Vol.2, No.11, 1189-1194 (2010) Natural Science
http://dx.doi.org/10.4236/ns.2010.211147
Chiral palladium complexes based on derivatives of
benzylamine and 2α-hydroxypinan-3-one
Olga A. Zalevskayaa, Yana A. Gur'evab,*, Larisa L. Frolovab, Igor N. Alekseevb, Alexander V.
Kutchinb
a Syktyvkar State University, Syktyvkar, Petrozavodskaja, Syktyvkar, Russia
b Institute of Chemistry of Komi Scientific Centre, Ural Branch of Russian Academy of Sciences, Pervomaiskaja, Syktyvkar, Russia;
*Corresponding author:
Received 30 July 2010; revised 2 September 2010; accepted 5 September 2010.
ABSTRACT
Synthesized and characterized new chiral palla-
dium complexes, some of which contain asym-
metric donor nitrogen atom. Nitrogen-containing
derivatives (+) - and (-)-2α-hydroxypinan-3-one-
(1R,2R,5R)-3-(benzylimino)-2,6,6-trimethylbicy-
clo[3.1.1]heptane-2-ol (HL1), (1S,2S,3S,5S)-3-
(benzylamino)-2,6, 6-trimethylbicyclo[3.1.1]-
heptane-2-ol (HL2), (1R,2R,5R)-3-((S)-α-methyl-
benzylimino)-2,6,6-trimethylbicyclo[3.1.1]-
heptane-2-ol (HL3), (1R,2R,3R,5R)-3-((S)-α-methyl-
benzylamino)-2,6,6-trimethylbicyclo[3.1.1]-
heptane-2-ol (HL4) -were studied as optically ac-
tive ligands.
Keywords: Palladium Complexes; Cyclopalladation;
Chiral Imine; Amine
1. INTRODUCTION
Chiral palladium complexes of various types are
widely used in modern asymmetric synthesis, the goal of
which is to obtain enantiopure compounds. Cyclopal-
ladated complexes (CPCs) form a special group of com-
pounds with a σ-connection palladium-carbon [1]. These
complexes show reasonably high activity and thermal
stability. Chiral CPCs are very successfully used in
asymmetric synthesis, both as the original matrix [2-7]
and as catalysts [8-12]. They have been used in NMR
studies as shifting reagents [13-15] and as effective res-
olution agents [16-18]. This is especially significant for
obtaining enantiopure phosphines, which are efficient
ligands for asymmetric catalysis of transition metal
complexes. Currently, the CPCs are received with dif-
ferent types of chirality [1]. The compounds of a variety
of classes have been tested for their ability to become
ligands for CPCs. However, the synthetic accessibility of
chiral ligands remains an important problem.
2. EXPERIMENTAL
2.1. General
The 1H and 13C NMR spectra were recorded with a
Bruker Avance-300 spectrometer operating at the fre-
quencies 300 and 75 MHz for 1H and 13C nucleus, re-
spectively. The measurements were carried out at ambi-
ent temperature in CDCl3. Chloroform signals were used
as an internal standard (δН 7.27 ppm, δС 77.00 ppm). The
assignment of signals was carried out using 13C NMR
spectra recorded in the mode of J-modulation, and ac-
cording to two-dimensional correlation spectra of 1H{1H}
(COSY) and 1H{ 13C} (HSQC) and NOE experiments.
IR spectra were measured in a thin layer or in KBr pel-
lets on a device "IR Prestige 21" made by Shimadzu.
Optical rotations were measured on a Kruss P3002RS
polarimeter (Germany) with a 10 cm cell and were re-
ported as follows:

tC
D

 (concentration in g/10 mL,
solvent). Elemental analyses were performed using an
automatic analyzer ЕА 1110 CHNS-O.
All reactions were monitored on a thin layer chroma-
tography (TLC) using Merck silica gel (70-230 mesh)
and benzene acetone mixtures as eluents; the TLC spots
were visualized with J2 and KMnO4/H2SO 4. Column
chromatography was carried out using Merck silica gel
(70-230 mesh) and benzene acetone mixtures as eluents.
2.2. Solvents and Starting Reagents
Benzene was dried with CaCl2, refluxed with Na,
and then distilled from Na. Methanol was distilled
from MeONa. Hexane was distilled from Na. Palla-
dium chloride was used without additional purifica-
tion. (SC)-α-Methylbenzylamine of 99% ee was pur-
chased from Merck and used without purification.

