.,
XVII. Yield 80 mg (65%), yellowish oily substance.
IR spectrum, cm–1: 3478, 3431, 3086, 3055, 2241,
1784, 1738, 1703, 1674, 1626, 1505, 1445, 1404,
1369, 1329, 1292, 1271, 1213, 1161, 1138, 1099,
1030, 926, 909, 854, 835, 755, 762, 748, 731. UV
spectrum (EtOH), λmax, nm (log ε): 210 (4.32), 220
(4.21), 237 (4.19), 298 (3.51), 326 (3.73), 371 (3.24).
1Н NMR spectrum (CDCl3–CD3OD), δ, ppm: 1.37 s
(3H, С3"Н3), 1.55 s (3H, C4"Н3), 3.72 s (3H, OСН3),
4.26 s (1Н, Н2'), 4.31 d (1Н, NН, J 6.2 Hz), 4.68 d
(1Н, Н5', J 4.3 Hz), 5.48 d.d (1Н, Н6', J 6.2, 4.3 Hz),
6.40 d (1Н, Н3, J 9.7 Hz), 7.11 s (1Н, Н8), 7.82 d (1Н,
Н4, J 9.7 Hz), 8.12 s (1Н, Н5). 13С NMR spectrum
(CDCl3–CD3OD), δ, ppm: 27.24 (СН3), 29.16 (СН3),
51.75 (OСН3), 63.54 (С6'), 67.02 (С5'), 68.08 (С3'),
73.86 (С2'), 103.10 (C6), 111.57 (C8), 112.06 (C4а),
113.27 (C3), 118.11 (CN), 130.16 (C5), 142.44 (C4),
145.29 (C7), 157.36 (C8a), 161.11 (C2), 165.26 (С7'),
169.88 (C=O, С2'). Found, %: C 57.35; H 4.67; N
10.31. С19Н17N3O5S. Calculated, %: С 57.13; H 4.29;
N 10.52.
and Maddi, V.S., Eur. J. Med. Chem., 2010, vol. 45, p. 89.
9. Kathuria, A., Jalal, S., Tiwari, R., Shirazi, A.N., Gup-
ta, S., Kumar, S., Parang, K., and Sharma, S.K., Chem.
Biol. Interface, 2011, vol. 1, p. 279; Amin, K.M.,
Eissa, A.A.M., Abou-Seri, S.M., Awadallah, F.M., and
Hassan, G.S., Eur. J. Med. Chem., 2013, vol. 60, p. 187.
10. Sandler, J.S., Fenical, W., Gulledge, B.M.,
Chamberlin, A.R., and La Clair, J.J., J. Am. Chem. Soc.,
2005, vol. 127, p. 9320.
11. Rosen, T., Comp. Org. Synth., 1991, vol. 2, p. 395;
Frere, S., Thiery, V., and Besson, T., Tetrahedron Lett.,
2001, vol. 42, p. 2791; Kitamura, N., Fukagawa, T.,
Kohtani, S., Kitoh, S., Kunimoto, K., and Nakagaki, R.,
J. Photochem. Photobiol. A: Chem., 2007, vol. 188,
p. 378.
12. Morris, J.C., McMurtrie, J.C., Bottle, S.E., and Fairfull-
Smith, K.E., J. Org. Chem., 2011, vol. 76, p. 4964.
13. Fedorov, A.Yu., Nyuchev, A.V., and Beletskaya, I.P.,
Chem. Heterocycl. Comp., 2012, vol. 48, p. 166.
14. Jin, X., Uttamapinant, C., and Ting, A.Y., Chem. Bio.
Chem., 2011, vol. 12, p. 65.
15. Paunescu, E., Louise, L., Jean, L., Romieu, A., and
This work was carried out under the financial
support of the Russian Foundation for Basic Research
(grants nos. 11-03-00242-а, 12-03-92200).
Renard, P.-Y., Dyes Pigments, 2011, vol. 91, p. 427.
