5,6-Membered CNN palladium pincer complexes of 3-benzyl-8-dimethylamino -3-azabicyclo[3.2.1]octane and 3-benzyl-9-dimethylamino-3-azabicyclo[3.3.1]nonane

Article abstract of DOI:10.1016/j.jorganchem.2019.02.017

The unsymmetrical CNN pincer ligand precursors 4 and 7b based on the structures of bicyclo[3.2.l]octane and bicyclo[3.3.l]nonane have been synthesized. The corresponding palladium pincer 5,6-membered complexes 5 and 9 were prepared by direct cyclopalladat

Full text of DOI:10.1016/j.jorganchem.2019.02.017

Accepted Manuscript
5,6-Membered CNN palladium pincer complexes of 3-benzyl-8-dimethylamino -3-
azabicyclo[3.2.1]octane and 3-benzyl-9-dimethylamino-3-azabicyclo[3.3.1]nonane
Ludmila A. Bulygina, Natalya S. Khrushcheva, Konstantin A. Lyssenko, Aleksander S.
Peregudov
PII:
S0022-328X(19)30070-1
DOI:
https://doi.org/10.1016/j.jorganchem.2019.02.017
JOM 20719
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 2 January 2019
Revised Date: 31 January 2019
Accepted Date: 21 February 2019
Please cite this article as: L.A. Bulygina, N.S. Khrushcheva, K.A. Lyssenko, A.S. Peregudov, 5,6-
Membered CNN palladium pincer complexes of 3-benzyl-8-dimethylamino -3-azabicyclo[3.2.1]octane
and 3-benzyl-9-dimethylamino-3-azabicyclo[3.3.1]nonane, Journal of Organometallic Chemistry (2019),
doi: https://doi.org/10.1016/j.jorganchem.2019.02.017.
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ACCEPTED MANUSCRIPT
5,6-Membered CNN palladium pincer complexes of 3-benzyl-8-
dimethylamino -3-azabicyclo[3.2.1]octane and 3-benzyl-9-dimethylamino-3-
azabicyclo[3.3.1]nonane.
Ludmila A. Bulygina a, Natalya S. Khrushcheva a, *, Konstantin A. Lyssenko a, b
Aleksander S. Peregudov a
,
a A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of
Sciences, 28 Vavilov St., 119991 Moscow, Russian Federation
b Plekhanov Russian University of Economics, Stremyanny per. 36, Moscow,
117997, Russian Federation
* Corresponding author
E-mail address: stemos@ineos.ac.ru (N.S.Khrushcheva)
Abstract
The unsymmetrical CNN pincer ligand precursors 4 and 7b based on the
structures of bicyclo[3.2.l]octane and bicyclo[3.3.l]nonane have been
synthesized. The corresponding palladium pincer 5,6-membered complexes 5
and 9 were prepared by direct cyclopalladation of ligand precursors with
Li2PdCl4 in MeOH. The molecular structure of the palladacycles was determined
1
13
by H and C NMR and confirmed by X-ray diffraction analysis. The obtained
complexes 5 and 9 exhibited good catalytic activity in the Suzuki reactions of
aryl bromides with phenylboronic acid.
Keywords: Unsymmetrical CNN pincer palladium complexes; Bicyclic ligand
precursors; Catalytic activity; Suzuki reaction

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1. Introduction
Palladium pincer complexes represent the class of palladacycles that is
containing at least one σ-metal-carbon bond and two intramolecular coordinating
linkages with heteroatoms. They are the point of active studies due to their high
stability, possibility of structural modification and exhibited catalytic activity.
For a long time only symmetric palladium pincer complexes based on aryl
groups with equal side arms forming the combination of two identical typically
5-, less often 6-membered fused palladacycles were known. At the present time
growing attention is focused on the development of new unsymmetrical pincer
palladium complexes with two unequivalent side arms (YCY`) or with one side
arm, but containing two heteroatoms, in places suitable for metal complexation
(CYY`). Structural modifications of the lateral coordination fragments affect the
electronic properties of the palladium center and allow variation of chemical and
catalytic features of the complex for the required use. Several reviews dedicated
to the synthesis, properties and catalytic applications of symmetric and
unsymmetrical palladium pincer complexes have been published for today [1-8].
Among them is a rather small group of CNN unsymmetrical pincer complexes in
which the σ-bond Pd-C is stabilized by coordination with two nitrogen atoms [9-
18]. Most of them have proven to be active catalysts and (pre)catalysts. It should
be noted that in all these complexes at least one N atom is sp2 hybridized. In our
previous works we have described the synthesis of the novel and very stable
CNN pincer cyclopalladates based on 3,7- diazabicyclo[3.3.1]nonane (bispidine)
structure with asymmetrically substituted N atoms, which are both sp3
hybridized [19, 20].

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The bicyclo[3.3.l]nonane derivatives can be described as the equilibrium
between three main conformations - chair-chair, chair-boat and boat-boat, where
in the most cases the twin-chair or boat-chair conformations are favored [21].
The bispidine derivatives with chair-chair preferential conformation look like the
perfect ligand precursors to form metallocomplexes (Fig.1, 1). Prior to the
beginning of our research work, only bispidines with symmetrically substituted
nitrogen atoms were used to obtain complexes with Pd and they formed
exclusively NN coordination complexes (Fig.1, 2) [22-25].
N
N
N
N
N
N
N
N
Pd
1
1
Pd
Pd
R
R
R
R
X
X
Cl
Cl
1
Fe
1 R=R
1
2 R=R
2a
2b
1
1a R=Me R =Bn
1
1b R=Me R =FcCH
2
Fig.1. The bispidine ligand precursors 1, 1a, and 1b, NN coordination Pd
complex 2 and unsymmetrical CNN pincer palladium complexes 2a and 2b.
However, when we used the bispidines with unsymmetrically substituted
nitrogen atoms (Fig.1, 1a, 1b) for complexation with Pd only CNN pincer
cyclopalladates were obtained in a good yield (Fig.1, 2a, 2b) [19, 20]. But when
we took as a ligand precursor 3-benzyl-3-azabicyclo[3.3.1]nonane containing
only one nitrogen atom rapid formation of palladium black was observed and we
have failed to isolate any stable CN or NN palladium complexes. It can be
assumed that for the compounds with the structure of 3-azabicyclo[3.3.l]nonane
and 3-azabicyclo[3.2.l]octane the pincer complexes will be more stable. In order
to form a pincer complex, it is necessary to insert a second heteroatom into the