O. A. Zalevskaya et al. / Natural Science 2 (2010) 1189-1194 1190
Imines HL1, HL3 and amines HL2, HL4 were pre-
pared by a reported method [19].
2.3. Di-µ-Chlorobis{(1R,2R,5R)-3-
(Benzylimino)-2,6,6-Trimethylbicyclo
[3.1.1]Heptane-2-ol-C,N}
Dipalladium(II), 1
A suspension of palladium chloride (II) (0.09 g, 0.5
mmol) and lithium chloride (0.04 g, 1.0 mmol) in
methanol (5 ml) was boiled in a water bath with a
reflux condenser for one hour. The resulting solution
of lithium tetrachloropalladate (dark-red color) added
to a solution of imine HL1 (0.13 g, 0.5 mmol) and so-
dium acetate (0.04 g, 0.5 mmol) in methanol (5 ml). Af-
ter stirring at room temperature for 1 hour the solvent
was removed from the reaction mixture, the complex 1
was extracted with benzene (3×20 mL). The crude
product was purified using column chromatography on
silica gel with benzene and benzene/acetone 10:1 mix-
ture as eluents. After precipitation from benzene by
hexane and drying in vacuum, complex 1 was obtained
in the yield of 40% (0.080 g, mmol) as a yellow amor-
phous powder: mp (dec) 166-167 °C, Rf 0.71 (5:1 ben-
zene/acetone),

25
D

= -415.9 (c 0.06, CHCl3).
IR, ν, cm-1: 3441 (OH), 1618 (C = N). 1H NMR
(CDCl3, δ / ppm., J / Hz): 0.73 (s, 3H, H9, Me), 0.98 (d,
1H, 7-Hα, J 7α,7β 11.0), 1.10 (s, 3H, H8, Me), 2.12 (ddd,
1H, 7-Нβ, J 2.0, J 5.8, J 7β,7α 11.0), 2.26 (d, 1H, H4α, J
4α,4β 18,3), 2.56 (dd, 1H, H4β, J 4.1, J 4β,4α 18.3), 2.94 (s,
3H, H10, Me), 4.22 (d, 1H, H11α, J 11α,11β 14.5), 4.47 (d,
1H, H11β, J 11β,11α 14.5), 7.15-7.45 m (4H, arom.). 13C
NMR (CDCl3, δ, ppm): 23.27 (C9), 26.88 (C8), 28.18
(C7), 32.10 (C10), 32.94 (C 4), 39.17 (C 5), 40.13 (C6),
51.41 (C1), 55.06 (C11), 92.46 (C2), 127.27 (C18), 127.55
(C17), 128.33 (C16), 128.57 (C14), 128.85 (C15), 135.24
(C13), 197.63 (C3).
2.4 Dichloro{(1R,2R,5R)-3-
(Benzylimino)-2,6,6-Trimethylbicyclo
[3.1.1]Heptane-2-ol-
N,N}Palladium(II), 2
A suspension of palladium chloride(II) (0.04 g, 0.2
mmol) and lithium chloride (0.02 g, 0.4 mmol) in
methanol (5 ml) was boiled in a water bath with a
reflux condenser for one hour. The resulting solution
of lithium tetrachloropalladate (dark-red) color was
added to a solution of imine HL1 (0.1 g, 0.4 mmol) in
methanol (2 ml). After stirring at room temperature
for 1 h the solvent was removed from the reaction
mixture, the coordinated complex 2 was extracted
with benzene (3×20 mL). The crude product was pu-
rified using column chromatography on silica gel with
benzene and benzene/acetone 10:1 mixture as eluents.
After precipitation from benzene by hexane and dry-
ing in vacuum, complex 2 was obtained in the yield of
50% (0.070 g, mmol) as a yellow amorphous powder:
mp (dec) 153-154 °C, Rf 0.8 (5:1 benzene/acetone),

