N-heterocyclic carbenes: III. N-heterocyclic carbene ligands based on abietane in Suzuki-Miyaura reaction

Article abstract of DOI:10.1134/S1070428011020114

By reactions of N-alkyl- and N-arylimidazoles with methyl 12-bromoacetyldehydroabietate a series of unsymmetrically substituted chiral imidazolium bromides with the abietane fragment was synthesized. The salts obtained were suggested as new N-heterocyclic carbene ligands in the Suzuki-Miyaura reaction.

Full text of DOI:10.1134/S1070428011020114

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 2, pp. 230235. Pleiades Publishing, Ltd., 2011.
Original Russian Text  V.A. Glushkov, M.S. Valieva, O.A. Maiorova, E.V. Baigacheva, A.A. Gorbunov, 2011, published in Zhurnal Organicheskoi Khimii,
2011, Vol. 47, No. 2, pp. 238243.
N-Heterocyclic Carbenes: III.*
N-Heterocyclic Carbene Ligands Based on Abietane
in Suzuki–Miyaura Reaction
V. A. Glushkova, M. S. Valievab, O. A. Maiorovaa, E. V. Baigachevaa, and A. A. Gorbunova
aInstitute of Engineering Chemistry, Ural Division, Russian Academy of Sciences, Perm, 614013 Russia
e-mail: glusha55@gmail.com
bPerm State University, Perm, Russia
Received July 20, 2010
Abstract—By reactions of N-alkyl- and N-arylimidazoles with methyl 12-bromoacetyldehydroabietate a series of
unsymmetrically substituted chiral imidazolium bromides with the abietane fragment was synthesized. The salts
obtained were suggested as new N-heterocyclic carbene ligands in the Suzuki–Miyaura reaction.
DOI: 10.1134/S1070428011020114
Nowadays the ligands underlain by the N-heterocyclic
carbenes (NHC) firmly occupied an important place in the
homogeneous metallocomplex catalysis [2–4] partially
replacing the traditional tertiary phosphanes. The ligands
based on NHC are more advantageous due to their thermal
and hydrolytic stability, and also due to the resistance to
oxidation [3]. The most frequently used NHC are gener-
ated from the imidazolium salts at the treatment with
strong bases; therewith the complexing of the metal with
the NHC-ligand is conveniently carried out directly in the
reaction mixture (in situ), although an approach is now
under development where the preparation and storage of
the NHC–Pd complexes is performed in the form of the
precatalysts of a definite stereochemistry (“well-defined
precatalysts”) [5]. Notwithstanding the versatility of NHC
types known by now [6] the research on the synthesis of
new imidazolium salts is going on with high intensity all
over the world since the efficient catalytic centers as a rule
are characterized by certain topology of the reaction site
[4, 7] and their discovery requires experimental testing of
various versions of the electronic and spatial structure of
ligands.
of spatially hindered imidazolium salts. Among the mul-
titude of such compounds recently synthesized the salts
can be mentioned based on substituted naphthalene [9],
terphenyl [10], phenanthrene [11], phenanthroline [12],
and diamantane (adamantane dimer) [13].
Imidazolium salts have been synthesized from mono-
terpenes [14], whereas di- and triterpenes yet do not
attract the attention. We formerly prepared chiral asym-
metric imidazolium salts proceeding from the methyl
12-chloromethyldehydroabietate [1, 15]. The presumed
high efficiency of this series of salts was provided by the
sterical loading of the isopropyl group of abietane. The
goal of this study was the synthesis of imidazolium salts
from the methyl 12-bromoacetyldehydroabietate and the
investigation of their catalytic activity as NHC-ligands
in the model Suzuki–Miyaura reaction.
We established that the reaction of N-alkyl- and
N-aryl-1Н-imidazoles Iа–Ij with methyl 12-bromo-
acetyldehydroabietate (II) [16] in toluene afforded un-
symmetrical imidazolium salts IIIа–IIIj.
N-Alkylimidazoles reacted with bromoketone II in
toluene already at room temperature, while the reaction of
N-arylimidazoles required a short heating of the reaction
mixture.All obtained bromides IIIа–IIIj except for com-
pound IIIg separated from toluene in 50–89% yield in the
form of analytically pure colorless crystals. Compound
IIIg is well soluble in toluene but precipitated under the
The sterically loaded ligands are known to accelerate
the stage of the reductive elimination in the catalytic cycle
[4, 7, 8], and therefore one of the directions of the search
for efficient catalytic systems consists in the application
* For Communication II, see [1].
230

N-HETEROCYCLIC CARBENES: III.
O
231
O
+
2
N
+
N
N
N
3
Br
R
R
1
_
Iа_Ij
Br
4
10
9
5
6
8a
8
COOMe
IIIa_IIIj
COOMe
7
II
R = Н (а), Mе (b), Vin (c), i-Pr (d), t-Bu (e), Bn (f), Ph (g), 2-MeC6H4 (h), 2,6-Me2C6H3 (i), 2,4,6-Me3C6H2 (j).
action of ethyl ether on its acetonitrile solution. The low
yield (25%) of the imidazolium salt with vinyl substitu-
ent is apparently due to the competing oligomerization
reactions of the initial imidazole.
version 81–96%, yields in the range 60–88%). Note the
activity of the unsubstituted imidazole IIIа. The reac-
tion practically does not proceed without addition of
salts IIIа–IIIj. For instance, in the blank run without a
ligand [dioxane, 110°С, 5 mol% Pd(OAc)2] the yield of
the cross-coupling products was only 8%. To exclude the
possibility of the homo-coupling a control experiment
was performed with bromobenzene. The reaction of
p-tolylboric acid with bromobenzene in the presence of
1 mol% of palladium(II) acetate and ligand IIIe (DMF,
K2CO3, 90°С, 4 h) gave the product of the homo-coupling
(di-p-tolyl) in the yield not exceeding 10% showing that
the formation of the di-p-tolyl in the model reaction was
due prevailingly to the normal Suzuki–Miyaura reaction.