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structure of bicyclic molecule. This requirement can be satisfied by introducing
the amino group at a suitable place - at C9 and C8 of bicyclic framework
respectively. In this case, the boat-chair conformation of the bicyclic ligand
precursors will be convenient for the complexation with the metal and the
formation of 5,6-membered CNN pincer palladacycles can be expected.
In this paper we report on the synthesis of two new unsymmetrical CNN pincer
ligand precursors based on the bicyclic structures of bicyclo[3.3.l]nonane and
bicyclo[3.2.l]octane and its corresponding palladium 5,6-membered complexes
where both N are sp3 hybridized. The obtained Pd complexes were examined as
catalysts in the cross-coupling reactions of aryl halides with phenylboronic acid.
2. Result and discussion
2.1. Synthesis and characterization
The unsymmetrical CNN pincer ligand precursors 4 and 7b was prepared as
shown in Schemes 1 and 2.
O
O
(MeOCH2)2NBn
Me3SiCl, MeCN
Me2NH, STAB
AcOH, CH2Cl2
NBn
3
15
16
10
Cl
NMe2
H
14
13
17
10
N
9
Pd
Li2PdCl4
8
12
NaOAc 3H2O
MeOH
1
N
3
2
7
11
NBn
5
4
5
6
4
Scheme 1. Synthesis of the ligand precursor 4 and unsymmetrical CNN pincer
palladium complex 5.

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Scheme 2. Synthesis of the ligand precursor 7b and unsymmetrical CNN pincer
palladium complex 9.
In the published syntheses of bicyclic ketones 3-benzyl-3-azabicyclo [3.2.1]
octan-9-one (3) [26, 27] and 3-benzyl-3-azabicyclo [3.3.1] nonan-9-one (6) [26-
28] the best yields of the target products are obtained in a double Mannich
reaction
from
cyclopentanone
or
cyclohexanone
with
N,
N-
bis(methoxymethyl)benzylamine in the presence of trimethylchlorosilane [27].
Using this technique afforded a 15% yield of ketone 3 and a 64% yield of ketone
6 (Schemes 1 and 2). At the next stage, the dimethylamino groups were

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introduced in the bicyclic molecules by the reaction of reductive amination of
ketones 3 and 6 with dimethylamine and sodium triacetoxyborohydride. It is
known that the addition or reduction reactions on the keto group in azabicyclic
ketones take place with the possible formation of a mixture of diastereomers, the
composition of which is controlled by steric effects and depends on the structure
of the bicycle. Only the syn diastereomer is formed during the addition of
MeMgBr to 3-methyl-3-azabicyclo [3.2.1] octan-8-one containing a saturated
five-membered cycle [29, 30]. When this compound is reduced by different
methods, the syn isomer is also obtained mainly, and the anti compound is
present only as a small admixture [31]. However, both the addition of
organomagnesium and the reduction of the keto group for 3-methyl-3-azabicyclo
[3.3.1] nonan-9-one lead to the formation of a mixture of the syn and the anti
diastereomers, and the anti-compound is predominant [29-32]. As a result of the
reductive amination of ketones 3 and 6, we can also expect the formation of
different diastereomers. However, the complexation with metals for ligand
precursors with such a structure is possible only for their syn isomers.
The reductive amination of ketone 3 with dimethylamine and sodium
triacetoxyborohydride in the presence of AcOH afforded a 69% yield of 3-
benzyl-8-dimethylamino-3-azabicyclo[3.3.1]octane 4 (Scheme 1) as a single
isomer. By analogy with the literature data, we have assumed that it is the syn
isomer.
The reductive amination of ketone 6, conducted under the same conditions, gave
much more complicated results. In addition to the target 3-benzyl-9-
dimethylamino-3-azabicyclo[3.3.1]nonane 7, the product of the reduction of the
ketone group 3-benzyl-9-hydroxy-3-azabicyclo[3.3.1]nonane 8 was obtained in

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an appreciable amount. These compounds were separated by SiO2
chromatography. According to NMR data, both amine 7 and alcohol 8 turned out
to be mixtures of isomers with a significant predominance of one of them
(Scheme 2).
In the 1H and 13C NMR spectra of compounds 7 and 8, two sets of well-separated
signals corresponding to two diastereomers were presented.
For amine 7, the ratio of diastereomers was determined by the comparing of the
integral intensities of the methylene protons of the benzyl group of the two
1
1
isomers in the H NMR spectrum and was defined as 25: 100. In the H NMR
spectrum, a significant difference in the shielding of exo and endo protons
adjacent to the cyclic amino group was observed. For the main isomer, this
difference was 0.77 ppm, for the minor isomer, all four protons appeared as one
broadened signal (Table 1, entry1), which indicated the proximity of the
shielding of these protons. In the 13C NMR spectrum, a distinction in the
shielding of C at positions 2,4 and 6,8 for different isomers was observed. The
signal of С(2,4) of the minor isomer is shifted to a strong field relative to the
main isomer by 6.70 ppm. At the same time, the signal of С(6,8) of the minor
isomer is shifted towards the lower field by 7.69 ppm regarding the main isomer.
Thus, the difference in chemical shifts of the signals С(2,4) and С(6,8) for the
main isomer is 35.34 ppm, and for the minor isomer this value is 20.95 ppm
(Table 1, entry 4).
Table 1. The difference in the chemical shifts of the syn and the anti isomers of 7
and 8 in 1H and 13C NMR spectra.