25
D

= +113.5 (c 0.07, CHCl3).
IR, ν, cm-1: 3410 (OH), 1612 (C = N). 1H NMR
(CDCl3, δ / ppm., J / Hz): 0.75 (s, 3H, H9, Me), 1.22 (s,
3H, H8, Me), 1.5 (d, 1H, H7α, J 7α,7β 9.0 ), 1.8 (m, 1H,
Н7β), 2.1 (m, 1H, H1), 2.2 (m, 2H, H4), 2.5 (m, 1H, H5),
2.8 (s, 3H, H10, Me), 5.1 (d, 1H, H11α, J 11α,11β 16.0), 5.9
(d, 1H, H11β, J 11β,11α 16.0), 7.4 (m, 5H, arom.). 13C NMR
(CDCl3, δ, ppm): 22.97 (C9), 26.71 (C8), 27.61 (C7),
31.06 (C10), 37.97 (C4), 38.13 (C5), 38.54 (C6), 52.87
(C1), 63.00 (C11), 76.61 (C2), 127.21 (C15), 127.55 (C16),
128.83 (C14), 133.81 (C13), 192.35 (C3).
2.5. Dichloro{(1S,2S,3S,5S)-3-
(Benzylamino)-2,6,6-
Trimethylbicyclo
[3.1.1]Heptane-2-ol-N,N} Palladium(II), 3
A suspension of palladium chloride(II) (0.04 g, 0.2
mmol) and lithium chloride (0.02 g, 0.4 mmol) in
methanol (5 ml) was boiled in a water bath with a
reflux condenser for one hour. The resulting solution
of lithium tetrachloropalladate (dark-red color) was
added to a solution of imine HL2 (0.12 g, 0.4 mmol)
in methanol (2 ml). After stirring at room temperature
for 1 h the solvent was removed from the reaction
mixture, the coordinated complex 3 was extracted
with benzene (3×20 mL).The crude product was puri-
fied using column chromatography on silica gel with
benzene and benzene/acetone 10:1 mixture as eluents.
After precipitation from benzene by hexane and dry-
ing in vacuum, complex 3 was obtained in the yield of
60% (0.085 g, mmol) as a yellow amorphous powder:
mp (dec) 167-168 °C, Rf 0.85 (5:1 benzene/acetone),

25
D

= -62.6 (c 0.09, CHCl3).
IR, ν, cm-1: 3479 (OH), 3253 (NH). 1H NMR (CDCl3,
δ / ppm., J / Hz): 0.75 (s, 3H, H9,Me), 1.24 (s, 3H, H8,
Me), 1.43 (s, 3H, H10, Me), 1.46 (d, 1H, H7α, J 7α,7β 11.0),
1.73-1.81 (m, 2H, H1, H5), 1.88 (dd, 1H, H4α, J 4α,3 10.0,
J 4α,4β 14.1), 2.10 ddd (1H, H7β, J 5.7, J 6.1, J 7β,7α 11.0),
2.61 (ddd, 1H, H4β, J 4.9, J 4β,3 9.8, J 4β,4α 14.1), 3.08
(dd, 1H, H3, J 3,4β 9.8, J 3,4α 10.0), 4.04 m (2H, H (11)),
7.33 (d, 1H, H16, J 16,15 7.0), 7.40 (dd, 2H, H15, J 15,16 7.0 ,
J 15,14 7.6), 7.50 (d, 2H, H14, J 14,15 7.6). 13C NMR
(CDCl3, δ / ppm.): 23.22 (C9), 23.39 (C10), 24.05 (C7),
27.54 (C8), 32.14 (C4), 39.48 (C6), 40.58 (C5), 57.13 (C1),
57.55 (C11), 65.18 (C3), 76.60 (C2 ), 127.74 (C16), 128.38
(C15), 129.90 (C14), 135.53 (C13).