IR spectra of compounds IIIа–IIIj contain two
absorption bands of carbonyl groups: a strong band
at 1711–1728 (carboxy group) and a medium band at
1581–1655 cm–1 (keto group).Acharacteristic feature of
the crystals of salts IIIа–IIIj is the presence of crystal-
lization water as indicated by the elemental analysis and
by the IR spectra. The latter contain a broad band of OH
groups at 3376–3414 cm–1. The crystallization water is
not removed by drying in a vacuum (55°С, 2 mm Hg,
1
3 h). Н and 13С NMR spectra confirm the structure of
compounds IIIа–IIIj (see EXPERIMENTAL).
The experimental results permit a conclusion that
the imidazolium salts IIIа–IIIj we synthesized possess
a high catalytic activity in the Suzuki–Miyaura reaction
of p-bromotoluene with p-tolylboric acid.
The synthesized salts IIIа–IIIj were tested as N-hetero-
cyclic carbene ligands in the palladium-catalyzed Suzuki–
Miyaura reaction. The model reaction was the interaction
between p-tolylboric acid and p-bromotoluene. The
scheme of the homogeneous catalytic process with the
use of NHC-ligands is in general similar to the traditional
scheme of the cross-coupling with the complexes of
zero-valence palladium with phosphanes. The conditions
of the cross-coupling we optimized before [1]: amount
of the catalyst 1 mol%, solvent DMF. The reaction was
carried out in aerobic conditions at 90°С over 4–5 h (to
the end of the run palladium black formed). It is now
a common concept that the catalytic activity is inherent
to monocoordinated Pd(0) species generated in the reac-
tion mixture by the thermal decomposition of the initially
formed bicoordinated complexes [17], therefore we take
the ratio Pd/ligand equal 1 : 1.
EXPERIMENTAL
Imidazole, N-methylimidazole, N-benzylimidazole,
Catalytic activity of 1-R-imidazolium salts IIIа–IIIj in the
model Suzuki–Miyaura reaction
Compound no.
IIIа
Conversion %
Yield, %
68
84
94
88
96
93
89
95
81
96
90
IIIb
75
IIIc
78
IIId
88
IIIe
60
After the completion of the reaction and the workup
of the reaction mixture its composition was analyzed by
GC-MS method with dodecane as internal reference (see
the table).
IIIf
79
IIIg
87
IIIh
62
IIIi
81
As seen from the table, both alkyl- and aryl-containing
salts show approximately equal catalytic activity (con-
IIIj
78
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

GLUSHKOV et al.
232
N-vinylimidazole, and N-phenylimidazole were pur-
chased from Alfa Aesar (Lancaster); 1-isopropyl-1Н-
imidazole and 1-tert-butyl-1Н-imidazole were prepared
by procedure [18], 1-(2-methylphenyl)-1H-imidazole,
1-(2,6-dimethylphenyl)-1H-imidazole, and 1-mesityl-
1H-imidazole, by procedure [19]. The melting points
were measured on a device PTP. TLC was performed on
plates with silica gel Sorbfil; spots were visualized by
UV irradiation or by treating with 5% H2SO4 followed
by heating at 100–120°С. IR spectra were recorded on
a Fourier spectrophotometer Bruker IFS 66ps from mulls
in mineral oil or from thin films obtained by evapora-
1607, 1549, 1495, 1459, 1388, 1249, 1194, 1134, 1107,
1051, 976, 900. 1Н NMR spectrum, δ, ppm: 1.19 d (3Н,
Mе, J 7.2 Hz), 1.21 s (3Н, Mе), 1.22 d (3Н, Mе, J 7.2 Hz),
1.27 s (3Н, Mе), 1.47 m (2Н, Н1a,6a), 1.65–1.88 m (5Н,
С2Н2, С3Н2, Н6e), 2.10 d.d (1Н, Н5, J 12.3, 2.1 Hz),
2.29 m (1Н, Н1e), 2.91 m (2Н, С7Н2), 3.35 m (1Н, Н15,
J 7.2 Hz), 3.66 s (3Н, ОMе), 4.37 с (2Н, BrCH2), 7.08 s
(1Н, Н14), 7.38 s (1Н, Н11). Found, %: С 64.62; Н 6.74.
C24H33BrO3. Calculated, %: С 64.14; H 7.40.