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H
X
H
X
N R
R
N
anti
Minor isomer (syn), ppm
syn
Entry
X
R
Major isomer (anti), ppm
H2,4(a) H2,4(b)
∆
0
H2,4(a) H2,4(b)
∆
1
2
NMe2
OH
Bn
Bn
Me
2.60
2.60
2.60
2.67
2.99
2.97
2.22
2.29
0.77
0.68
0.67
∆
7
8
0.07
0.13
∆
3*
OH
2.47
2.60
2.87
2.20
A
C2,4
C6,8
C2,4
C6,8
4
5
NMe2
OH
Bn
Bn
Me
53.34
52.86
54.24
32.39
31.36
30.73
20.95
21.5
60.04
59.07
61.39
24.70
24.26
24.42
35.34
34.81
36.97
7
8
6*
OH
23.51
A
*From [33]
The ratio of diastereomers for compound 8 was determined by the comparing of
the integral intensities of the H9 protons of the bicyclic skeleton and the
1
methylene protons of the benzyl group of the two isomers in the H NMR
spectrum and turned up to be 30: 100. For this compound, the same differences
in the chemical shifts of exo and endo protons adjacent to N3, as in the case of
the amine 7 have been observed. For the main isomer, it is 0.68 ppm, which is
significantly higher than the similar value (0.07 ppm) for the minor isomer
(Table 1, entry 2).
In the 13C NMR spectrum, the C(2,4) signal of the minor isomer is shifted upfield
by 6.21 ppm and the signal C(6,8) of the minor isomer is shifted downfield by
7.10 relative to the main isomer. The difference in the chemical shifts of the
C(2,4) and C(6,8) signals for the main isomer is 34.81 ppm, whereas for the
minor isomer this value is 21.50 ppm. (Table 1 entry 5).

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Similar patterns in changes in the chemical shifts of H and C signals of the two
isomers were found for 3-methyl-9-hydroxy-3-azabicyclo [3.3.1] nonane (A),
which was obtained by the reduction of ketone with sodium borohydride [33]
(Table 1, entry 3 and 6). In this case, the main product have been defined as the
anti isomer, and the syn isomer acts as a minor product. This allows us to assume
that as a result of the reductive amination of ketone 6, a mixture of diastereomers
of alcohol 8 and amine 7 was obtained with a significant predominance of the
anti isomer in both compounds.
Direct cyclopalladiation of ligand precursor 4 was carried out by the reaction
with Li2PdCl4 in the presence of stoichiometric amounts of sodium acetate
monohydrate in methanol at room temperature. The interaction resulted in the
isolation of unsymmetrical CNN pincer palladium complex 5 as the single
product in a yield of 79%. When this reaction was carried out without sodium
acetate, i.e., under conditions favorable for the formation of NN coordination
complex, the only product was the same palladacycle 5 (59%).
Despite the fact that, according to our assumption, the main isomer in compound
7 is an anti isomer 7a which is not able to form CNN complexes with metals, we
hoped to obtain a cyclopalladation product from a mixture of isomers and isolate
it due to the large difference in solubility of the ligand precursore and the
complex. We managed to get the pincer complex 9 by direct cyclopalladation of
the amine 7 with Li2PdCl4 in the presence of NaOAc x 3H2O in methanol at
room temperature in a yield of 16%. Such a low yield testifies in favor of our
assumption that the syn isomer 7b is a minor in the ligand precursor 7.
Considering content of 7b in the mixture of isomers, the yield of complex 9 was
76%.

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1
In the H NMR spectra of CNN palladacycles, a decrease of the intensity of the
signals of aromatic protons from 5H in the case of ligand precursors 4 and 7 to
4H for complexes 5 and 9 is observed, which confirms the occurrence of
13
metalation of the phenyl ring. In the C NMR spectra of palladium complexes
the resonance of the new quaternary aromatic carbon C-Pd appeared at 144.55
ppm for 5 and 144.12 ppm for 9 and the resonance of another aromatic
quaternary carbon C-C shifted downfield in comparison with that for starting
ligand precursors. The chemical shift values of aromatic quaternary carbons of
both complexes are in good agreement with each other, as well as with the
previously obtained data for complex 2a [18].
The NMR spectra data for the obtained CNN palladium complexes agree well
with the microanalysis, IR and mass spectrometry data.
2.2. Crystal structure
The molecular structures of complexes 5 and 9 were confirmed by the X-ray
analysis (Figures 2 and 3). Single crystals of 5 and 9 were grown by slow
evaporation of CH2Cl2 solution. In both complexes the five-membered Pd-cycle
is characterized by the envelope conformation with the deviation of C(11) or
C(12) atom by 0.370(2) and 0.477(2) Å in 5 and 9, correspondingly. The
principal geometric parameters in complexes are almost identical. It should be
noted that in both isomers the palladium atom is characterized by distortion of
planar square coordination that can be illustrated by the values of dihedral angle
between PdNN and PdCl(1)C planes that is 7.2°.