O. A. Zalevskaya et al. / Natural Science 2 (2010) 1189-1194 1191
2.6. Di-µ-Chlorobis{(1R,2R,5R)-3-((1S)-
α-Methylbenzylimino)-2,6,6-
Trimethylbicyclo[3.1.1]
Heptane-2-ol-C,N}Dipalladium(II), 4
Synthesis is carried out similarly to that described for
(1). Dimer 4 as a yellow amorphous powder, yield
50% (0.103 g, mmol), mp (dec) 145-146 °C, Rf 0.4
(5:1 benzene/acetone),

25
D

= -32.0 (c 0.08, ace-
ton).
IR, ν, cm-1: 3337 (OH), 1631 (C = N). 1H NMR
(CDCl3, δ / ppm., J / Hz): 0.99 (s, 3H, H9, Me), 1.29
(d, 3H, H12, Me, J 12,11 6.8), 1.39 (s, 3H, H8, Me),
1.91 (d, 1H, H7α, J 7α,7β 11.8), 1.95 (s, 3H, H10,
Me), 2.12 (m, 1H, H5, J 5,1 5.5 ), 2.27 (m, 1H, H1, J
1,5 5.5, J 5.5), 2.59 (m, 2H, H4α, H7β), J 3.9, J 4β,4α
18.3 ), 2.73 (dd, 1H, H4β, J 3.9, J 4β,4α 18.3 ), 4.05
(sq, 1H, H11, J 11,12 6.8), 6.57 (d, 1H, H18, J 18,17
7.6), 6.84 (dd, 1H, H17, J 17,18 7.6, J 17,16 8.0), 7.04
(dd, 1H, H16, J 16,17 8.0, J 16,15 8.0), 7.44 (d, 1H,
H15, J 15,16 8.0). 13C NMR (CDCl3, δ, ppm): 22.43
(C12), 23.18 (C9), 27.23 (C8), 27.90 (C10), 28.87 (C7),
33.90 (C4), 38.41 (C5), 40.52 (C6), 51.78 (C1), 67.00
(C11), 88.64 (C2) ), 122.33 (C18), 124.61 (C16), 124.75
(C17), 135.51 (C15), 138.84 (C13), 156.52 (C14), 185.10
(C3).
2.7. Di-µ-Chlorobis{(1R,2R,3R,5R)-3-
((S)-α-Methylbenzylamino)-2,6,6-
Trimethylbicyclo[3.1.1]
Heptane-2-ol-C,N}Dipalladium(II), 5
Synthesis is carried out similarly to that described
for (1). Dimer 5 as a yellow amorphous powder, yield
55% (0.114 g, mmol), mp (dec) 169-170 °C, Rf 0.3
(5:1 benzene/acetone),