16. Makhneva, E.A., Lipeeva, A.V., Shults, E.E.,
Shakirov, M.M., and Tolstikov, G.A., Russ. J. Org.
Chem., 2012, vol. 48, p. 1094.
17. Kienle, M., Dubbaka, S.R., Brade, K., and Knochel, P.,
Eur. J. Org. Chem., 2007, p. 4166; Surry, D.S., and
Buchwald, S.L., Chem. Sci., 2011, vol. 2, p. 27.
REFERENCES
1. Lipeeva, A.V., Shul’ts, E.E., Shakirov, M.M.,
Bagryanskaya, I.Yu., and Tolstikov, G.A., Russ. J. Org.
Chem., 2013, vol. 49, p. 403.
18. Lipeeva, A.V., Shul’ts, E.E., Shakirov, M.M., and
Tolstikov, G.A., Russ. J. Org. Chem., 2011, vol. 47, p. 1390.
2. Motai, T. and Kitanaka, S., Chem. Pharm. Bull., 2004,
vol. 52, p. 1215; Raghav, S.K., Gupta, B., Shrivastava, A.,
and Das, H.R., Eur. J. Pharm., 2007, vol. 560, p. 69.
3. Nakamura, T., Kodama, N., Oda, M., Tsuchiya, S.,
Arai, Y., Kumamoto, T., Ishikawa, T., Ueno, K., and
Yano, S., J. Nat. Med., 2009, vol. 63, p. 15.
4. Kontogiorgis, C.A. and Hadjipavlou-Litina, D.J.,
J. Med. Chem., 2005, vol. 48, p. 6400; Timonen, J.M.,
Nieminen, R.M., Sareila, O., Goulas, A., Moilanen, L.J.,
Haukka, M., Vainiotalo, P., Moilanen, E., and Aulas-
kari, P.H., Eur. J. Med. Chem., 2011, vol. 46, p. 3845.
19. Bolm, C., Hildebrand, J.P., and Rudolph, J., Synthesis,
2000, p. 911; Huang, X., Anderson, K.W., Zim, D.,
Jiang, L., Klapars, A., and Buchwald, S.L., J. Am.
Chem. Soc., 2003, vol. 125, p. 6653.
20. Josephine, H.R., Kumar, I., and Pratt, R.F., J. Am.
Chem. Soc., 2004, vol. 126, p. 8122; Schobert, R. and
Stangl, A., Tetrahedron Lett., 2005, vol. 46, p. 1127;
Turos, E., Reddy, G.S.K., Greenhalgh, K., Ramaraju, P.,
Abeylath, S.C., Jang, S., Dickey, S., and Lim, D.V.,
Bioorg. Med. Chem. Lett., 2007, vol. 17, p. 3468.
21. Schobert, R. and Stangl, A., Tetrahedron Lett., 2005,
5. Starcevic, S, Brozic, P., Turk, S., Cesar, J., Rizner, T.L.,
vol. 46, p. 1127.
and Gobec, S., J. Med. Chem., 2011, vol. 54, p. 248.
22. Shul’pin, G. B., Organic Reactions Catalyzed by Metal
Complexes, Moscow, Nauka, 1988.
23. Nikonov, G.K., Zh. Obszch. Khimii, 1961, vol. 31, p. 305.
6. Sakai, H., Hirano, T., Mori, S., Fujii, S., Masuno, H.,
Kinoshita, M., Kagechika, H., and Tanatani, A., J. Med.
Chem., 2011, vol. 54, p. 7055.
24. Bagryanskaya, I.Yu., Gatilov, Yu.V., Osadchii, S.A.,
Martynov, A.A., Shakirov, M.M., Shul’ts, E.E., and
Tolstikov, G.A., Chem. Nat. Comp., 2005, vol. 41, p. 657.
7. Amin, K.M., Awadallah, F.M., Eissa, A.A.M., Abou-
Seri, S.M., and Hassan, G.S., Bioorg. Med. Chem.,
2011, vol. 19, p. 6087.
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