3-{2-[(4bS,8R)-2-Isopropyl-4b,8-dimethyl-8-
(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-octa-
hydrophenanthren-3-yl]-2-oxoethyl}-1Н-imidazol-
3-olium bromide, hydrate (IIIа). Yield 50%, mp
1
tion of the compound solution in chloroform. Н and
13С NMR spectra were registered on a spectrometer
Varian Mercury+300 (300 and 75 MHz), solvent CDCl3,
internal reference HMDS and the residual solvent signal
(CHCl3, 13C NMR spectra, δ 77.0 ppm). The specific
rotation was measured on an instrument Perkin-Elmer
341 in chloroform stabilized with 0.5% of ethanol; the
results are reported in the units 10–1 deg g–1 cm2. Mass
spectra were obtained on an instrument Agilent 6890N
with the mass-detector MSD 5975В (ionizing energy
70 eV). Elemental analyses were carried out on an ana-
lyzer Leco CHNS 9321P.
22
217–218°С, [α]D +75.9 (с 1, СНCl3). IR spectrum,
cm–1 (from thin film): 3373 (ОН), 3090, 2929, 2869,
1711, 1581, 1555, 1440, 1389, 1249, 1181, 1134, 1105,
1052, 972, 755. 1Н NMR spectrum, δ, ppm: 1.17 d (3Н,
Mе, J 6.6 Hz), 1.19 d (3Н, Mе, J 6.6 Hz), 1.25 s (3Н,
Mе), 1.28 s (3Н, Mе), 1.49 m (2Н, Н9a, Н5a), 1.68-
1.88 m (5Н, С6Н2, С7Н2, Н9e), 2.17 d.d (1Н, Н8а, J 12.6,
2.4 Hz), 2.58 m (1Н, Н5e), 2.93 m (2Н, С10Н2), 3.45 m
(1Н, СНMе2, J 7.2 Hz), 3.67 s (3Н, ОMе), 4.80 br.s
(2Н, HN+OH), 5.92 d (1Н, NСН2, J 18.0 Hz), 6.16 d
(1Н, NСН2, J 18.0 Hz), 7.13 s (1Н, Н1), 7.17 m (1НHt),
7.51 m (1НHt), 7.76 s (1Н, Н4), 8.28 s (1/3Н, NCH=N),
10.26 s (2/3H, NCH=N). 13С NMR spectrum, δ, ppm:
16.35, 18.25, 21.12, 23.88, 23.95, 24.85, 28.62, 30.08,
36.49, 37.07, 37.79, 44.58, 47.39, 51.85, 57.23, 119.07,
123.23, 125.35, 127.69, 130.46, 132.94, 138.68, 141.50,
146.76, 147.48, 178.79, 192.54. Found, %: С 60.12;
Н 7.30; N 5.90. C26H35BrN2O3·H2O. Calculated, %:
С 59.88; H 7.15; N 5.37.
1-(2-Methylphenyl)-1Н-imidazole (Ih). Yield 63%.
Yellow thick oily or light-yellow crystalline substance,
1
bp 200–205°С (15 mm Hg), mp 65–68°С. Н NMR
spectrum, δ, ppm: 2.16 s (3Н, Mе), 7.04 m (1НHt),
7.18–7.35 m (4Нarom), 7.61 m (1НHt), 8.99 br.s. (1Н,
Н2Ht). 1Н NMR spectrum is consistent with that published
in [20].
1-(2,6-Dimethylphenyl)-1Н-imidazole (Ii). Yield
35%. Light-yellow crystals, bp 215–220°С (15 mm
Hg), mp 76–78°С. Н NMR spectrum, δ, ppm: 2.02 s
(6Н, 2Mе), 6.90 d (1Н, НHt, J 1.2 Hz), 7.13 d (2Н, Н3',
Н5', J 7.2 Hz), 7.22–7.27 m (1Н, Н4'), 7.24 m (1Н, НHt,
J 1.2 Hz), 7.44 s (1Н, NCH=N).
1-Methyl-3-{2-[(4bS,8R)-2-isopropyl-4b,8-
dimethyl-8-(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-
octahydrophenanthren-3-yl]-2-oxoethyl}-1Н-
imidazol-3-olium bromide (IIIb). Yield 78%, mp
221–223°С, [α]D22 +66.6 (с 1, СНCl3). IR spectrum,
cm–1 (from thin film): 3414 (ОН), 2940 (С–Н), 1715
(О–С=О), 1607 (С=О), 1561, 1499 (С=С), 1459 (С–Н),
1388 (С–Н), 1353, 1249, 1176, 1107, 1052, 973. 1Н NMR
spectrum, δ, ppm: 1.16 d (3Н, Mе, J 7.2 Hz), 1.18 d (3Н,
Mе, J 7.2 Hz), 1.24 s (3Н, Mе), 1.26 s (3Н, Mе), 1.46 m
(2Н, Н5a,9a), 1.65-1.87 m (5Н, С6Н2, С7Н2, Н9e), 2.17 d.d
(1Н, Н8а, J 12.6, 1.8 Hz), 2.66 m (1Н, Н5e), 2.91 m (2Н,
С10Н2), 3.40 m (1Н, СНMе2, J 7.2 Hz), 3.66 s (3Н,
ОMе), 4.05 s (3Н, NMe), 6.06 d (1Н, NСН2, J 18.3 Hz),
6.28 d (1Н, NСН2, J 18.3 Hz), 7.01 s (1Н, Н1), 7.46 m
(1НHt), 7.53 m (1НHt), 7.83 s (1Н, Н4), 10.09 s (1Н,
NCH=N). 13С NMR spectrum, δ, ppm: 16.30, 18.20,
1
1-Mesityl-1Н-imidazole (Ij). Yield 51%. Light-
brown crystals, mp 106–108°С (mp 112–114°С [19]).
