N-heterocyclic carbenes. IV.1synthesis of symmetrical and unsymmetrical imidazolium salts with abietane moiety

Article abstract of DOI:10.1002/hc.20745

Methyl 12-chloromethyl-dehydroabie-tate reacts with 1-benzyl- and 1-arylimidazoles to give unsymmetrically substituted imidazolium chlorides (1a-i), with abietane moiety. Starting from methyl 12-aminodehydroabietate, symmetrically substituted diterpene-ba

Full text of DOI:10.1002/hc.20745

Heteroatom Chemistry
Volume 23, Number 1, 2012
1
N-Heterocyclic Carbenes. IV. Synthesis of
Symmetrical and Unsymmetrical Imidazolium
Salts with Abietane Moiety
V. A. Glushkov,1,3 K. A. Arapov,1 M. S. Kotelev,1 K. S. Rudowsky,1
K. Yu. Suponitsky,2 A. A. Gorbunov,3 O. A. Maiorova,3 and
P. A. Slepukhin4
1Faculty of Chemistry, Perm State University, 15, Bukireva Street, 614990 Perm, Russia
2A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28,
Vavilov Street, 119991 Moscow, Russia
3Institute of Technical Chemistry, Urals Branch of the Russian Academy of Sciences, 3,
Academician Korolev Street, 614013 Perm, Russia
4I. Ya. Postovsky Institute of Organic Synthesis, Urals Branch of the Russian Academy of Sciences,
22, S. Kovalevskoy Street, 620041 Ekaterinburg, Russia
Received 17 March 2011; revised 4 June 2011
INTRODUCTION
ABSTRACT: Methyl 12-chloromethyl-dehydroabie-
tate reacts with 1-benzyl- and 1-arylimidazoles to give
Substituted imidazolylidenes and imidazolinyli-
unsymmetrically substituted imidazolium chlorides
denes represent the largest group among other N-
(1a–i), with abietane moiety. Starting from methyl
heterocyclic carbenes (NHCs) [2]. N-Heterocyclic
12-aminodehydroabietate, symmetrically substituted
carbenes are widely used as reagents in modern
diterpene-based salts of imidazolinium (4) and im-
organic chemistry [3]; the NHC-transition metal
idazolium (5) were synthesized. Anion exchange af-
complexes have found wide applications in
forded corresponding (1e·BF4) and (1e·PF6). The new
organometallic chemistry [4], as well as in other
compounds were tested as ligands for a Pd-catalyzed
fields of chemistry [5]. Outstanding results were ob-
Suzuki-Miyaura reaction. The molecular structure of
tained with NHCs as ligands for the 2nd genera-
ꢀ
C
(1e) is reported.
2011 Wiley Periodicals, Inc. Het-
tion of Grubb’s catalysts [6] and Pd-mediated cross-
coupling reactions [7]. In the latter case, to obtain
reasonable yields, sterically demanding NHCs need
to be used, of which their high activity may be ra-
tionalized by the acceleration of the reductive elim-
ination stage in the catalytic cycle [7b,8]. Despite
the availability of a wide variety of versatile NHC-
based ligands, the intensive development of new im-
idazolium salts continues today due to the fact that
varying the steric bulk of the substituents surround-
ing the metal center offers promising opportunities
for tuning the NHC ligands. Currently, a great deal
of imidazolium salts exhibiting diverse structural
eroatom Chem 23:5–15, 2012; View this article online at
wileyonlinelibrary.com. DOI 10.1002/hc.20745
Correspondence to: Vladimir Glushkov; e-mail: glusha55@
gmail.com.
Contract grant sponsor: Russian Fund of Basic Research.
Contract grant numbers: 07-03-96033-a, 09-03-00841-a.
Contract grant sponsor: Presidium of the Russian Academy
of Sciences.
Contract grant number: 09-P-3-1016.
1For III see ref. [1].
c
ꢀ
2011 Wiley Periodicals, Inc.
5

6
Glushkov et al.
motifs with high steric demands has been syn-
thesized. Among them are derivatives of substi-
tuted naphthalene [9], terphenyl [10], phenanthrene
and anthracene [11], phenanthroline [12], diaman-
tane (dimer of adamantane) [13], and highly hin-
dered aromatics [14]. Imidazolium salts contain-
ing monoterpenes have been described [15], but
derivatives of di- and triterpenes are still unknown.
In our preliminary communication [16], we dis-
closed unsymmetrical diterpene imidazolium salts
from methyl 12-chloromethyl-dehydroabietate and
alkylimidazoles. In this work, we report the synthesis
of imidazolinium and imidazolium salts from diter-
penes, methyl 12-aminodehydroabietate and methyl
12-chloromethyldehydroabietate, and the study of
their catalytic activity in the Suzuki-Miyaura reac-
tion. Compounds 1 and 5 represent the class of chi-
ral imidazolium salts; some representative examples
are documented [17].
FIGURE 1 ORTEP view of compound 1e; displacement el-
lipsoids drawn at 30% probability level. Only the first indepen-
dent cation structure is shown.
An asymmetric unit of 1e contains two cations
(C31H39N2O+2 ), two Cl−, and two quarters of disor-
dered water molecules. It is interesting to note that
the formation of hydrates is a distinguishing char-
acteristic for all chlorides 1a–i (but not for tetraflu-
oroborate Ie·BF4 and hexafluorophosphate Ie·PF6)
as evidenced by elemental analysis data and IR spec-
tra (broad absorption band OH at 3329–3468 cm−1).
The ester group displays strong bands at 1715–
1727 cm−1.
We suppose that diterpene moiety with an ortho-
iso-propyl group provides the necessary steric bulk
of new ligands 1,4,5.
RESULTS AND DISCUSSION
Our initial efforts were focused on the un-
symmetrical ligands 1a–i. Asymmetrical imida-
zolium salts were obtained by the reaction of
methyl 12-chloromethyl-dehydroabietate [18] with
corresponding 1-alkyl-, 1-benzyl-, or 1-aryl-1H-
imidazoles (Scheme 1) in MeCN under reflux for 5 h.
We had supposed that changing the R substituent
allows for variation of the electronic and steric char-
acter of NHCs over a wide range.
The structure of compound 1e was confirmed by
the single-crystal X-ray diffraction analysis as shown
in Fig. 1. It crystallizes in chiral space group P21 in
the hydrate form with 1e: water ratio = 1:4.
Anion exchange in chloride 1e gave rise to cor-
responding tetrafluoroborate Ie·BF4 and hexafluo-
rophosphate Ie·PF6 (Scheme 2).
Compound 2 was synthesized from methyl 12-
aminodehydroabietate [19]. The structure of 2 is
confirmed by the single-crystal X-ray diffraction
analysis (Fig. 2). The central diimine moiety is nearly
planar. The structure of tricyclic fragments is similar
to that described earlier [20].
Compounds 4 and 5 were synthesized from di-
imine 2 by the Arduengo method [21] (Scheme 3).
Reduction of compound 2 resulted in bis-amine
3 dihydrochloride. Heating the compound 3 with
ethyl orthoformate afforded imidazolinium salt 4.
N
N
Cl
R
Cl
2
N
N
4
R
5
N
Ph
N
1
6
7
X
MeCN, 5-6 h
reflux
10
NH4BF4 or NH4PF6
EtOH - H2O
8
9
1e
CO2Me
CO2Me
1a-i
1
a
b
c
: R = ( ) Me (62%), ( ) Pr (57%), ( ) Bu (44%),
i- t-
CO2Me
(d) Bn (75%), (e) Ph (44%), (f) 2-MeC6H4 (52%),
(g) 4-MeC6H4 (45%), (h) 2,6-Me2C6H3 (33%),
( ) 2,4,6-Me3C6H2 (73%)
1e.BF4
62%
63%
X = BF4
X = PF6
i
1e.PF6
SCHEME 1
SCHEME 2
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Imidazolium Salts with Abietane Moiety
7
H
H
O
2 RNH2
+
RN
O
NR
(83%)
H
H
2
HC(OEt)3, HCOOH
MeCN, reflux
1. NaBH4 THF/MeOH
2. HCl
N
N
NHR
2HCl
RNH
2
2
R
R
Cl
4
(37%)
3
(37%)
ClCH2OC3H7
MeCN, rt
R =
N
Cl
N
R
R
5
(56%)
CO2Me
SCHEME 3
Compound 5 was synthesized by the reaction of di-
imine 2 with chloromethyl-propyl ether [10].