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Fig. 2. The general view of 5 in representation of atoms by thermal ellipsoids
(p=50%). The selected bond lengths(Å): Pd(1)-Cl(1) 2.3197(3), Pd(1)-N(3)
2.064(1), Pd(1)-N(9) 2.176(1), Pd(1)-C(17) 1.986(1); bond angles (°): C(17)-
Pd(1)-N(3) 84.82(5), C(17)-Pd(1)-N(9) 169.56(5), N(3)-Pd(1)-N(9) 87.74(4),
C(17)-Pd(1)-Cl(1) 94.34(4), N(3)-Pd(1)-Cl(1) 178.83(3), N(9)-Pd(1)-Cl(1)
93.19(3)
Fig. 3. The general view of 9 in representation of atoms by thermal ellipsoids
(p=50%). The selected bond lengths(Å): Pd(1)-Cl(1) 2.3220(4), Pd(1)-N(3)
2.070(1), Pd(1)-N(10) 2.179(1), Pd(1)-C(18) 1.985(2); bond angles (°): C(17)-
Pd(1)-N(3) 84.40(6), C(17)-Pd(1)-N(9) 169.51(6), N(3)-Pd(1)-N(9) 87.99(5),

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C(17)-Pd(1)-Cl(1) 94.41(5), N(3)-Pd(1)-Cl(1) 178.80(4), N(9)-Pd(1)-Cl(1)
93.16(4)
2.3. Catalytic studies
The palladium pincer complexes 5 and 9 were tested as precatalysts in several
Suzuki cross-coupling reactions. All experiments were conducted under the
conditions similar to those we used earlier in studies of the catalytic activity of
other bicyclic cyclopalladates 2a and 2b (Fig.1) [19, 20]. This allowed us to
compare the results obtained in this and previous works.
The Suzuki cross-coupling reactions were conducted with the phenylboronic acid
and three aryl bromides in MeOH/H2O for 5 h at 55° C with K2CO3 as a base. In
our previous studies, we used a catalyst loading of 0.5 mol%. In this work, we
decided first of all to check the possibility of reducing the amount of catalyst.
When using 0.5 mol% of catalysts 5 or 9 in the reaction of bromoanisole with
phenylboronic acid, the yield of 4-methoxybiphenyl turned out to be close to
quantitative (Table 2, entries 1 and 6). A decrease in catalyst loading in the same
reaction to 0.1 mol% also leads to a high yield of the cross-coupling product
(Table 2, entries 2 and 7). However, with a subsequent decrease in the loading of
catalysts 5 or 9 to 0.05 mol%, the yield of the product drops sharply (Table 2,
entries 3 and 8). Further experiments were carried out using 0.1 mol% of
catalysts. When interacting with phenylboronic acid under the described
conditions, both 4-bromotoluene (Table 2, entries 4 and 5) and 4-
bromoacetophenone (Table 2, entries 9 and 10) form the corresponding
biphenyls in high yields. Very similar results were obtained during the study of
the interaction of 4-bromoanisole with phenylboronic acid under the same
conditions using other CNN bicyclic pincer cyclopalladates 2a and 2b [19, 20].

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In this case, it seems that the structure of the bicyclic ligand does not have a
noticeable effect on the catalytic activity of the complexes in cross-coupling
reactions. However, CNN pincer Pd complexes 5 and 9 with two sp3 N seem to
be slightly more active catalysts for this reaction than the unsymmetric NCN
pincer cyclopalladates with two sp2 N presented in [34], considering the higher
yield of the product in milder conditions in our case.
In some cross-coupling experiments the formation of small amounts of palladium
black was observed. These inactive conglomerates are formed from active Pd0
nanoparticles which are likely to be true catalists in the reaction. Such formation
is typical for the processes involving phosphine-free cyclopalladated catalytic
systems [35].
Table 2. Catalytic cross-coupling Suzuki reaction a.
Entry
R
MeO
MeO
MeO
Me
Cat
5
Mol %
0.5
Product
11a
11a
11a
11b
11c
Yield b (%)
1
2
99
89
13
91
98
99
94
9
0.1
5
3
0.05
0.1
5
4
5
5
MeC=O
MeO
MeO
MeO
Me
0.1
5
6
0.5
9
11a
11a
11a
11b
11c
7
0.1
9
8
0.05
0.1
9
9
95
95
9
10
MeC=O
0.1
9

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a Reaction conditions: aryl bromide (1 mmol), PhB(OH)2 (1.5 mmol), K2CO3
(2.0 mmol), cat. 5 or 9, MeOH (8 mL), H2O (4 ml), 55° C, 5 h.
b Isolated yields after column chromatography.
3. Conclusion.
We have synthesized two new unsymmetrical pincer ligand precursors 4 and 7b
based
on
the
structures
of
3-azabicyclo[3.2.l]octane
and
3-
azabicyclo[3.3.l]nonane. In the molecules of ligand precursors, the bicyclic
structure of which contains one N atom, the second heteroatom necessary for
obtaining stable pincer cyclopalladates was introduced as NMe2. The bicycle 4
was isolated as a single syn isomer. The only suitable for metal complexation syn
isomer 7b was obtained as a minor one in the mixture with its anti isomer. The
corresponding CNN pincer complexes 5 and 9 where the palladium is
coordinated with two sp3 N atoms, was prepared by direct cyclopalladation of the
ligand precursors. Both palladacycles 5 and 9 appeared to be the efficient catalyst
in some cross-coupling reactions of aryl bromides with phenylboronic acid.
4. Experimental
4.1. General
The NMR experiments were carried out using a Bruker AvanceTM 600
1
spectrometer operating at 600.22 MHz for H and 150.93 MHz for 13C and
1
Bruker AvanceTM 500 (500.13 and 125,77 MHz). H chemical shift data are
given in units δ relative TMS calibrated with CHCl3 at 7.26 ppm. The
multiplicity of a signal is indicated as follows: br, broad; s, singlet; d, doublet; m,
multiplet; dd, doublet of doublets. 13С сhemical shifts are given relative TMS