1Н NMR spectrum, δ, ppm: 1.98 s (6Н, 2Mе), 2.33 s (3Н,
Mе), 6.88 m (1НHt), 6.96 s (2Н, Н3',5'), 7.22 m (1НHt),
7.42 s (1Н, NCH=N). The substance is sufficiently pure
to be used in the amination of bromoketone II.
Methyl 12-bromoacetyldehydroabietate (II) was
obtained by procedure [16] by the bromination of the
methyl 12-acetyldehydroabietate with molecular bromine
in acetic acid. Yield 93%, mp 114–116°С (mp 115–117°С
[16]). IR spectrum, cm–1 (from thin film): 1722, 1683,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

N-HETEROCYCLIC CARBENES: III.
233
21.07, 23.85, 23.90, 24.76, 28.56, 30.03, 36.44, 36.60,
37.04, 37.69, 44.57, 47.34, 51.77, 57.22, 122.61, 123.90,
125.38, 127.49, 130.60, 138.04, 141.17, 146.49, 147.39,
178.77, 193.15. Found, %: С 62.17; Н 6.62; N 5.30.
C27H37BrN2O3. Calculated, %: С 62.66; H 7.21; N 5.41.
28.46, 29.95, 36.38, 37.00, 37.61, 44.50, 47.27, 51.68,
53.11, 57.04, 119.22, 123.99, 125.35, 127.34, 130.68,
136.42, 140.92, 146.31, 147.31, 178.70, 193.25. Found,
%: С 63.28; Н 6.95; N 5.10. C29H41BrN2O3. Calculated,
%: С 63.85; H 7.58; N 5.13.
1-tert-Butyl-3-{2-[(4bS,8R)-2-isopropyl-4b,8-
dimethyl-8-(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-
octahydrophenanthren-3-yl]-2-oxoethyl}-1Н-
imidazole-3-olium bromide (IIIe). Yield 75%,
mp 244–246°С, [α]D22 +62.6 (с 1, СНCl3). IR spectrum,
cm–1 (from thin film): 3404 br (ОН), 2938 (С–Н), 1715
(О=С–О), 1606 (С=О), 1551, 1466, 1388, 1355, 1248,
1200, 1134, 1054, 970, 882, 754. 1Н NMR spectrum, δ,
ppm: 1.19 d (3Н, Mе, J 6.9 Hz), 1.21 d (3Н, Mе, J 6.9 Hz),
1.27 s (6Н, 2Mе), 1.47 m (2Н, Н9a, Н5a), 1.68-1.84 m
(14Н, tert-С4Н9, С6Н2, С7Н2, Н9e), 2.18 d.d (1Н, Н8а,
J 12.3, 1.8 Hz), 2.73 m (1Н, Н5e), 2.92 m (2Н, С10Н2),
3.43 m (1Н, СНAr, J 6.9 Hz), 3.66 s (3Н, ОMе), 6.16 d
(1Н, NСН2, J 18.6 Hz), 6.40 d (1Н, NСН2, J 18.6 Hz),
7.10 s (1Н, Н1), 7.34 m (2Н, НHt), 7.90 s (1Н, Н4), 10.77 s
(1Н, NCH=N). 13С NMR spectrum, δ, ppm: 16.21, 17.37,
18.09, 18.11, 21.03, 23.87, 24.59, 28.35, 30.02, 36.36,
37.01, 37.53, 44.53, 47.27, 51.63, 57.74, 121.89, 125.75,
127.16, 128.88, 130.73, 134.51, 138.45, 146.11, 147.31,
178.73, 193.20. Found, %: С 63.88, Н 7.47; N 5.12.
C30H43BrN2O3. Calculated, %: С 64.39; H 7.75; N 5.01.
1-Vinyl-3-{2-[(4bS,8R)-2-isopropyl-4b,8-di-
methyl-8-(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-
octahydrophenanthren-3-yl]-2-oxoethyl}-1Н-
imidazol-3-olium bromide, hemihydrate (IIIc).
Yield 25%, mp 200–202°С, [α]D22 +71.9 (с 1, СНCl3).
IR spectrum, cm–1 (from thin film): 3401 (ОН), 2940
(С–Н), 1714 (О–С=О), 1655 (С=О), 1608 (С=С), 1551,
1499 (С=С), 1459 (С–Н), 1386 (С–Н), 1355 (С–Н),
1249 (С–О–С), 1180, 1135, 1108, 1052, 1014, 967, 914.