The screening of salts 1a-i, 4, and 5 as possi-
ble ligands for the Suzuki-Miyaura reaction of 4-
bromotoluene and 4-tolylboronic acid was carried
out (Scheme 4).
Solvent/base optimization was fulfilled using
compounds 1a–c, synthesized earlier [16]. A sum-
mary of the more relevant results obtained is listed
in Table 1. We had initially conducted the reac-
tion using 5 mol% of Pd(OAc)2 as a catalyst pre-
cursor and K3PO4 as a base in dioxane (Table 1, en-
tries 2–4), dimethoxyethane (entry 6), and toluene
(entry 7); after 5 h, heating at 90◦C under aero-
bic conditions produced only modest conversion
(60%–67%) and low yield (47%–57%). At the end
of the reaction, palladium black was formed. In the
presence of PPh3 (1 equiv. to Pd(OAc)2) as a coli-
gand (entry 5) in dioxane, the yield was still mod-
erate (56%), though conversion was high (96%). It
is worth noting that Pd(OAc)2 alone led to 8% yield
(entry 1).
The reaction yields were significantly improved
when DMF was introduced as a solvent and K2CO3
as a base (entry 8). Loading of 1 mol% instead of
5 mol% of catalyst slightly reduces yields (compare
entries 8 and 9, 12 and 13); nevertheless, we had con-
ducted the following experiments using 1 mol% of
Pd(OAc)2. In the initial runs, we had taken two equiv-
alents of ligand to palladium [7a,22]. Now it is con-
sidered reasonable that monoligated palladium(0)
complexes, generated by thermal decomposition of
the initially formed diligated species [7g,8], are in-
volved in the reaction [23]; so, starting from entry 11,
we had taken the ratio [Pd]/L 1:1, although the yield
in dioxane was reduced from 72% to 50% (entry 11
versus entry 10).
FIGURE 2 ORTEP view of compound 2; displacement el-
lipsoids drawn at 50% probability level. Hydrogen atoms are
omitted for clarity.
[Pd]
(HO)2B
Me
Me
Me
+
Br
Me
SCHEME 4
Heteroatom Chemistry DOI 10.1002/hc

8
Glushkov et al.
TABLE 1 Catalytic Activities of Salts 1a–e,g,i; 4,5
Entrya
Compound (R)
L/[Pd]
[Pd] (mol%)
Base
Solvent
Conversion, (%)
Yield (%)c
1
2
3
4
5
6
7
8
none
1a (Me)
1b (i-Pr)
1c (t-Bu)
1c (t-Bu)
1c (t-Bu)
1c (t-Bu)
1c (t-Bu)
1c (t-Bu)
1d (Bn)
1d (Bn)
1d (Bn)
1d (Bn)
1e (Ph)
1g (p-Tolyl)
1i (Mesityl)
4
–
5
5
5
5
5
5
5
5
1
5
5
5
1
1
1
1
1
1
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K2CO3
K2CO3
K3PO4
K3PO4
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
dioxane
dioxane
dioxane
dioxane
dioxane
DME
toluene
DMF
DMF
dioxane
dioxane
DMF
DMF
DMF
56
60
63
67
96
38
45
99
94
72
58
88
84
82
94
78
83
94
8
57
55
47
56
24
41
92
88
72
50
88
84
82
89
69
39
77
2/1
2/1
2/1
1/1b
2/1
2/1
1/1
1/1
2/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
9
10
11
12
13
14
15
16
17
18
DMF
DMF
DMF
DMF
5
aConditions: 2.8 mmol of 4-bromotoluene, 2.8 mmol of 4-tolylboronic acid, and 5.6 mmol of base in 50 mL of solvent at 90◦C, 5 h under aerobic
conditions.
bEq. (1) of Ph3P to Pd was added.
cGC yield with pentadecane as the internal standard.
It appears that the steric hindrance has little in-
fluence on catalytic activities of ligands (compare
entries 9,13-16). The most active ligands are com-
pounds 1c,d,g, bearing tert-Bu, benzyl-, or p-tolyl-
groups (entries 8,12,15). Ligands 4 and 5 show a
modest level of activity (entries 17,18).
To exclude homo-coupling, the reaction of para-
tolylboronic acid with bromobenzene in optimized
conditions (Pd(OAc)2 (1 mol%), 1c (1 mol%), DMF,
K2CO3, 90◦C, 5 h) was studied; it was shown that
the yield of homo-coupling product did not ex-
ceed 9%–10%. To our regret, our catalytic system is
not appropriate for cross-coupling of aryl chlorides:
4-chloroanisole as a deactivated challenging sub-
strate does not enter into coupling reactions in our
conditions.
EXPERIMENTAL
1-Benzyl-1H -imidazole, 1-phenyl-1H -imidazole,
para-tolylboronic acid, and DME were supplied
from Alfa Aesar (Lancaster). DMF (analytical grade)
and dichloromethane were products of Russia
and were used without special purification. 1-
(4-Tolyl)-1H-imidazole was synthesized by aryla-
tion of imidazole by 1-(4-tolyl)-boronic acid [24];
1-(2-tolyl)-1H-imidazole, 1-(2,6-dimethylphenyl)-
1H - imidazole, and 1 - (2,4,6 - trimethylphenyl) - 1H-
imidazole were synthesized according to the re-
cently published protocol [25]. Analytical thin-layer
chromatography was performed using silica gel
plates Sorbfil in a chloroform-acetone mixture (10:1,
v/v); compound spots were visualized by UV light
(254 nm). IR spectra, obtained by dissolving com-
pounds in CHCl3 with consequent evaporation of
chloroform were recorded on a Fourier spectrom-
CONCLUSION
1
eter Bruker IFS 66ps in nujol or in thin film; H
Starting from the derivatives of dehydroabietic acid,
we had prepared the family of sterically demanding
ligands for the Suzuki–Miyaura reaction: six new
asymmetrically (1d–i) and two symmetrically sub-
stituted (4,5) chiral imidazolium salts bearing the
diterpene moiety. Some of them showed activity as
ligands for the Pd-mediated coupling reaction of
4-bromotoluene and 4-tolylboronic acid, although
coupling of 4-chloroanisole was inefficient. We had
found that DMF as a solvent and K2CO3 as a base ap-
peared to be quite suitable for the coupling reactions
of new ligands.
and 13C NMR spectra were obtained on a Varian
Mercury+300 instrument at 300 and 75 MHz respec-
tively, in CDCl3 or DMSO-d6, and were referenced to
HMDS (1H NMR δ = 0.055 ppm), residual CHCl3 (13C
NMR δ = 77.0 ppm), or residual DMSO (13C NMR δ =
39,6 ppm). Mass-spectra were recorded on a GC-MS
system Agilent 6890N series with a mass-selective
detector MSD 5975B (EI, 70 eV). Optical rotation
was measured on a Perkin-Elmer 341 polarimeter in
CHCl3 containing 0.5% of EtOH as a stabilizer. Ele-
mental analyses (C,H,N) were obtained using a Leco
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Imidazolium Salts with Abietane Moiety
9
CHNS 9321P elemental analyzer at the Institute of
Technical Chemistry, Perm.
0.63 mL) of 1-phenyl-1H-imidazole in 50 mL MeCN.
Yield 1.74 g (67%), colorless prisms, mp 195–196◦C
(from AcOEt-MeCN); [α]2D0 + 47.6 (C 0.5, CHCl3).