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calibrated to the solvent, CDCl3 at 77.26 ppm. The assignment of the signals in
13
1H and С NMR spectra has been performed by use of 2D COSY, HMQC and
HMBC techniques on the basis of the Bruker program standard library. 2D
inverse proton detected heteronuclear shift correlation spectra, gs-HMQC (1H-
13C) and gs-HMBC (1H-13C) were obtained using standard pulse sequence from
the Bruker library. The numbering of atoms used for NMR assignment is shown
in Schemes 1 and 2. EI mass spectra were taken on a FINNIGAN POLARIS Q
spectrometer at 70 eV and the temperature of the ion chamber 250° C. IR spectra
were recorded on a FT-IR Tensor 37 spectrometer (Bruker) in KBr pellets, thin
film or nujol. The assignment of absorption bands in the IR spectra was made
according to reference [36]. The TLC on Silufol UV-254 (Merck) was used to
follow the course of reactions.
4.2. 3-Benzyl-3-azabicyclo[3.2.1]octan-9-one (3)
To a solution of N,N-Bis(methoxymethyl)benzylamine (50 g, 0.26 mol) in MeCN
(200 ml) Me3SiCl (56 ml, 0.44 mol) was added dropwise. After 15 min stirring
cyclopentanone (23.2 ml, 0.26 mol) was added dropwise and the reaction mixture
was stirred for 24 h. Then the mixture was concentrated, diluted with water (100
ml), treated with concentrated HCl (100 ml) and refluxed with stirring for 1 hour.
After cooling, the mixture was basified with solid sodium hydroxide to pH 10,
extracted with AcOEt, washed with water and brine, dried over Na2SO4 and
evaporated. The residue was purified by SiO2 column chromatography with
AcOEt/petroleum ether (0/100 – 3/97) to afford 3 (8.4 g, 15 %) as a colorless oil,
slowly crystallizing in the refrigerator. M.p. 37-38 °C. Anal.: C, 78.08; H, 7.89;
N, 6.49 %. Calc. for C14H17NO: C, 78.10; H, 7.96; N, 6.51%. IR (KBr, ν, cm -1):

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1751 (C=O), 734, 699 (C6H5). EI-MS, m/z (RI, %): 215 [M]+ (51), 124 [M –
Bn]+ (42). 1H NMR (600 MHz, CDCl3) δ 7.42 – 7.30 (m, 4H, o- and m-Ph), 7.28
(t, J = 7.0 Hz, 1H, p-Ph ), 3.62 (s, 2H, CH2Ph), 3.00 (dd, J = 11.1, 3.2 Hz, 2H,
CH2N), 2.57 (d, J = 10.8 Hz, 2H, CH2N), 2.18 (br s, 2H, H1, H5), 2.09 (q, J =
4.9 Hz, 2H, H6, H7), 1.91 – 1.85 (m, 2H, H6, H7). 13C NMR (151 MHz, CDCl3)
δ 220.49 (C=O), 138.82 (ipso-Ph), 128.63 (o-Ph), 128.37 (m-Ph), 127.19 (p-Ph),
61.72 (CH2N), 60.20 (CH2Ph), 45.44 (C1, C5), 22.76 (C6, C7).
4.3. 3-Benzyl-3-azabicyclo[3.3.1]nonan-9-one (6)
To a solution of N,N-Bis(methoxymethyl)benzylamine (15 g, 0.077 mol) in
MeCN (60 ml) Me3SiCl (14.6 ml, 0.116 mol) was added dropwise. After 15 min
stirring cyclohexanone (8.0 ml, 0.077 mol) was added dropwise and the reaction
mixture was stirred for 24 h. Then the mixture was concentrated, diluted with
water (30 ml), treated with concentrated HCl (30 ml) and refluxed with stirring
for 1 hour. After cooling, the mixture was basified with solid sodium hydroxide
to pH 10, extracted with AcOEt, washed with water and brine, dried over Na2SO4
and evaporated. The residue was washed with hexane after SiO2 column
chromatography (AcOEt/petroleum ether: 0/100 – 5/95) to give 6 (11.1 g, 64 %)
as white crystals. M.p. 46-47 °C. Anal.: C, 78.63; H, 8.48; N, 6.27 %. Calc. for
-1
C15H19NO: C, 78.56; H, 8.35; N, 6.11%. IR (KBr, ν, cm ): 1728 (C=O), 734,
1
700 (C6H5). EI-MS, m/z (RI, %): 229 [M]+ (16), 138 [M – Bn]+ (16). H NMR
(600 MHz, CDCl3) δ 7.39 – 7.32 (m, 4H, o- and m-Ph), 7.33 – 7.27 (m, 1H, p-
Ph), 3.49 (s, 2H, CH2Ph), 3.18 (d, J = 11.1 Hz, 2H, CH2N), 3.06 – 2.95 (m, 1H,
H7), 2.58 (d, J = 11.6 Hz, 2H, CH2N), 2.37 (br s, 2H, H1, H5), 2.19 (dd, J =
14.1, 5.6 Hz, 2H, H6, H8), 2.09 – 2.01 (m, 2H, H6, H8), 1.60 – 1.53 (m, 1H, H7).