1Н NMR spectrum, δ, ppm: 1.17 d (3Н, Mе, J 6.6 Hz),
1.19 d (3Н, Mе, J 6.6 Hz), 1.25 s (3Н, Mе), 1.27 s (3Н,
Mе), 1.44 m (2Н, Н5a,9a), 1.66–1.87 m (5Н, С6Н2, С7Н2,
Н9e), 2.18 m (1Н, Н8a), 2.68 m (1Н, Н5e), 2.92 m (2Н,
С10Н2), 3.42 m (1Н, СНMе2, J 6.6 Hz), 3.66 s (3Н, ОMе),
5.44 d.d (1Н, СН=, J 9.0, 3.0 Hz), 5.90 d.d (1Н, СН=,
J 15.0, 3.0 Hz), 6.15 d (1Н, NСН2, J 18.0 Hz), 6.39 d
(1Н, NСН2, J 18.0 Hz), 7.11 s (1Н, Н1), 7.28 d.d (1Н,
СН, J 15.0, 9.0 Hz), 7.56 s (1НHt), 7.66 s (1НHt), 7.86 s
(1Н, Н4), 10.74 s (1Н, NCH=N). 13С NMR spectrum,
δ, ppm: 16.48, 18.39, 21.25, 24.04, 24.95, 28.81, 30.25,
36.67, 37.28, 37.90, 44.76, 47.55, 51.91, 57.55, 58.32,
110.47, 118.04, 124.57, 125.79, 127.75, 128.15, 137.17,
141.74, 146.86, 147.81, 153.65, 178.95, 192.76. Found,
%: С 62.71; Н 6.33; N 5.62. C28H37BrN2O3·1/2H2O.
Calculated, %: С 62.44; H 7.11; N 5.20.
1-Benzyl-3-{2-[(4bS,8R)-2-isopropyl-4b,8-dimeth-
yl-8-(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-octahydro-
phenanthren-3-yl]-2-oxoethyl}-1Н-imidazol-3-olium
bromide (IIIf). Yield 78%, mp 232–234°С, [α]D22 +60.5
(с 1, СНCl3). IR spectrum, cm–1 (from thin film): 3398
(ОН), 2943 (С–Н), 1715 (О–С=О), 1607 (С=О), 1557,
1498 (С=С), 1455 (С–Н), 1387 (С-Н), 1360 (С-Н), 1248,
1192, 1161, 1135, 1109, 1045, 971. 1Н NMR spectrum, δ,
ppm: 1.17 d (3Н, Mе, J 7.2 Hz), 1.19 d (3Н, Mе, J 7.2 Hz),
1.26 s (3Н, Mе), 1.27 s (3Н, Mе), 1.46 m (2Н, Н9a, Н5a),
1.64–1.88 m (5Н, С6Н2, С7Н2, Н9e), 2.18 d.d (1Н, Н8а,
J 12.3, 2.1 Hz), 2.67 m (1Н, Н5e), 2.91 m (2Н, С10Н2),
3.42 m (1Н, СНMе2, J 7.2 Hz), 3.66 s (3Н, ОMе), 5.47 s
(2Н, PhCH2), 6.06 d (1Н, NСН2, J 18.0 Hz), 6.31 d (1Н,
NСН2, J 18.0 Hz), 7.11 s (1Н, Н1), 7.16 m (1НHt), 7.37 m
(1НHt), 7.42 m (5Н, Ph), 7.84 s (1Н, Н4), 10.63 s (1Н,
NCH=N). 13С NMR spectrum, δ, ppm: 16.32, 18.21,
21.09, 23.89, 23.93, 24.78, 28.56, 30.06, 36.45, 37.07,
37.71, 44.57, 47.36, 51.78, 53.22, 57.24, 120.96, 124.17,
125.48, 127.51, 128.64, 129.29, 129.34, 130.58, 132.51,
137.65, 141.21, 146.52, 147.46, 178.78, 192.97. Found,
%: С 67.32; Н 6.93; N 4.72. C33H41BrN2O3. Calculated,
%: С 66.77; H 6.96; N 4.72.
1-Isopropyl-3-{2-{(4bS,8R)-2-isopropyl-4b,8-
dimethyl-8-(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-
octahydrophenanthren-3-yl]-2-oxoethyl}-1Н-
imidazol-3-olium bromide (IIId). Yield 64%, mp
237–238°С, [α]D22 +64.1 (с 1, СНCl3). IR spectrum,
cm–1 (from thin film): 3410 (ОН), 2937 (С–Н), 1716
(О–С=О), 1608 (С=О), 1553, 1499 (С=С), 1463 (С–Н),
1386 (С–Н), 1347, 1247, 1181, 1154, 1134, 1110, 1047,
1
971, 887. Н NMR spectrum, δ, ppm: 1.18 d (3Н, Mе,
J 7.2 Hz), 1.20 d (3Н, Mе, J 7.2 Hz), 1.26 s (3Н, Mе),
1.27 s (3Н, Mе), 1.47 m (2Н, Н9a, Н5a), 1.65 d [6Н,
NСН(СН3]2, J 6.6 Hz), 1.69–1.88 m (5Н, С6Н2, С7Н2,
Н9e), 2.18 d.d (1Н, Н8а, J 12.6, 2.1 Hz), 2.71 m (1Н, Н5e),
2.92 m (2Н, С10Н2), 3.43 m (1Н, СНAr, J 7.2 Hz), 3.66 s
(3Н, ОMе), 4.76 m [1Н, NСН(СН3]2, J 6.6 Hz), 6.11 d
(1Н, NСН2, J 18.3 Hz), 6.34 d (1Н, NСН2, J 18.3 Hz),
7.10 s (1Н, Н1), 7.33 m (1НHt), 7.39 m (1НHt), 7.87 s
(1Н, Н4), 10.60 s (1Н, NCH=N). 13С NMR spectrum,
δ, ppm: 16.23, 18.14, 21.01, 22.76, 23.83, 23.87, 24.67,
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GLUSHKOV et al.