IR, ν (Nujol) 3468, 3376 (OH), 1724 (O C O), 1597
(C C), 1565 (C C), 1549 (C N), 1498 (C C), 1435,
General Procedure for the Synthesis of
Compounds 1d–i
1
1247, 1212, 1176, 1132, 1111, 1081, 763 cm−1. H
Methyl 12-chloromethyl-dehydroabietate [18] (1.81
g, 5 mmol) and 5 mmol of corresponding 1-R-1H-
imidazole were refluxed in dry acetonitrile (50 mL)
for 6 h. The residue, after evaporation of MeCN,
was treated with 30 mL of hot ethylacetate, result-
ing in the formation of compounds 1a–i as white
solids, which were dried at 55◦C in vacuo. Analytical
samples were obtained after recrystallization from
EtOAc-MeCN mixture. Compounds 1a–c were syn-
thesized earlier [16].
NMR (CDCl3) δ: 1.09 (d, 3H, J = 6.9 Hz, Me),
1.14 (d, 3H, J = 6.9 Hz, Me), 1.19 (s, 3H, Me),
1.26 (s, 3H, Me), 1.42 (m, 2H, C(5)Hax, C(6)Hax),
1.63–1.90 (m, 5H, C(6)Heq, H2C(7), H2C(9)), 2.18
(m, 1H, C(5)Heq), 2.35 (m, 1H, HC(8a)), 2.90 (m,
2H, H2C(10)), 3.10 (m, 1H, J = 6.9 Hz, ArCH),
3.66 (s, 3H, OMe), 5.73 (d, 1H, J = 14.4 Hz,
NCH2Ar), 5.81 (d, 1H, J = 14.4 Hz, NCH2Ar), 7.01
(s, 1H, HC(1)), 7.10 (m, 1H, CHimidazole), 7.28 (m, 1H,
CHimidazole), 7.45-7.56 (m, 3H, HC(4)+2Harom), 7.82
(m, 3H, Harom), 11.55 (s, 1H, NCH N). 13C NMR
(CDCl3) δ: 16.22, 18.15, 21.18, 23.72, 23.81, 24.89,
28.49, 29.52, 36.34, 36.72, 37.69, 44.38, 47.28, 51.43,
51.73, 120.62, 121.45, 121.69, 125.97, 126.90, 127.05,
129.77, 130.25, 134.32, 135.75, 135.74, 137.34,
144.72, 148.04, 178.70. Found: C, 72.34; H, 7.39; N,
5.87%. Calcd for C31H39ClN2O2× 0.25 H2O: C, 72.78;
H, 7.78; N, 5.47%.
1-Benzyl-3-[((4bS,8R,8aR)-2-isopropyl-8-
(methoxycarbonyl)-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
methyl]-1H-imidazol-3-ium chloride,
semihydrate (1d)
Synthesized according to general procedure from
1.32 g (3.6 mmol) of methyl 12-chloromethyl-
dehydroabietate and 576 mg (3.6 mmol) of 1-benzyl-
1H-imidazole in 40 mL MeCN. Yield 1.43 g (75%),
colorless prisms, mp 208-210◦C, [α]D25 + 45.4 (c 1,
CHCl3). IR, ν (thin film): 3398 (OH), 2943 (C-H),
1715 (O C = O), 1607 (C C), 1557, 1498 (C C),
1455 (C H), 1387 (C H), 1360 (C H), 1248, 1192,
3-[((4bS,8R,8aR)-2-Isopropyl-8-
(methoxycarbonyl)-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
methyl]-1-phenyl-1H-imidazol-3-ium
tetrafluoroborate (Ie·BF4)
1
1161, 1135, 1109, 1045, 971 cm−1. H NMR (CDCl3)
δ: 1.04 (d, 3H, J = 6.9 Hz, Me), 1.08 (d, 3H, J =
6.9 Hz, Me), 1.25 (s, 3H, Me), 1.16 (s, 3H, Me),
1.40 (m, 2H, C(5)Hax, C(6)Hax), 1.63–1.87 (m, 5H,
C(6)Heq, C(7)H2, C(9)H2), 2.15 (m, 1H, C(5)Heq), 2.22
(m, 1H, HC(8a)), 2.42 (br.s, 1H, OH), 2.87 (m, 2H,
H2C(10)H2), 3.65 (s, 3H, OMe), 2.96 (m, 1H, ArCH),
5.46 (d, 1H, J = 14.7 Hz, NCH2Ar), 5.53 (d, 1H, J =
14.7 Hz, NCH2Ar), 5.64 (s, 2H, PhCH2), 6.85 (m, 1H,
CHimidazole), 6.97 (s, 1H, C(1)H), 7.08 (s, 1H, C(4)H),
7.27 (m, 2H, Harom), 7.37 (m, 3H, Himidazole+2Harom),
7.48 (m, 2H, Harom), 11.11 (s, 1H, NCH = N). 13C
NMR (CDCl3) δ: 16.0, 18.0, 21.0, 23.4, 23.5, 24.7,
28.2, 29.3, 36.1, 36.5, 37.4, 44.2, 47.0, 50.8, 51.5,
52.8, 120.8, 122.1, 125.9, 126.1, 126.7, 128.5, 128.77,
128.82, 133.3, 136.7, 136.9, 144.1, 147.7, 178.4 (C =
O). Found: C, 72.57; H, 7.78; N, 5.30%. Calcd for
To a solution of compound 1e (570 mg, 1.12 mmol)
in ethanol (40 mL) NH4BF4 (151 mg, 1.43 mmol) in
H2O (40 mL) was added. Ethanol was evaporated in
vacuo; the residue was filtered, washed with water,
dried in air, and crystallized from a AcOEt-MeCN
mixture. Yield 390 mg (62%), colorless plates, mp
168–170◦C; [α]D20 + 39.2 (c 0.5, CHCl3). IR, ν (thin
film): 3164, 3075, 2946, 2869, 1723, 1597, 1551, 1496,
1463, 1431, 1384, 1248, 1190, 1133, 1058, 760 cm−1.
1H NMR (CDCl3) δ: 1.10 (d, 3H, J = 7.2 Hz, Me), 1.14
(d, 3H, J = 7.2 Hz, Me), 1.20 (s, 3H, Me), 1.27 (s, 3H,
Me), 1.44 (m, 2H, C(5)Hax, C(6)Hax), 1.55–1.90 (m,
5H, C(6)Heq, C(7)H2, C(9)H2), 2.18 (m, 1H, C(5)Heq),
2.34 (m, 1H, HC(8a)), 2.89 (m, 2H, C(10)H2), 2.96 (m,
1H, ArCH), 3.66 (s, 3H, OMe), 5.57 (d, 1H, J = 14.7
Hz, NCH2Ar), 5.62 (d, 1H, J = 14.7 Hz, NCH2Ar),
7.02 (s, 1H, HC(1)), 7.14 (m, 1H, CHimidazole), 7.29
(s, 1H, HC(4)), 7.46 (m, 1H, CHimidazole), 7.55–7.63
(m, 5H, Ph), 9.30 (s, 1H, NCH N). 13C NMR (CDCl3)
δ: 16.4, 18.3, 21.3, 23.7, 24.9, 28.5, 29.7, 36.5, 36.8,
37.6, 44.5, 47.4, 51.5, 51.8, 121.3, 121.9, 122.6, 126.0,
127.0, 127.4, 130.2, 130.4, 133.9, 134.4, 137.6, 144.8,
148.3, 178.8 (C O). Found: C, 66.37; H, 6.99; N,
1
C32H41ClN2O2· /2H2O: C, 72.50; H, 7.99; N, 5.28%.
3-[((4bS,8R,8aR)-2-Isopropyl-8-(methoxycarbo-
nyl)-4b,8-dimethyl-4b,5,6,7,8,8a,9,10-octahydrop-
henanthren-3-yl)-methyl]-1-phenyl-1H-imidazol-
3-ium chloride × 0.25 H2O (1e)
Synthesized from 1.81 g (5 mmol) of methyl 12-
chloromethyl-dehydroabietate and 721 mg (5 mmol,
Heteroatom Chemistry DOI 10.1002/hc

10 Glushkov et al.
5.02%. Calcd for C31H39BF4N2O2: C, 66.67; H, 7.04;
N, 5.02%.