ACCEPTED MANUSCRIPT
13C NMR (151 MHz, CDCl3) δ 218.90 (C=O), 138.72 (ipso-Ph), 128.69 (o-Ph),
128.42 (m-Ph), 127.15 (p-Ph), 62.23 (CH2Ph), 60.42 (CH2N), 47.89 (C1, C5),
34.77 (C6, C8), 21.40 (C7).
4.4. 3-Benzyl-8-dimethylamino-3-azabicyclo[3.2.1]octane (4)
To a solution of 3 (5.2 g, 24 mmol) in CH2Cl2 (150 ml) were added
dimethylamine (40% solution in water, 5.4 ml, 48 mmol), AcOH (1.4 ml, 24
mmol) and by portions sodium triacetoxyborohydride (STAB) (15.3 g, 72
mmol). The mixture was stirred for 8 h at room temperature, diluted with cold
water, basified with sodium hydroxide solution to pH 10, extracted with CH2Cl2,
washed with brine, dried over Na2SO4 and evaporated. The residue was purified
by SiO2 column chromatography with AcOEt/petroleum ether (10/90-20/80) to
afford 4 (4.9 g, 69 %) as a pale yellow oil. Anal.: C, 78.71; H, 9.83; N, 11.39 %.
-1
Calc. for C16H24N2: C, 78.64; H, 9.90; N, 11.46%. IR (thin film, ν, cm ): 732,
697 (C6H5). EI-MS, m/z (RI, %): 245 [M+H]+ (53), 244 [M]+ (40), 200 [M-
NMe2]+ (30), 153 [M-Bn]+ (100). 1H NMR (500 MHz, CDCl3) δ 7.37 (d, J = 7.4
Hz, 2H, o-Ph), 7.34 – 7.28 (m, 2H, m-Ph), 7.23 (t, J = 7.2 Hz, 1H, p-Ph), 3.56 (s,
2H, CH2Ph), 2.64 (d, J = 10.1 Hz, 2H, CH2N), 2.38 (dd, J = 10.3, 3.6 Hz, 2H,
CH2N), 2.25 (s, 6H, NMe2), 2.10 (br s, 2H, H1, H5), 1.91 (t, J = 4.2 Hz, 1H, H
8), 1.86 (q, J = 5.5 Hz, 2H, H6, H7), 1.71 – 1.64 (m, 2H, H6, H7). 13C NMR (126
MHz, CDCl3) δ 140.34 (ipso-Ph), 128.66 (o-Ph), 128.04 (m-Ph), 126.51 (p-Ph),
70.48 (C8), 62.27 (CH2Ph), 52.86 (CH2N), 44.53 (NMe2), 36.66 (C1, C5), 27.31
(C6, C7).

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4.5. 3-Benzyl-9-dimethylamino-3-azabicyclo[3.3.1]nonane (7) and 3-benzyl-9-
hydroxy-3-azabicyclo[3.3.1]nonane (8)
To a solution of 6 (10 g, 44 mmol) in CH2Cl2 (300 ml) were added
dimethylamine (40% solution in water, 11 ml, 87 mmol), AcOH (2.5 ml, 44
mmol) and by portions STAB (28 g, 132 mmol). After the stirring for 8 h at room
temperature to the reaction mixture were added more STAB (13 g, 61 mmol) and
AcOH (1.3 ml, 0.023m) and the stirring was continued for 6 hours else. Then the
reaction mixture was diluted with cold water, basified with sodium hydroxide
solution to pH 10, extracted with CH2Cl2, washed with brine, dried over Na2SO4
and evaporated. The residue was purified by SiO2 column chromatography with
AcOEt/petroleum ether (10/90-20/80) to afford 7 (4.1 g, 36 %) as a pale yellow
oil and 8 (3.8 g, 37%) as a white powder.
3-Benzyl-9-dimethylamino-3-azabicyclo[3.3.1]nonane 7
Anal.: C, 79.11; H, 10.18; N, 10.71 %. Calc. for C17H26N2: C, 79.02; H, 10.14;
-1
N, 10.84 %. IR (KBr, ν, cm ): 747, 700 (C6H5). EI-MS, m/z (RI, %): 259
[M+1]+ (24), 258 [M]+ (11), 214 [M-NMe2]+ (26), 167 [M – Bn]+ (100). Major
isomer: 1H NMR (600 MHz, CDCl3) δ 7.37 – 7.30 (m, 4H, o- and m-C6H5), 7.28
– 7.22 (m, 1H, p-C6H5), 3.40 (s, 2H, CH2Ph), 2.99 (d, J = 10.8 Hz, 2H, CH2N),
2.68 – 2.64 (m, 1H, H7), 2.24 (s, 6H, 2NMe2), 2.24 - 2.21 (m, 2H, CH2N), 1.93
(br s, 2H, H1, H5), 1.98 – 1.87 (m, 2H, H6, H8), 1.71 (br s, 1H, H9), 1.58 – 1.51
(m, 1H, H7), 1.49 – 1.46 (m, 2H, H6, H8). 13C NMR (151 MHz, CDCl3) δ
139.65 (ipso-C6H5), 128.62 (o-C6H5), 128.19 (m-C6H5), 126.64 (p-C6H5), 68.29
(C9), 63.45 (CH2Ph), 60.04 (CH2N), 43.02 (NCH3), 31.41 (C1, C5), 24.70 (C6,
1
C8), 21.28 (C7). Minor isomer: H NMR (600 MHz, CDCl3) δ 7.37 – 7.30 (m,
4H, o- and m-C6H5), 7.28 – 7.22 (m, 1H, p-C6H5), 3.43 (s, 2H, CH2Ph), 2.79 –