25
D

= +19.7 (c 0.04,
CHCl3).
IR, ν, cm-1: 3421 (OH), 3217 (NH). 1H NMR
(CDCl3, δ / ppm., J / Hz): 0.96 (s, 3H, H9, Me), 1.29
(s, 3H, H8, Me), 1.56 (s, 3H, H10, Me), 1.66 (dd, 1H,
H4α, J 4α,3 11.3, J 4α,4β 13.9), 1.75 (d, 1H, H7α, J
7α,7β 10.9), 1.81 (d, 3H, H12, J 12,11 6.4), 1.95 (m,
1H, H1, J 1,7β 5.6), 2.01 (m, 1H, H5), 2.17 (dd, 1H,
H7β, J 7β,1 5.6, J 7β,7α 10.9), 2.46 (s, OH), 2.56 (ddd,
1H, H4β, J 5.6, J 4β,3 9.0, J 4β,4α 13.9), 4.14 (sq, 1H,
H11, J 11,12 6.4), 4.18 (dd, 1H, H3, J 3,4β 9.0, J 3,4α
11.3), 4.40 (s, NH)), 6.74 (dd, 1H, H18, J 18,16 1.3, J
18,17 7.2), 6.87 (ddd, 1H, H16, J 16,181.3, J 16,17
7.3, J 16,15 8.5), 6.96 (dd, 1H, H17, J 17,18 7.2, J
17,16 7.3), 7.24 (d, 1H, H15, J 15,16 8.5). 13C NMR
(CDCl3, δ, ppm): 22.89 (C9), 24.02 (C7), 24.24 (C10),
25.88 (C12), 28.05 (C8), 28.48 (C4), 40.16 (C6), 40.62
(C5), 55.47 (C1), 64.39 (C11), 67.51 (C3), 77.55 (C2),
119.89 (C18), 124.79 (C17), 125.10 (C16), 134.01 (C15),
141.92 (C13), 156.95 (C14).
3. RESULTS AND DISCUSSION
Earlier, we reported on the synthesis of chiral imines
and amines on the basis of 2α-hydroxypinan-3-one [19].
These ligands, containing in its composition ben-
zylamine fragment, are of interest from the standpoint of
the possibility of obtaining ortho-palladated complexes.
In the present work we investigated the interaction of the
obtained ligands HL1, HL2, HL3, HL4 with lithium tet-
rachloropalladate (Li2PdCl4) in the method of Cope [20].
Reaction of cyclopalladation is accompanied by the re-
lease of hydrogen chloride. An insertion of an additional
base is necessary for the neutralization of the hydrogen
chloride.
The structure of obtained complex compounds is con-
firmed by NMR, IR spectroscopy and elemental analysis
data, last are given in Table 1 .
On the basis of imine HL1 we managed to get binu-
clear palladacycle 1 with the yield of 40% in the pres-
ence of sodium acetate as base at a molar ratio of re-
agents 1:1. In the absence of the base at a molar ratio of
reagents 1:2 mononuclear coordinated complex 2 was
obtained in 50% yield (Scheme 1). Complex compounds
1 and 2 were isolated from the reaction mixture by col-
umn chromatography and further purified by crystalliza-
tion from a mixture of benzene-hexane.
The signals of protons of methylene group -CH2N =
were observed in the 1H NMR spectrum of compound
1 in the form of two doublets with geminal constant of
14.5 Hz (two-proton singlet was observed in the spec-
trum of the initial ligand), which confirms the formation
of the cycle. The change of the multiplicity and the inte-
grated intensity of signals of protons of benzene ring
corresponds to the ortho-disubstituted ring. The preser-
vation of the multiplicity and the integral intensity of
proton signals of the monosubstituted benzene ring in
the 1H NMR spectrum of compound 2 excludes or-
tho-palladation.
In contrast to the corresponding imine HL1 amine
HL2 forms only mononuclear coordinated complex 3
even in the presence of a base (AcONa) (Scheme 2).
This result can be explained by the fact that the secon-
dary amino group exhibits stronger electron donor prop-
erties than the imine, and reduces the electrophilic activ-
ity of palladium, preventing the ortho-palladation.
The interaction of amine HL2 with Li2PdCl4 may form
a mixture of diastereomeric complexes in which the con-
figuration of tetragonal nitrogen atom consolidates with
the metal and the nitrogen becomes an additional center
of chirality. There is only one set of signals in the 1H
NMR spectrum of compound 3 that indicates the forma-