NCH2), 7.01 (s, 1H, C(1)H), 7.21 (s, 1H, Himidazole),
7.27–7.48 (m, 6H, 4Harom+C(4)H+Himidazole), 10.95 (s,
1H, NCH N). 13C NMR (CDCl3) δ: 16.2, 17.6, 18.2,
21.2, 23.7, 23.8, 28.4, 29.5, 36.3, 36.7, 37.7, 44.4,
47.3, 51.6, 51.7, 121.5, 123.0, 126.0, 126.3, 126.9,
127.0, 127.5, 130.7, 131.8, 132.9, 133.7, 137.2, 137.5,
144.7, 148.0, 178.7 (C O). Found: C, 67.37; H, 7.10;
N, 4.52%. Calcd for C32H41ClN2O2·2.5 H2O: C, 67.91;
H, 8.19; N, 4.95%.
3-[((4bS,8R,8aR)-2-Isopropyl-8-
(methoxycarbonyl)-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
methyl]-1-phenyl-1H-imidazol-3-ium
hexafluorophosphate (Ie·PF6)
To a solution of compound 1e (540 mg, 1.06 mmol)
in ethanol (10 mL), NH4PF6 (240 mg, 1.5 mmol) in
H2O (10 mL) was added. The resulting crystals were
filtered, washed with water, and dried in air. Yield
410 mg (63%), colorless powder, mp 209–211◦C
(from AcOEt-MeCN); [α]2D0 + 38.0 (c 0.5, CHCl3). IR, ν
(Nujol): 1724 (O C = O), 1599 (C = C), 1567 (C = C),
1554 (C = N), 1498 (C = C), 1413, 1247, 1204, 1186,
1135, 1111, 1076, 847, 821 cm−1. 1H NMR (CDCl3) δ:
1.07 (d, 3H, J = 6 Hz, Me), 1.12 (d, 3H, J = 6 Hz,
Me), 1.19 (s, 3H, Me), 1.26 (s, 3H, Me), 1.41 (m, 2H,
C(5)Hax, C(6)Hax), 1.58-1.90 (m, 5H, C(6)Heq, C(7)H2,
C(9)H2), 2.17 (m, 1H, C(5)Heq), 2.35 (m, 1H, C(8a)H),
2.90 (m, 2H, C(10)H2), 2.94 (m, 1H, ArCH), 3.66 (s,
3H, OMe), 5.42 (d, 1H, J = 14.4 Hz, NCH2Ar), 5.49
(d, 1H, J = 14.4 Hz, NCH2Ar), 7.01 (s, 1H, C(1)H),
7.21 (m, 1H, CHimidazole), 7.25 (m, 1H, CHimidazole), 7.28
(s, 1H, C(4)H), 7.52 (m, 5H, Ph), 8.80 (s, 1H, NCH =
N). 13C NMR (CDCl3) δ: 16.3, 16.4, 18.3, 21.4, 23.7,
23.8, 24.9, 28.6, 29.7, 36.6, 36.9, 37.6, 44.6, 47.5,
51.9, 121.4, 122.1, 122.2, 122.7, 125.6, 127.2, 127.5,
130.4, 133.5, 134.4, 137.8, 144.9, 148.4, 178.9 (C =
O). Found: C, 60.25; H, 6.09; N, 4.78%. Calcd for
C31H39F6N2O2P: C, 60.38; H, 6.38; N, 4.54%.
1-(4-Methylphenyl)-3-[((4bS,8R,8aR)-2-
Isopropyl-8-(methoxycarbonyl)-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
methyl]-1H-imidazol-3-ium chloride,
hydrate (1g)
Prepared from 726 mg (2 mmol) of methyl 12-
chloromethyl-dehydroabietate and 314 mg (2 mmol)
of 1-(4-methylphenyl)-1H-imidazole in 30 mL
MeCN. Yield 458 mg (44%), colorless prisms, mp
144-146◦C (from ꢁA-MeCN); [α]2D0 + 23.8 (c 0.5,
CHCl3). IR, ν (Nujol): 3456 (OH), 3067 (C–Harom),
1728 (O C = O), 1614 (C = C), 1556 (C = N), 1517
(C = C), 1306, 1244, 1186, 1173, 1132, 1076, 819
cm−1.1H NMR (CDCl3) δ: 1.10 (d, 3H, J = 6.6 Hz,
Me), 1.14 (d, 3H, J = 6.6 Hz, Me), 1.19 (s, 3H, Me),
1.26 (s, 3H, Me), 1.43 (m, 2H, C(5)Hax, C(6)Hax), 1.63–
1.90 (m, 5H, C(6)Heq, C(7)H2, C(9)H2), 2.16 (m, 1H,
C(5)Heq), 2.32 (m, 1H, C(8a)H), 2.39 (s, 3H, Ar-Me),
2.89 (m, 2H, C(10)H2), 3.09 (m, 1H, ArCH), 3.66
(s, 3H, OMe), 5.73 (d, 1H, J = 14.7 Hz, NCH2Ar),
5.82 (d, 1H, J = 14.7 Hz, NCH2Ar), 7.01 (s, 1H,
C(1)H), 7.07 (m, 1H, CHimidazole), 7.28 (s, 1H, C(4)H),
7.33 (d, 2H, J = 8.1 Hz, C(2’,6’)Harom), 7.58 (m, 1H,
CHimidazole), 7.65 (d, 2H, J = 8.1 Hz, C(3’,5’)Harom),
1-(2-Methylphenyl)-3-[((4bS,8R,8aR)-2-
Isopropyl-8-(methoxycarbonyl)-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
methyl]-1H-imidazol-3-ium chloride,
hydrate (1f)
1
11.43 (s, 1H, NCH = N). 3C NMR (CDCl3) δ: 16.2,
18.2, 20.8, 21.2, 23.7, 23.8, 24.8, 28.4, 29.5, 36.3,
36.7, 37.7, 44.4, 47.3, 51.3, 51.7, 120.6, 121.3, 121.6,
126.0, 126.8, 127.0, 130.7, 132.0, 135.5, 137.3, 140.1,
144.7, 148.0, 178.7 (C = O). Found: C, 70.70; H, 7.87;
N, 5.17%. Calcd for C32H41ClN2O2·H2O: C, 71.29; H,
8.04; N, 5.20%.