ACCEPTED MANUSCRIPT
2.70 (m, 1H, H7), 2.60 (br s, 4H, CH2N), 2.23 (s, 6H, 2 NCH3), 2.02 (br s, 2H,
H1, H5), 1.98 – 1.87 (m, 2H, H6, H8), 1.72 (s, 1H, H9), 1.65 – 1.58 (m, 2H, H6,
H8), 1.49 – 1.46 (m, 1H, H7). 13C NMR (151 MHz, CDCl3) δ 140.11 (ipso-
C6H5), 128.70 (o-C6H5), 128.11 (m-C6H5), 126.49 (p-C6H5), 67.92 (C9), 63.81
(CH2Ph), 53.34 (CH2N), 43.13 (NCH3), 32.39 (C6, C8), 31.48 (C1, C5), 21.76
(C7).
3-benzyl-9-hydroxy-3-azabicyclo[3.3.1]nonane 8
Anal.: C, 77.88; H, 9.07; N, 6.09 %. Calc. for C15H21NO: C, 77.88; H, 9.15; N,
6.05 %. IR (KBr, ν, cm -1): 730, 697 (C6H5). EI-MS, m/z (RI, %): 231 [M]+ (43),
140 [M–Bn]+ (42). Major isomer: 1H NMR (600 MHz, CDCl3) δ 7.36 – 7.32 (m,
4H, o- and m-C6H5), 7.28 – 7.24 (m, 1H, p-C6H5), 3.78 (d, J = 2.8 Hz, 1H, H9),
3.40 (s, 2H, CH2Ph), 2.97 (d, J = 10.4 Hz, 2H, CH2N), 2.72 – 2.63 (m, 1H, H7),
2.29 (d, J = 11.6 Hz, 2H, CH2N), 2.03 – 1.95 (m, 2H, H6, H8), 1.81 (br s, 2H,
H1, H5), 1.51 – 1.59 (m, 3H, H6, H8, ОН), 1.50 (dt, J = 12.7, 6.3 Hz, 1H, H7).
13C NMR (101 MHz, CDCl3) δ 139.52 (ipso-C6H5), 128.62 (o-C6H5), 128.23 (m-
C6H5), 126.74 (p-C6H5), 72.35 (C9), 63.24 (CH2Ph), 59.07 (CH2N), 35.54 (C1,
1
C5), 24.26 (C6, C8), 21.29 (C7). Minor isomer: H NMR (600 MHz, CDCl3) δ
7.36 – 7.32 (m, 4H, o- and m-C6H5), 7.28 – 7.24 (m, 1H, p-C6H5), 3.69 (t, J = 3.1
Hz, 1H, H9), 3.41 (s, 2H, CH2Ph), 2.67 (d, J = 12.6 Hz, 2H, CH2N), 2.60 (d, J =
11.4 Hz, 2H, CH2N), 2.57 – 2.49 (m, 1H, H7), 2.08 (br s, 1H, OH), 1.90 (br s,
2H, H1, H5),1.86 - 1.84 (m, 2H, H6, H8), 1.68 – 1.60 (m, 2H, H6, H8), 1.43 (dt,
13
J = 12.6, 6.3 Hz, 1H, H7). C NMR (101 MHz, CDCl3) δ 139.40 (ipso-C6H5),
128.70 (o-C6H5), 128.23 (m-C6H5), 126.74 (p-C6H5), 71.79 (C9), 63.64 (CH2Ph),
52.86 (CH2N), 36.20 (C1, C5), 31.36 (C6, C8), 20.35 (C7).

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4.6. (8-Dimethylamino--3-azabicyclo[3.2.1]octane-3-ylmethyl)phenyl]-(C,N,N)-
palladium chloride, 5
Method A. A mixture of PdCl2 (0.138 g, 0.78 mmol) and LiCl (0.066 g, 1.56
mmol) in MeOH (20 ml) was refluxed with stirring for 1 h and cooled. To the
obtained solution was added a solution of 4 (0.191 g, 0.78 mmol) and sodium
acetate monohydrate (0.107 g, 0.78 mmol) in MeOH (10 ml). The mixture was
stirred for 24 h at room temperature and evaporated. The crude was diluted with
water and extracted with CH2Cl2. The organic layers were washed with water
and brine, dried over Na2SO4, filtered and evaporated. The solid residue was
washed with ether and small amount of acetone and dried to afford 5 (0.237 g,
79%).
Method B. To a solution of Na2PdCl4 (0.125 g, 0.43 mmol) in MeOH (10 ml)
was added a solution of 4 (0.104 g, 0.43 mmol) in MeOH (10 ml). The mixture
was stirred for 24 h at room temperature and evaporated. The crude was diluted
with water and extracted with CH2Cl2. The organic layers were washed with
water and brine, dried over Na2SO4, filtered and evaporated. The solid residue
was washed with ether and small amount of acetone and dried to afford 5 (0.097
g, 59%) as off-white crystals. Decomposes without melting at about 160 °C.
Anal.: C, 49.54; H, 6.14; N, 7.15 %. Calc. for C16H23ClN2Pd: C, 49.88; H, 6.02;
-1
-1
N, 7.27 %. IR (KBr, ν, cm ): 738 (o-C6H4); IR (nujol, ν, cm ): 322 (Pd-Cl).
EI-MS, m/z (RI, %): 384 [M]+ (12), 243 [M-PdCl]+ (98), 198 [M-PdCl-NHMe2]+
1
(44). H NMR (500 MHz, CDCl3) δ 7.70 (dd, J = 7.1, 1.8 Hz, 1H, H16), 6.99 –
6.90 (m, 2H, H14, H15), 6.82 (dd, J = 7.0, 1.4 Hz, 1H, H13), 4.23 – 4.12 (m, 2H,
CH2N), 3.99 (s, 2H, CH2Ph), 2.76 (s, 6H, 2 NCH3), 2.62 (br s, 2H, H1, H5), 2.42
(d, J = 12.5 Hz, 2H, CH2N), 2.13 (t, J = 3.7 Hz, 1H, H8), 2.04 – 1.96 (m, 2H, H6,