234
3-{2-[(4bS,8R)-2-Isopropyl-4b,8-dimethyl-8-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl]-2-
oxoethyl}-1Н-imidazol-3-olium bromide, hemihydrate
(IIIi). Yield 58%, mp 243–245°С, [α]D22 +65.0 (с 1,
СНCl3). IR spectrum, cm–1 (from thin film): 3376 (ОН),
2937, 1720 (О-С=О), 1548, 1465, 1380 1249 1185 1105,
1050, 959, 888. 1Н NMR spectrum, δ, ppm: 1.19 d (3Н,
Mе, J 6.9 Hz), 1.22 d (3Н, Mе, J 6.9 Hz), 1.27 s (6Н,
2Mе), 1.47 m (2Н, Н9a, Н5a), 1.63–1.88 m (11Н, С6Н2,
С7Н2, Н9e, 2MеAr), 2.19 m (1Н, Н8а), 2.74 m (1Н, Н5e),
2.91 m (2Н, С10Н2), 3.42 m (1Н, СНMе2, J 6.9 Hz),
3.66 s (3Н, ОMе), 6.16 d (1Н, NСН2, J 18.3 Hz), 6.39 d
(1Н, NСН2, J 18.3 Hz), 7.10 s (1Н, Н1), 7.25 s (2Н,
НHt), 7.36 m (3Нarom), 7.90 с (1Н, Н4), 10.70 s (1Н,
NCH=N). 13С NMR spectrum, δ, ppm: 16.30, 18.22,
21.09, 23.92, 24.74, 28.55, 29.83, 30.03, 36.47, 37.07,
37.66, 44.59, 47.37, 51.73, 57.10, 60.23, 118.53, 124.01,
125.54, 127.37, 130.81, 136.48, 140.96, 146.30, 147.45,
178.80, 193.57. Found, %: С 63.95; Н 7.79; N 4.90.
C34H43BrN2O3·1/2H2O. Calculated, %: С 64.29; H 6.87;
N 4.54.
(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-octa-hydro-
phenanthren-3-yl]-2-oxoethyl}-1-phenyl-1Н-imidazol-
3-olium bromide, hydrate (IIIg). Yield 61%, mp 170–
22
172°С (MeCN–ether), [α]D +65.3 (с 1, СНCl3). IR
spectrum, cm–1 (from thin film): 3402 ш (ОН), 2944
(С–Н), 1715 (О–С=О), 1602 (С=О), 1553, 1497, 1460,
1355, 1248, 1134, 1108, 1071, 972, 910, 813. 1Н NMR
spectrum, δ, ppm: 1.18 d (3Н, Mе, J 6.6 Hz), 1.20 d
(3Н, Mе, J 6.6 Hz), 1.25 s (3Н, Mе), 1.26 s (3Н, Mе),
1.46 m (2Н, Н9a, Н5a), 1.64–1.90 m (5Н, С6Н2, С7Н2,
Н9e), 2.16 d.d (1Н, Н8а, J 12.3, 2.1 Hz), 2.72 m (1Н, Н5e),
2.92 m (2Н, С10Н2), 3.45 m (1Н, СНMе2, J 6.6 Hz), 3.66 s
(3Н, ОMе), 6.30 d (1Н, NСН2, J 18.0 Hz), 6.54 d (1Н,
NСН2, J 18.0 Hz), 7.11 s (1Н, Н1), 7.51–7.57 m (3H,
2Нarom + НHt), 7.64 m (1НHt), 7.69 m (3Нarom), 7.92 s (1Н,
Н4), 10.64 s (1Н, NCH=N). 13С NMR spectrum, δ, ppm:
16.19, 18.08, 20.99, 23.84, 24.61, 28.48, 29.95, 36.34,
36.97, 37.53, 37.54, 44.51, 47.24, 51.63, 57.51, 119.78,
121.52, 124.96, 125.49, 127.30, 129.93, 130.21, 130.73,
134.15, 136.29, 140.88, 146.31, 147.29, 178.67, 193.24.
Found, %: С 64.47; Н 7.05; N 4.67. C32H39BrN2O3·H2O.
Calculated, %: С 64.30; H 6.91; N 4.69.