Prepared from 726 mg (2 mmol) of methyl 12-
chloromethyl-dehydroabietate and 314 mg (2 mmol)
of 1-(2-methylphenyl)-1H-imidazole in 30 mL
MeCN. Yield 541 mg (52%), off-white powder, mp
201–203◦C; [α]D21 + 45.2 (c 1, CHCl3). IR, ν (Nu-
jol): 3380 (OH), 1727 (O-C = O), 1553, 1500, 1302,
1246, 1187, 1130, 1046, 984, 916, 761 cm−1. 1H NMR
(CDCl3) δ: 1.10 (d, 3H, J = 6.6 Hz, Me), 1.15 (d,
3H, J = 6.6 Hz, CH), 1.20 (s, 3H, Me), 1.27 (s, 3H,
Me), 1.43 (m, 2H, C(9)Hax, C(5)Hax), 1.64–1.90 (m,
5H, C(6)H2, C(7)H2, C(9)Heq), 2.18 (dd, 1H, J = 12.3,
2.1 Hz, C(8a)H), 2.29 (s, 3H, MeAr), 2.32 (m, 1H,
C(5)Heq), 2.89 (m, 2H, C(10)H2), 3.12 (m, 1H, J =
6.6 Hz, CH(Me)2), 3.67 (s, 3H, OMe), 5.84 (d, 1H,
J = 14.7 Hz, NCH2), 5.93 (d, 1H, J = 14.7 Hz,
1-(2,6-Dimethylphenyl)-3-[((4bS,8R,8aR)-2-
Isopropyl-8-(methoxycarbonyl)-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
methyl]-1H-imidazol-3-ium chloride, trihydrate
(1h)
Prepared from 726 mg (2 mmol) of methyl 12-
chloromethyl-dehydroabietate and 344 mg (2 mmol)
of 1-(4-methylphenyl)-1H-imidazole in 30 mL
MeCN. Yield 353 mg (33%), white powder, mp 241–
243◦C, [α]D22 +47.7 (c 1, CHCl3). IR, ν (thin film): 3376
(OH), 2937, 1720 (O-C = O), 1548, 1465, 1380, 1249,
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Imidazolium Salts with Abietane Moiety 11
1185, 1105, 1050, 959, 888 cm−1. 1H NMR (CDCl3) δ:
1.11 (d, 3H, J = 6.6 Hz, Me), 1.16 (d, 3H, J = 6.6 Hz,
Me), 1.20 (s, 3H, Me), 1.27 (s, 3H, Me), 1.44 (m, 2H,
C(9)Hax, C(5)Hax), 1.62-1.90 (m, 5H, C(6)H2, C(7)H2,
C(9)Heq), 2.12 (m, 6H, 2Me), 2.18 (dd, 1H, J = 12.3,
2.1 Hz, C(8a)H), 2.31 (m, 1H, C(5)Heq), 2.90 (m, 2H,
C(10)H2), 3.12 (m, 1H, J = 6.6 Hz, CH(Me)2), 3.67
(s, 3H, OMe), 5.90 (d, 1H, J = 14.4 Hz, NCH2), 5.98
(d, 1H, J = 14.4 Hz, NCH2), 7.01 (s, 1H, C(1)H),
7.14–7.32 (m, 6H, 3Harom+C(4)H+2Himidazole), 10.93
(s, 1H, NCH N). 13C NMR (CDCl3) δ: 16.3, 17.6,
18.28, 18.29, 21.3, 23.97, 24.04, 25.0, 28.6, 29.6,
36.4, 36.8, 37.9, 44.5, 47.4, 51.86, 51.94, 121.9, 122.8,
126.5, 126.9, 127.1, 129.1, 130.9, 133.1, 134.4, 137.3,
138.1, 144.8, 148.1, 178.8 (C O). Found: C, 67.36;
H, 7.10; N, 4.52%. Calcd for C33H43ClN2O2·3H2O: C,
67.28; H, 8.38; N, 4.75%.
and 0.93 mL (6.37 mmol) of glyoxal (40% aq. soln.)
was added in one portion; after 4 h of stirring at
room temperature, the bright yellow crystals were
filtered, washed with propanol-2, and dried. Yield
3.60 g (83%). Compound 2 was used further without
additional purification. An analytical sample was re-
crystallized from ethanol, bright yellow prisms, mp
225–228◦C; [α]D22 +300.0 (c 1, CHCl3). IR, ν (Nujol):
1715 (O C O), 1600 (C C), 1245, 1135, 1045, 990,
880 cm−1; 1H NMR (CDCl3) δ: 1.13 (d, 6H, J = 7 Hz,
Me), 1.14 (d, 6H, J = 7 Hz, Me), 1.18 (s, 6H, Me),
1.22 (s, 6H, Me), 1.35–1.86 (m, 14H, 2 C(5)Hax, 2
C(6)H2, 2 C(7)H2, 2 C(9)H2), 2.18 (m, 2H, C(5)Heq),
2.27 (m, 2H, C(8a)H), 2.85 (m, 4H, C(10)H2), 3.44 (m,
2H, ArCH), 3.61 (s, 6H, OMe), 6.80 (s, 2H, C(1)H),
6.92 (m, 2H, C(4)H), 8.23 (m, 2H, CH N). 13C NMR
(CDCl3) δ: 16.5, 18.5, 21.6, 23.2, 23.5, 25.0, 27.4, 29.8,
36.6, 37.2, 38.1, 44.8, 47.6, 51.9, 113.0, 126.2, 134.7,
140.4, 146.5, 147.7, 158.8, 178.9 (C O). Found: C,
77.28; N, 8.63; H, 4.07%. Calcd for C44H60N2O4: C,
77.61; N, 8.88; H, 4.11%.
3-[((4bS,8R,8aR)-2-Isopropyl-8-
(methoxycarbonyl)-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
methyl]-1-mesityl-1H-imidazol-3-ium chloride
(1i)
1,4-Bis-((4bR,8S,8aS)-2-isopropyl-8-
methoxycarbonyl-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
1,4-diazabutane dihydrochloride,
hydrate (3)
Obtained from 726 mg (2 mmol) of methyl 12-
chloromethyl-dehydroabietate and 372 mg (2 mmol)
of 1-mesityl-1H-imidazole in 30 mL MeCN. Yield
802 mg (73%), white powder, mp 198–200◦C, [α]2D5
+ 44.4 (c 1, CHCl3). IR, ν (Nujol) 3329 (br., OH),
1720 (C O), 1609 (v.), 1543, 1245, 1198, 1133, 1112,
1061, 1044, 758, 722 cm−1.1H NMR (CDCl3) δ: 1.09
(d, 3H, J = 6.6 Hz, Me), 1.14 (d, 3H, J = 6.6 Hz,
Me), 1.19 (s, 3H, Me), 1.26 (s, 3H, Me), 1.43 (m,
2H, C(5)Hax, C(6)Hax), 1.72 (m, 5H, C(6)Heq, C(7)H2,
C(9)H2), 2.06 (s, 6H, 2Me), 2.18 (m, 1H, C(5)Heq),
2.32 (s, 3H, Me), 2.45 (m, 1H, C(8a)H), 2.88 (m, 2H,
C(10)H2), 3.11 (m, 1H, ArCH), 3.66 (s, 3H, OMe),
5.84 (d, 1H, J = 14.7 Hz, NCH2Ar), 5.92 (d, 1H, J
= 14.7 Hz, NCH2Ar), 6.97 (s, 2H, C(3’,5’)H), 7.00
(s, 1H, C(1)H), 7.23 (s, 2H, Himidazole), 7.32 (s, 1H,
C(4)H), 10.66 (s, 1H, NCH = N). 13C NMR (CDCl3)
δ: 16.3, 17.4, 18.3, 20.9, 21.3, 23.9, 24.0, 25.0, 28.5,
29.6, 36.5, 36.8, 37.9, 44.5, 47.4, 51.8, 121.9, 123.0,
126.6, 126.9, 127.0, 129.7, 130.7, 134.0, 137.2, 138.2,
141.0, 144.8, 148.0, 178.8 (C O). Found: C, 68.69; H,
7.68; N, 4.64%. Calcd for C34H45ClN2O2·2.5 H2O: C,
68.71; H, 8.48; N, 4.71%.
To diimine 2 (0.9 g, 1.27 mmol), dissolved in a
mixture of 40 mL THF and 10 mL MeOH, 150
mg (2.63 mmol) of NaBH4 was added. Suspension
was stirred for 12 h at room temperature; 50 mg
of NaBH4 was added and heated under reflux for
1 h; after cooling, 30 mL of cold water was added
and stirred until gaseous products ceased to evalu-
ate from the solution (∼1 h); then 30 mL of 3N HCl
was added. In 12 h, white crystals of dihydrochlo-
ride of 3 were filtered, washed with water, and dried
in air for 12 h, then in a desiccator over P2O5 in
vacuo for 12 h. Yield 365 mg (37%), white pow-
der, mp 207–210◦C, [α]2D4 +67.7 (c 1, CHCl3). IR, ν
(Nujol): 3400 (HN+, br., OH), 1700 (O C O), 1200,
1
1170, 1130, 990 cm−1. H NMR (CDCl3) δ: 1.05 (s,
6H, Me), 1.06 (d, 6H, J = 6 Hz, Me), 1.07 (d, 6H, J
= 6 Hz, Me), 1.13 (s, 6H, Me), 1.18–1.69 (m, 14H,
2 C(5)Hax, 2 C(6)H2, 2 C(7)H2, 2 C(9)H2), 1.93 (m,
2H, C(5)Heq), 2.74 (m, 4H, C(10)H2), 3.06 (m, 2H,
ArCH), 3.45 (m, 4H, 2 NCH2), 3.54 (s, 6H, OMe),
3.97 (br. s, 2H, 2 HN+), 6.93 (s, 2H, C(1)H), 7.05 (s,
2H, C(4)H). 13C NMR (CDCl3) δ: 16.2, 17.9, 20.9, 23.6,
24.4, 26.0, 28.7, 36.1, 36.6, 37.6, 44.6, 44.7, 45.4, 46.8,
51.7, 115.0, 127.2, 131.5, 134.1, 136.4, 147.8, 177.8
(C O). Found: C, 64.96; H, 8.58; N, 3.78%. Calcd for
1,4-Bis-((4bR,8S,8aS)-2-isopropyl-8-
methoxycarbonyl-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
1,4-diazabutadiene (2)
Methyl 12-aminodehydroabietate [19] (4.18 g,
12.7 mmol) was dissolved in propanol-2 (90 mL)
.