O. A. Zalevskaya et al. / Natural Science 2 (2010) 1189-1194 1192
Table 1. The analytical data for the complexes.
№. Complex Color Analytical Data
[Empirical formula] % Found (Calculated)
(Formula weight) C H N
1 C34H44N2O2Pd2Cl2 yellow 51.8 5.67 3.2
(795.75) (51.3) (5.53) (3.5)
2 C34H46N2O2PdCl2 yellow 57.2 6.62 3.9
(691.37) (59.1) (6.65) (4.0)
3 C34H50N2O2PdCl2 yellow 58.7 7.31 3.90
(695.36) (58.7) (7.20) (4.03)
4 C36H48N2O2Pd2Cl2 yellow 52.6 5.93 3.3
(823.77) (52.4) (5.93) (3.3)
5 C36H52N2O2Pd2Cl2 yellow 52.4 6.21 3.21
(827.76) (52.2) (6.28) (3.30)
11 17
14
16
15
13
2 1
HL1
Li2PdCl4
OH
N
HO
N
Pd Cl
Cl
Li2PdCl4
AcONa
HO
N
Pd Cl
OH
N
Pd
Cl
OH
N
123
4
5
6
7
8
9
10
12
Scheme 1
MeOH
+ Li2PdCl4
OH
NH
OH
NH
Pd
HO
HN
Cl
Cl
HL2
3
Scheme 2
tion of one of the possible diastereomers. Multiplicity
and integral intensity of proton signals corresponds to
the monosubstituted benzene ring.
The interaction of imine HL3 and amine HL4, con-
taining α-methylbenzylamine fragment with lithium tet-
rachloropalladate was investigated under the specified
above conditions. It was found that the imine HL3 ex-
posed cyclopalladation even in the absence of a base.
Binuclear palladacycle 4 was obtained in the presence of
sodium acetate at a molar ratio of reagents 1:1 and in the
absence of sodium acetate at a molar ratio of reagents
1:2 (Scheme 3). This result is quite understandable giv-
en the fact that the second molecule of imine can serve
as a base, binding hydrogen chloride, thereby stimulat-
ing cyclometallation.
Unlike amine HL2, that forms only the coordinated
complex in the investigated conditions, amine HL4, that
contains a methyl group in α-position, reacts with lith-
ium tetrachloropalladate in the presence of sodium ace-
tate at a molar ratio of reagents 1:1 to form a binuclear
palladacycle 5 with yield 55% (Scheme 4). A mixture of
two complex compounds - coordinated and palladacycle
are formed in the absence of sodium acetate at a molar
ratio of reagents 1:2, which was is confirmed by 1H

O. A. Zalevskaya et al. / Natural Science 2 (2010) 1189-1194 1193
18
17
14 16
15
13
12
4
OH
N
H
Pd
HO
N
H
Pd
Cl
Cl
HL3
OH
N
H
Li2PdCl4
Scheme 3
AcONa
Li2PdCl4
HL4
5
OH
NH
Pd
Cl Cl
Pd
HO
HN
OH
NH Ph
H
H
H
Scheme 4
NMR and 13C spectroscopy.
The formation of ortho-palladated complexes 4 and 5
is confirmed by NMR spectra: there are four nonequiva-
lent signals of aromatic protons in the 1H spectra with a
particular splitting (two doublets and two doublets of
doublets) and four aromatic methine groups in the 13C
spectra. All set of signals of terpene fragments remains
in the spectra. A slight shift is reported (compared to the
ligands) for nucleis located close to palladium. One set
of signals in the spectra of the complexes 4 and 5 is ob-
served which indicates the symmetry of the complexes.
The ease of the cyclopalladation of the α-methylbenzi-
lamine derivatives HL3 and HL4 once again underlines
the role of spatial factors in reactions of the metallocy-
cles formation.
4. CONCLUSIONS
Mononuclear coordination complexes - (HL1)2PdCl2
(2), (HL2)2 PdCl2 (3) and palladacycle dimers
PdL1Cl (1), PdL3Cl (4), PdL4Cl (5) have been iso-
lated separately, the structure of which was studied
and confirmed by spectral methods and by elemental
analysis
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