3-{2-[(4bS,8R)-2-Isopropyl-4b,8-dimethyl-8-
(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-octa-
hydrophenanthren-3-yl]-2-oxoethyl}-1-mesityl-1Н-
imidazol-3-olium bromide (IIIj). Yield 89%, mp
225–226°С, [α]D22 +61.2 (с 1, СНCl3). IR spectrum, cm–1
(mull in mineral oil): 3400 w (ОН), 1728 (О–С=О), 1697,
1608 (С=О), 1549, 1245, 1209, 1132, 1109, 1063, 1045,
3-{2-[(4bS,8R)-2-Isopropyl-4b,8-dimethyl-8-
(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-octa-hydro-
phenanthren-3-yl]-2-oxoethyl]-1-(2-methylphenyl)-
1Н-imidazol-3-olium bromide, hydrate (IIIh). Yield
88%, mp 241–243°С, [α]D22 +59.4 (с 1, СНCl3). IR
spectrum, cm–1 (from thin film): 3407 (ОН воdы), 2939,
1715, 1606, 1551, 1464, 1388 w, 1355 w, 1248, 1200,
1133, 1107, 1055, 970, 754. 1Н NMR spectrum, δ, ppm:
1.19 d (3Н, Mе, J 6.9 Hz), 1.22 d (3Н, Mе, J 6.9 Hz),
1.26 s (3Н, Mе), 1.27 s (3Н, Mе), 1.47 m (2Н, Н9a, Н5a),
1.62-1.88 m (5Н, С6Н2, С7Н2, Н9e), 2.17-2.21 m (4Н, Н8а
+ MеAr), 2.82 m (1Н, Н5e), 2.92 m (2Н, С10Н2), 3.47 m
(1Н, СНMе2, J 6.9 Hz), 3.66 s (3Н, ОMе), 6.38 d (1Н,
NСН2, J 18.0 Hz), 6.83 d (1Н, NСН2, J 18.0 Hz), 7.11 s
(1Н, Н1), 7.21 t (1Н, НHt, J 1.8 Hz), 7.23 s (1Нarom), 7.35-
7.48 m (3Нarom), 7.68 t (1Н, НHt, J 1.8 Hz), 8.04 s (1Н,
Н4), 10.30 t (1Н, NCH=N, J 1.8 Hz). 13С NMR spectrum,
δ, ppm: 16.18, 17.48, 18.05, 20.99, 23.84, 24.55, 28.32,
28.40, 29.98, 36.33, 36.98, 37.50, 44.51, 47.24, 51.59,
57.72, 121.88, 124.89, 125.69, 125.77, 127.13, 128.84,
130.69, 130.74, 130.77, 132.87, 134.49, 138.42, 140.59,
146.07, 147.27, 178.68, 193.21. Found, %: С 64.59;
Н 6.62; N 4.15. C33H41BrN2O3·H2O. Calculated, %:
С 64.80; H 7.09; N 4.58.
1
970, 871. Н NMR spectrum, δ, ppm: 1.18 d (3Н, Mе,
J 7.2 Hz), 1.21 d (3Н, Mе, J 7.2 Hz), 1.26 s (6Н, 2Mе),
1.45 m (2Н, Н9a, Н5a), 1.64–1.89 m (5Н, С6Н2, С7Н2,
Н9e), 2.10 m (7Н, Н8а + 2MеAr), 2.34 s (3Н, MеAr),
2.82 m (1Н, Н5e), 2.91 m (2Н, С10Н2), 3.46 m (1Н,
СНMе2, J 7.2 Hz), 3.66 s (3Н, ОMе), 6.37 d (1Н, NСН2,
J 18.0 Hz), 6.79 d (1Н, NСН2, J 18.0 Hz), 7.00 s (2Н, Н3',
Н5'), 7.10 s (1Н, Н1), 7.19 m (1НHt), 7.76 m (1НHt), 8.03 s
(1Н, Н4), 10.19 s (1Н, NCH=N). 13С NMR spectrum, δ,
ppm: 16.11, 17.17, 18.00, 20.70, 20.94, 23.80, 24.46,
28.24, 29.92, 36.25, 36.91, 37.41, 44.45, 47.18, 51.54,
57.63, 122.04, 124.77, 125.65, 127.03, 129.36, 130.37,
130.76, 134.00, 138.39, 140.44, 140.79, 145.97, 147.17,
178.66, 193.24. Found, %: С 67.94; Н 6.92; N 4.50.
C35H45BrN2O3. Calculated, %: С 67.62; H 7.30; N 4.51.
General procedure of Suzuki–Miyaura cross-
coupling. Amixture of 6 mg (0.028 mmol) of Pd(OAc)2,
0.028 mmol of imidazolium salt, 60 mg (4.34 mmol)
of K2CO3 in 70 ml of DMF was heated at 90°C for
15–20 min till the dissolution of the most part of
Pd(OAc)2 with the formation of a yellow solution of
the complex Pd(0)–NHC, then was added 480 mg
1-(2,6-Dimethylphenyl)-3-{2-[(4bS,8R)-2-
isopropyl-4b,8-dimethyl-8-(methoxycarbonyl)-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

N-HETEROCYCLIC CARBENES: III.
235
Kantchev, E.A.B., Er, J.-C., and Ying, J.Y., Chem. Eur. J.,
2010, vol. 16, p. 4010.
(2.8 mmol) of p-bromotoluene (2 ml of a solution in DMF
of the concentration 240 mg/ml), 380 mg (2.8 mmol)
of p-tolylboric acid, 770 mg (5.6 mmol) of K2CO3,
and 0.4 ml of dodecane as an internal reference. The
mixture was heated at 90°С over 5 h (to the end of the
experiment palladium black started to form), afterwards
the reaction mixture was cooled, the inorganic salts were
filtered off, washed with 20 ml of DMF, the solution
was evaporated in a vacuum to the volume 4–5 ml, the
residue was diluted with 100 ml of water, 30 ml of brine
(to destroy the emulsion), and the mixture was extracted
with dichloromethane (3–4 × 25 ml) till the transparent
solution, the extract was dried with MgSO4, and the
composition of the mixture was analyzed by GC-MS
method. The quantitative determination was performed
using the calibration plots obtained with specially
prepared mixtures from pure p-bromotoluene, dodecane,
and di-p-tolyl. The conversion was estimated from the
amount of the recovered p-bromotoluene, the yield, from
the amount of the formed di-p-tolyl.