C44H64N2O42HCl·3.5H2O: C, 64.38; H, 8.96; N, 3.41%.
Heteroatom Chemistry DOI 10.1002/hc

12 Glushkov et al.
47.5, 51.9, 54.0, 123.9, 127.2, 130.3, 138.4, 140.7,
150.3, 156.6, 179.0 (C O). Found: C, 68.98; H, 8.09;
N, 3.45%. Calcd for C45H63BF4N2O4: C, 69.04; H, 8.11;
N, 3.58%.
1,3-Bis-((4bR,8S,8aS)-2-isopropyl-8-
methoxycarbonyl-4b,8-dimethyl-4b,5,6,7,8,8a,9,
10-octahydrophenanthren-3-yl)-4,5-dihydro-1H-
imidazol-3-ium chloride, hydrate (4·Cl)
Suspension of 478 mg (0.59 mmol) of compound
3 was refluxed in 10 mL of ethyl orthoformate and
two drops of formic acid (99%) for 30 min, cooled to
70◦C, and 10 mL of MeCN was added. Volatiles were
distilled (from 80◦ up to 140◦C) until the formation
of crystalline compound (4·Cl), which was filtered
after cooling, washed with 5 mL of ether, and dried
in vacuo. Yield 156 mg (37%), white powder, mp
200-204◦C (decomp.),[α]D20 + 109 (c 1.56, CHCl3).
IR, ν (Nujol): 3370 (br., OH), 1716 (O C O), 1622
(C C), 1308, 1250, 1174, 1132, 1122, 1084, 896
1,3-Bis-((4bR,8S,8aS)-2-isopropyl-8-
methoxycarbonyl-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
1H-imidazol-3-ium chloride,
trihydrate (5)
This compound was synthesized by the method
referenced in [10], which is the modification of
Arduengo methodology [21]. To 458 mg (0.67 mmol)
of bis-imine 2, 1.5 mL of chloromethyl-propyl ether
was added and the brown solution was stirred for
5 min. Afterwards 3 mL of MeCN was added and
stirred at room temperature for 1 h. The residue, af-
ter evaporation of volatiles in vacuo, was treated by
ethyl ether; ether was evaporated and the residue
was treated with 5 mL of ethyl acetate to afford
274 mg (56%) of compound 5. Off-white prisms, mp
235–238◦C, [α]D24 +76.4 (c 0.5, CHCl3). IR, ν (Nujol):
3400 (br., OH), 1722 (O C O), 1632 (C C), 1546,
1
cm−1. H NMR (CDCl3) δ: 1.17 (s, 6H, Me), 1.19 (d,
6H, J = 6 Hz, Me), 1.20 (d, 6H, J = 6 Hz, Me), 1.23
(s, 6H, Me), 1.36–1.83 (m, 14H, 2 C(5)Hax, 2 C(6)H2,
2 C(7)H2, 2 C(9)H2), 2.07 (m, 2H, C(5)Heq), 2.50 (m,
2H, HC(8a)), 2.85 (m, 4H, C(10)H2), 2.87 (m, 2H,
CHAr), 3.60 (s, 6H, OMe), 4.67 (m, 4H, 2 NCH2),
6.94 (s, 2H, C(1)H), 7.72 (s, 1H, N = CHN), 7.93
(m, 2H, C(4)H). 13C NMR (CDCl3) δ: 16.2, 17.7, 20.6,
23.7, 23.8, 24.3, 27.0, 28.8, 36.2, 36.7, 37.6, 44.4,
46.7, 51.7, 53.6, 99.4, 122.7, 127.2, 131.3, 137.0,
141.4, 148.4, 177.7 (C = O). Found: C, 66.25; H,
8.34; N, 3.73%. Calcd for C45H63ClN2O4·4H2O: C,
67.27; H, 8.91; N, 3.49%.
1
1248, 1174, 1132, 1122, 1084, 896 cm−1. H NMR
(DMSO-d6) δ: 1.20 (d, 6H, J = 6.3 Hz, Me), 1.24
(d, 6H, J = 6.3 Hz, Me), 1.25 (s, 6H, Me), 1.28 (s,
6H, Me), 1.42–1.95 (m, 14H, C(5)Hax, 2 C(6)H2, 2
C(7)H2, 2 C(9)H2), 2.08 (m, 2H, C(5)Heq), 2.35 (m,
2H, C(8a)H), 2.63 (m, 2H, CHAr), 3.00 (m, 4H, 2
C(10)H2), 3.60 (s, 6H, OMe), 7.33 (s, 2H, C(4)H), 7.54
(s, 2H, C(4)H), 8.31 (d, 2H, J = 1.5 Hz, 2 Himidazole),
9.91 (t, J = 1.5 Hz, 1H, NCH = N). 13C NMR (CDCl3)
δ: 16.3, 18.0, 20.9, 23.5, 23.7, 24.8, 26.4, 28.9, 36.2,
36.7, 37.7, 44.6, 46.9, 52.0, 119.3, 126.6, 127.3, 134.9,
139.1, 147.9, 177.9 (C = O). Found: C, 69.08; N, 8.55;
H, 3.85%. Calcd for C45H61ClN2O4·3H2O: C, 68.99; H,
8.62; N, 3.58%.
1,3-Bis-((4bR,8S,8aS)-2-isopropyl-8-
methoxycarbonyl-4b,8-dimethyl-
4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)-
4,5-dihydro-1H-imidazol-3-ium
tetrafluoroborate (4·BF4)
Suspension of 320 mg (0.39 mmol) of compound 3
was refluxed in 10 mL of ethyl orthoformate and
two drops of formic acid (99%) for 20 min, then
50 mg (0.47 mmol) of NH4BF4 and 10 mL of MeCN
were added. Volatiles were distilled (from 80◦ up to
140◦C) until the formation of crystalline compound
(4·BF4), which was filtered after cooling, washed
with 5 mL of ether, and dried in air. Yield 220 mg
(67%), white powder, mp 298–300◦C. IR, ν (Nujol):
1716 (O C O), 1622 (C C), 1308, 1250, 1174, 1132,
General Procedure for Suzuki Coupling Reaction
A 250 mL flask was charged by Pd(OAc)2 (6 mg,
0.028 mmol), 0.028 mmol of appropriate imida-
zolium salt 1a-i, 60 mg (0.43 mmol) of K2CO3, and
70 mL of DMF, and was heated at 90◦C for 15–
20 min for the formation of precatalyst in situ. Then
480 mg (2.8 mmol) of 4-bromotoluene was added
(2 mL of the working solution in DMF, contain-
ing 1 mL, 240 mg of 4-bromotoluene), 380 mg
(2.8 mmol) of 4-tolylboronic acid, 770 mg (5.6 mmol)
of K2CO3, and 0.4 mL of pentadecane as the inter-
nal standard. The flask was heated for 5 h at 90◦C
while stirring in aerobic conditions (at the end of the
experiment, some quantity of palladium black was
formed). After cooling, inorganic salts were filtered,
washed with 20 mL of DMF, and the solvent was
1
1122, 1084, 896 cm−1. H NMR (CDCl3) δ: 1.17 (s,
6H, Me), 1.19 (d, 6H, J = 6 Hz, Me), 1.20 (d, 6H,
J = 6 Hz, Me), 1.23 (s, 6H, Me), 1.36–1.83 (m, 14H,
2 C(5)Hax, 2 C(6)H2, 2 C(7)H2, 2 C(9)H2), 2.07 (m,
2H, C(5)Heq), 2.50 (m, 2H, HC(8a)), 2.85 (m, 6H, 2
C(10)H2+CHAr), 3.60 (s, 6H, OMe), 4.67 (m, 4H, 2
NCH2), 6.94 (s, 1H, C(1)H), 7.72 (s, 1H, NCH=N),
7.93 (m, 2H, C(4)H). 13C NMR (CDCl3) δ: 16.5, 18.4,
21.3, 24.1, 24.4, 24.8, 24.7, 28.0, 29.8, 36.7, 37.3, 44.5,
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Imidazolium Salts with Abietane Moiety 13
TABLE 2 Crystal Data and Structure Refinement for Compounds 1e and 2
1e
2
Empirical formula
Formula weight
Crystal size, mm
Crystal color
Temperature, K
Crystal system
Space group
(C31H39N2O2)+,Cl−,0.25H2O
C44H60N2O4
680.94
511.60
0.43 × 0.37 × 0.29
colorless
0.15 × 0.15 × 0.10
yellow
295(2)
Monoclinic
P21
12.3927(4)
8.7349(3)
120(2)
Monoclinic
P21
14.893(3)
7.9435(14)
˚
a, A
˚
b, A
˚
c, A
26.3703(9)
94.766(3)
2844.69(17)
17.257(3)
110.342(4)
1914.2(6)
β, deg.
Volume A
Z
3
˚
4
2
Density (calculated) g/cm3
Absorption coefficient, mm−1
Reflections collected
Independent reflections
θ range, deg.
1.195
0.165
11529
1.181
0.074
19965
8870 (Rint= 0.0149)
2.80–26.37
98.8
4936 (Rint = 0.1154)
1.46–28.00
99.7
Completeness to θ, %
Refined parameters
Goodness-of-fit on F2
Reflections with I > 2 σ (I )
R1(F)[I > 2σ(I )]a
667
1.009
5877
0.0359
461
0.978
2754
0.0723
wR2 (F2)[all data]
Largest diff. peak/hole, eA
0.0915
0.1122
−3
˚
0.191/–0.169
0.229/–0.279
ꢀ
ꢀ
aR1 = |Fo–|Fc||/ (Fo).
ꢀ
ꢀ
1
bwR2 = ( [w(Fo2– Fc2)2]/ [w(Fo2)2]
.
/
2
evaporated in vacuo until 5–10 mL volume. 70 mL of
brine were added, following extraction with CH2Cl2
(4 × 25 mL) and drying over MgSO4. The resulting
solution was analyzed on a GC-MS system Agilent
6890N.
CCDC 794333 (1e) and 794334 (2) contain
the supplementary crystallographic data for struc-
tures 1e and 2. These data can be obtained from
the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data request/cif.
CRYSTALLOGRAPHY
ACKNOWLEDGMENTS
X-ray experiments were carried out using an Oxford
The authors are very much obliged to Elena
Baigacheva, for elemental analysis, and Valery Kar-
manov, for recording IR spectra.
Diffraction Xcalibur S diffractometer (λ(Mo-Kα) =
˚
0.71073 A, graphite monochromator, ω/2θ scans)
for 1e and SMART 1000 CCD diffractometer (λ(Mo-
˚
Kα) = 0.71073 A, graphite monochromator, ω-scans)
for 2. All structures were solved by direct methods
and refined by the full-matrix least-squares proce-
dure in anisotropic approximation for nonhydrogen
atoms. Hydrogen atoms connected to carbon atoms
were placed in geometrically calculated positions,
whereas positions of disordered water hydrogens
were found in a difference Fourier synthesis. All the
hydrogen atoms were included in the refinement us-
ing riding approximation. The details of data collec-
tion and crystal structures refinement for which we
used SAINT Plus [26], SADABS [27] and SHELXTL-
97 [28] program packages are summarized in
Table 2.
REFERENCES
[1] Glushkov, V. A.; Valieva, M. S.; Maiorova, O. A.;
Baigacheva, E. V.; Gorbunov, A. A. Russ J Org Chem
2011, 47, 230–235.
[2] (a) Bourissou, D.; Guerret, O.; Bertrand, G. Chem
Rev 2000, 100, 39–92; (b) Melaimi, M.; Soleihavoup,
M.; Bertrand, G. Angew Chem, Int Ed 2010, 49,
8810–8849; (c) N-Heterocyclic Carbenes in Transi-
tion Metal Catalysis, Top Organomet Chem Vol. 21;
Glorius F. (Ed.); Springer: Berlin, 2007; (d) Hahn,
F. E.; Angew Chem, Int Ed 2008, 47, 3122–3172; (e)
Jahnke, M. C.; Hahn, F. E. Top Organomet Chem
2010, 30, 95–129; (f) D´ıez-Gonza´lez, S.; Marion, N.;
Nolan, S. P. Chem Rev 2009, 109, 3612–3676.
Heteroatom Chemistry DOI 10.1002/hc

14 Glushkov et al.
[3] (a) Enders, D.; Neimeier, O.; Henseler, A. Chem
Rev 2007, 107, 5606–5655; (b) Nair, V.; Bindu, S.;
Sreekumar, V. Angew Chem Int Ed 2004, 43, 5130–
5135.
[4] Herrmann, W. A. Angew Chem, Int Ed 2002, 41,
1290–1309.
[5] (a) Mercs, L.; Albrecht, M. Chem Soc. Rev 2010, 39,
1903–1912; (b) John, A.; Ghosh, P. Dalton Trans 2010,
39, 7183–7206.
[11] (a) Ma, Y.; Song, C.; Jiang, W.; Wu, Q.; Wang, Y.;
Liu, X.; Andrus, M. B. Org Lett 2003, 5, 3317–3319;
(b) Tapu, D.; Owens, C.; VanDerveer, D.; Gwaltney, K.
Organometallics 2009, 28, 270–276; (c) Fei, Z.; Zhu,
D.-R.; Yang, X.; Meng, L.; Lu, Q.; Ang, W. H.; Scopel-
liti, R.; Hartinger, C. G.; Dyson, P. J. Chem Eur J
2010, 16, 6473–6481.
[12] Metallinos, C.; Barrett, F. B.; Wang, Y.; Xu, S.; Tailor,
N. J. Tetrahedron 2006, 62, 11145–11157.
[6] (a) Grubbs, R. H. Tetrahedron 2004, 60, 7117–7140;
(b) Grubbs, R. H. Angew Chem, Int Ed 2006, 45,
3760–3765; (c) Vougioukalakis, G. C.; Grubbs, R. H.
Chem Rev 2010, 110, 1746–1787; (c) Ackermann, L.;
Fu¨rstner, A.; Weskamp, T.; Kohl, F. J.; Herrmann,
W. A. Tetrahedron Lett 1999, 40, 4787–4790; (d) Ja-
farpour, L.; Nolan, S. P. Organometallics 2000, 19,
2055–2057; (e) Fu¨rstner, A. Angew Chem, Int Ed
2000, 39, 3012–3043; (f) Hoveyda, A. H., Gillingham,
D. D.; Van Veldhuizen, J. J.; Kataoka, O.; Garber,
S. B.; Kingsbury, J. S.; Harrity, J. P. A. Org Biomol
Chem 2004, 2, 8–23; (g) Michrowska, A.; Bujok, R.;
Harutyunyan, S.; Sashuk, V.; Dolgonos, G.; Grela, K.
J Am Chem Soc 2004, 126, 9318–9325; (h) Connon, S.
J.; Blechert, S. Angew Chem, Int Ed 2003, 42, 1900–
1923.