6. Hahn, F.E., Angew. Chem., Int. Ed., 2008, vol. 47, p. 3122;
Jahnke, M.C. and Hahn, F.E., Top. Organometal. Chem.,
2010, vol. 30, p. 95.
7. Würtz, S. and Glorius, F., Acc. Chem. Res., 2008, vol. 41,
p. 1523.
8. Dowlut, M., Mallik, D., and Organ, M.G., Chem. Eur. J.,
2010, vol. 16, p. 427.
9. Lee, C.-C., Ke, W.-C., Chan, K.-T., Lai, C.-L., Hu, C.-
H., and Lee, H.M., Chem. Eur. J., 2007, vol. 13, p. 582;
Luan, X., Mariz, R., Gatti, M., Costabile, C., Poater, A.,
Cavallo, L., Linden, A., and Dorta, R., J. Am. Chem. Soc.,
2008, vol. 130, p. 6848; Vieille-Petit, L., Clavier, H., Lin-
den, A., Blumentritt, S., Nolan, S., and Dorta, R., Organo-
metallics, 2010, vol. 29, p. 775.
10. Alexander, S.G., Cole, M.L., and Morris, J.C., New J.
Chem., 2009, vol. 33, p. 720.
11. Ma, Y., Song, C., Jiang, W., Wu, Q., Wang, Y., Liu, X., and
Andrus, M.B., Org. Lett., 2003, 5, 3317.
12. Metallinos, C., Barrett, F.B., Wang, Y., Xu, S., and Tai-
lor, N.J., Tetrahedron, 2006, vol. 62, 11145.
ACKNOWLEDGMENTS
13. Richter, H., Schwertfeger, H., Shreiner, P.R., Fröhlich, R.,
and Glorius, F., Synlett., 2009, p. 193.
The authors express their gratitude to V.I. Karmanov
and I.A. Borisova for registering the IR spectra.
14. Lee,S.and Hartwig,J.F,J.Org.Chem., 2001,vol.66,p.3402;
Pernak, J., Feder-Kubis, J., Cieniecka-Rosłonkiewicz, A.,
Fischmeister, C., Griffin, S.T., Rogers, R.D. New, J. Chem.,
2007, 31, 879; Würtz, S., Lohre, C., Fröhlich, R., Bergan-
der, K., and Glorius, F., J. Am. Chem. Soc., 2009, vol. 131,
p. 8344.
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant
no.09-03-00841-а) and of the Presidium of the Russian
Academy of Sciences (program no. 09-П-3-1016).
15. Glushkov, V.A., Kotelev, M.S., Rudovskii, K.S., Maio-
rova, O.A., Tarantin,A.V., Tolstikov,A.G., Zh. Org. Khim.,
2009, vol. 45, p. 416.
REFERENCES
1. Glushkov, V.A. and Valieva, M.S., Tekhnicheskaya khimiya.
Ot teorii k praktike. Sbornik, statei. II, Mezhdunarodnaya,
konferentsiya (Technical Chemistry: from Theory to Prac-
tice. Collections of Papers. 2nd International Conference),
Perm, 2010, vol. 1, p. 137.
16. Irismetov, M.P., Tolstikov, G.A., Goryaev, M.I., and
Von, G.P., Kaz. SSR, Gylym, Akad. Khabarlary, Izv. Akad.
Nauk, Kaz.SSR, Ser. Khim., 1968, vol. 5, p. 85; Ref. Zh.
Khim., 1969, 13Zh581.
17. Christmann, U. and Vilar, R., Angew. Chem. Int. Ed., 2005,
vol. 44, p. 366; Marion, N., Navarro, O., Stevens, E.D.,
Ecarnot, E.C., Bell,A.,Amoroso, D., and Nolan, S.P. Chem.
Asian, J., 2010, vol. 5, p. 841.
2. Herrmann, W.A., Elison, M., Fisher, J., Köcher, C., andAr-
tus, G.R.J., Angew. Chem., Int. Ed., 1995, vol. 34, p. 2371.
3. Herrmann, W.A., Angew. Chem, Int. Ed., 2002, vol. 41,
p. 1290.
18. Gridnev, A.A. and Michaltseva, I.M. Synth. Commun.,
4. Kantchev, E.A.B., O`Brien, C.J., and Organ, M.G., Angew.
Chem. Int. Ed., 2007, 46, 2768.
1994, vol. 24, p. 1547.
19. Occhipinti, G., Jensen, V.R., Törnroos, K.W., Frøyste-
in, N.A., and Bjørsvik, H.-R., Tetrahedron, 2009, vol. 65,
p. 7186.
5. Marion, N. and Nolan, S.P., Acc. Chem. Res., 2008, vol. 41,
p. 1440; Selvakumar, K., Zapf, A., Spannenberg, A.,
and Beller, M., Chem. Eur. J., 2002, vol. 8, p. 3901; Or-
gan, M.G., Chass, G.A., Fang, D.-C., Hopkinson,A.C., and
Valente, C., Synthesis, 2008, vol. 17, p. 2776; Peh, G.-R.,
20. Collman, J.P. and Zhong, M., Org. Lett., 2000, vol. 2,
p. 1233.
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