[13] Richter, H.; Schwertfeger, H.; Shreiner, P. R.;
Fro¨hlich, R.; Glorius, F. Synlett 2009, 193–197.
[14] Berton-Gelloz, G.; Siegler, M. A.; Spek, A. L.; Tinant,
B.; Reek, J. N. H.; Marko´, I. E. Dalton Trans 2010, 39,
1444–1446.
[15] (a) Lee, S.; Hartwig, J. F. J Org Chem 2001, 66, 3402–
3415; (b) Markowicz, S. W.; Figlus, M.; Lejkowski, M.;
Karolak-Wojciechowska, J.; Dzierzawska-Majewska,
A.; Verpoort, F. Tetrahedron Asymmetry 2006, 17,
434–448; (c) Pernak, J.; Feder-Kubis, J.; Cieniecka-
Rosłonkiewicz, A.; Fischmeister, C.; Griffin, S.
T.; Rogers, R. D. New J Chem 2007, 31, 879–
892; (d) Malkov, A. V.; Stewart-Liddon, A. J.
P.; Teply´, F.; Kobr, L.; Muir, K. W.; Haigh, D.;
Kocˇovsky´, P. Tetrahedron 2008, 64, 4011–4025;
(e) Wu¨rtz, S.; Lohre, C.; Fro¨hlich, R.; Bergander,
K.; Glorius F. J Am Chem Soc 2009, 131, 8344–
8345.
[7] (a) Herrmann, W. A.; Elison, M.; Fisher, J.; Ko¨cher,
C.; Artus, G. R. J. Angew Chem Int Ed Engl 1995,
34, 2371–2374; (b) Kantchev, E. A. B.; O‘Brien, C.
J.; Organ, M. G. Angew Chem, Int Ed 2007, 46,
2768–2813; (c) Frey, G. D.; Schu¨tz, J.; Herdtweck, E.;
Herrmann, W. A. Organometallics 2005, 24, 4416–
4426; (d) Selvakumar, K.; Zapf, A.; Spannenberg, A.;
Beller M. Chem Eur J 2002, 8, 3901–3906; (e) Marion,
N.; Nolan, S. P. Acc Chem Res 2008, 41, 1440–1449;
(g) Marion, N.; Navarro, O.; Stevens, E. D.; Ecarnot,
E. C.; Bell, A.; Amoroso, D.; Nolan, S. P. Chem Asian
J 2010, 5, 841–846; (f) O‘Brien, C. J.; Kantchev, E.
A. B.; Valente, C.; Hadei, N.; Chass, G. A.; Lough, A.;
Hopkinson, A. C.; Organ, M. G. Chem Eur J 2006,
12, 4743–4748; (h) Organ, M. G.; Avola, S.; Dubovyk,
I.; Hadei, N.; Kantchev, E. A. B.; O‘Brien, C.J.; Va-
lente, C. Chem Eur J 2006, 12, 4749–4755; (i) Organ,
M. G.; Abdel-Hadi, M.; Avola, S.; Hadei, N.; Nasiel-
ski, J.; O‘Brien, C. J.; Valente, C. Chem Eur J 2007,
13, 150–157; (k) Organ, M. G.; Chass, G. A.; Fang,
D.-C.; Hopkinson, A. C.; Valente, C. Synthesis 2008,
2776–2797; (l) Peh, G.-R.; Kantchev, E. A. B.; Er, J.-C.;
Ying, J. Y. Chem Eur J 2010, 16, 4010–4017; (m) Dow-
lut, M.; Mallik, D.; Organ, M. G.; Chem Eur J 2010,
[16] Glushkov, V. A.; Kotelev, M. S.; Rudovsky, K. S.;
Tarantin, A. V.; Tolstikov, A. G. Russ J Org Chem
2009, 45, 404–407.
[17] (a) Perry, M.; Burgess, K. Tetrahedron Asymme-
try 2003, 14, 951–961; (b) Bonnet, L. G.; Douth-
waite, R. E.; Kariuki, B. M.; Organometallics 2003,
22, 4187–4189; (c) Ce´sar, V.; Bellemin-Laponnaz,
S.; Gade, L. H. Chem Soc Rev 2004, 33, 619–
636; (d) Struble, J. R.; Kaeobamrung, L.; Bode, J.
W. Org Lett 2008, 10, 957–960; (e) Struble, J. R.;
Bode, J. W. Tetrahedron 2008, 64, 6961–6972; (f)
R´ıos-Lombard´ıa, N.; Busto, E.; Gotor-Fernandez, V.;
Gotor, V.; Garc´ıa-Verdugo, E.; Luis, S. V.; Alfonso,
I.; Garc´ıa-Granda, S.; Mene´ndez-Vela´zquez, A. Chem
Eur J 2010, 16, 836–847; (g) Yoshida, K.; Horiuchi,
S.; Takeichi, T.; Shida, H.; Imamoto, T.; Yanagi-
sawa, A. Org Lett 2010, 12, 1764–1767; (h) Arduengo,
A. J., III; Iconaru, L. I. Dalton Trans 2009, 6903–
6914.
[18] Pratt, Y. T. U.S. Patent 2,472,437, 1949; Chem Abstr
1949, 43, 6665.
[19] Fieser, L. F.; Campbell, W. P. J Am Chem Soc 1939,
61, 2528–2534.
¨
16, 4279–4283; (n) Ozdemir, I.; Yasar, S.; Demir,
S.; C¸ etinkaya, B. Heteroatom Chem 2005, 16, 557–
561.
[8] Wu¨rtz, S.; Glorius, F. Acc Chem Res 2008, 41, 1523–
1533.
[20] Tolstikov, G. A.; Glushkov, V. A.; Tarantin, A. V.;
Kazanbaeva, G. F.; Shashkov, A. S.; Suponitsky, K.
Yu.; Dembitsky, V. M. Heteroatom Chem 2005, 16,
605–612.
[9] (a) Herrmann, W. A.; Goossen, L. J.; Ko¨cher, C.;
Artus, G. R. Angew Chem Int Ed Engl 1996, 35, 2805–
2807; (b) Lee, C.-C.; Ke, W.-C.; Chan, K.-T.; Lai, C.-L.;
Hu, C.-H.; Lee, H. M. Chem Eur J 2007, 13, 582; (c)
Luan, X.; Mariz, R.; Gatti, M.; Costabile, C.; Poater,
A.; Cavallo, L.; Linden, A.; Dorta, R. J Am Chem Soc
2008, 130, 6848–6858; (d) Vieille-Petit, L.; Clavier,
H.; Linden, A.; Blumentritt, S.; Nolan, S.; Dorta, R.
Organometallics 2010, 29, 775–788.
[21] Arduengo III, A. J.; Krafczyk, R.; Schmut-
zler,
R.
Tetrahedron
1999,
55,
14523–
14534.
[22] Fu¨rstner, A.; Leitner, A. Synlett 2001, 290–292.
[23] Christmann, U.; Vilar, R. Angew Chem, Int Ed 2005,
44, 366–374.
[24] Collman, J. P.; Zhong, M. Org Lett 2000, 2, 1233–
1236.
[25] Occhipinti, G., Jensen, V. R.; To¨rnroos, K. W.;
Frøystein, N. A.; Bjørsvik, H. R. Tetrahedron 2009,
65, 7186–7194.
[10] Alexander, S. G.; Cole, M. L.; Morris, J. C. New J
Chem 2009, 33, 720–724.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Imidazolium Salts with Abietane Moiety 15
[26] SMART and SAINT, Release 5.0, Area Detector con-
trol and Integration Software, Bruker AXS, Analyt-
ical X-Ray Instruments, Madison, Wisconsin, USA,
1998.
[27] Sheldrick, G. M. SADABS: A Program for Exploiting
the Redundancy of Area-detector X-Ray Data, Uni-
versity of Go¨ttingen, Go¨ttingen, Germany, 1999.
[28] Sheldrick, G. M. Acta Cryst 2008, A64, 112–122.
Heteroatom Chemistry DOI 10.1002/hc