ACCEPTED MANUSCRIPT
13
H7), 1.66 (q, J = 5.8 Hz, 2H, H6, H7). C NMR (126 MHz, CDCl3) δ 147.56
(ipso-C6H4, C-C), 144.55 (ipso-C6H4, C-Pd), 136.10 (C16), 125.28 and 124.17
(C14 and C15), 120.01 (C13), 73.06 (CH2Ph), 69.75 (C8), 64.43 (CH2N), 48.75
(NCH3), 33.91 (C1, C5), 30.85 (C6, C7).
4.7. (9-Dimethylamino-3-azabicyclo[3.3.1]nonane-3-ylmethyl)phenyl]-(C,N,N)-
palladium chloride, 9
A mixture of PdCl2 (0.182 g, 1.0 mmol) and LiCl (0.087 g, 2 mmol) in MeOH
(20 ml) was refluxed with stirring for 1 h and cooled. To the obtained solution
was added a solution of 7 (0.266 g, 1.0 mmol) and sodium acetate monohydrate
(0.140 g, 1.0 mmol) in MeOH (10 ml). The mixture was stirred for 24 h at room
temperature and evaporated. The crude was diluted with water and extracted with
CH2Cl2. The organic layers were washed with water and brine, dried over
Na2SO4, filtered and evaporated. The residue was washed with ether and acetone
and dried to afford 9 (0.064 g, 16%) as off-white crystals. Decomposes without
melting at about 167 °C. Anal.: C, 50.89; H, 6.30; N, 6.82; Cl, 8.95 %. Calc. for
C17H25ClN2Pd: C, 51.14; H, 6.31; N, 7.02; Cl, 8.88 %. IR (KBr, ν, cm -1): 743 (o-
-1
C6H4); IR (nujol, ν, cm ): 320 (Pd-Cl). EI-MS, m/z (RI, %): 399 [M+H]+ (30),
398 [M]+ (14), 257 [M-PdCl]+ (100). 1H NMR (600 MHz, CDCl3) δ 7.71 (d, J =
7.1 Hz, 1H, H17), 6.99 – 6.88 (m, 2H, H15, H16), 6.81 (d, J = 6.6 Hz, 1H, H14),
4.01 (s, 2H, CH2Ph), 3.94 (t, J = 11.3 Hz, 2H, CH2N), 2.81 (br s, 2H, H1, H5),
2.70 (s, 6H, 2 NCH3), 2.44 (d, J = 12.2 Hz, 2H, CH2N), 1.87 (br s, 1H, H9), 1.82
– 1.65 (m, 2H, H6, H8), 1.63 – 1.50 (m, 4H, H6, H8, H7). 13C NMR (151 MHz,
CDCl3) δ 147.94 (ipso-C6H4, C-C), 144.12 (ipso-C6H4, C-Pd), 136.16 (С17),

ACCEPTED MANUSCRIPT
125.23 and 124.17 (С15 and C16), 120.02 (С14), 72.85 (СH2Ph), 68.24 (C9),
59.28 (CH2N), 46.59 (NCH3), 31.15 (C6, C8), 29.14 (C1, C5), 14.18 (C7).
4.8. X-ray crystallography.
Crystals of the complexes 5 and 9 suitable for X-ray analysis were obtained by
recrystallization from CH2Cl2. The unit cells parameters and three-dimensional
sets of intensities for complexes 5 and 9 were obtained on an APEX II CCD
diffractometer using molybdenum radiation [λ (Mo Kλ) = 0.71073 Å, ω-scans].
The substantial redundancy in data allowed empirical absorption corrections to
be applied with SADABS by multiple measurements of equivalent reflections.
The structures were solved by direct methods and refined by the full-matrix least-
squares technique against F2 in the anisotropic-isotropic approximation. C-H
hydrogen atoms in all structures were placed in calculated positions and refined
within the riding model. All calculations were performed with the SHELXTL
software package [37]. Crystal data and structure refinement parameters are
listed in Table 3.
Table 3. Crystal data and structure refinement parameters for 5 and 9.
5
9
CCDC
1826817
C16H23ClN2Pd
385.21
1826818
C17H25ClN2Pd
399.24
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
120
120
Triclinic
P-1
Triclinic
P-1
Z(Z’)
a, Å
b, Å
c, Å
2(1)
2(1)
8.3929(3)
9.2936(3)
11.0549(4)
8.8441(5)
9.3276(5)
10.9346(6)

ACCEPTED MANUSCRIPT
98.4989(6)
112.0717(6)
95.1981(7)
780.21(5)
1.640
97.7403(10)
α, °
111.5282(10)
97.7537(10)
814.67(8)
1.628
β, °
γ, °
V, Å3
dcalc, g cm-3
µ, cm-1
F(000)
13.52
12.98
392
408
58 (1.00)
9657
58 (0.99)
9853
2θmax, ° (completeness)
Refl. collected
Refl. unique (Rint)
Refl. with I > 2σ(I)
Variables
4144 (0.0181)
4037
4333 (0.0280)
4001
184
190
Final R1 with I>2σ(I)
wR2 (all data)
GOF
0.0158
0.0207
0.0388
0.0483
0.973
1.055
Largest difference in peak /
hole (e/Å3)
0.458/-0.440
0.492/-0.420
4.9. General procedure for the Suzuki reaction
A mixture of aryl bromide (1 mmol), phenylboronic acid (1.5 mmol), K2CO3 (2
mmol), the palladium complex 5 or 9, MeOH (8 ml) and H2O (4 ml) was heated
at 55° C for 5 h. The reaction mixture was diluted with water and extracted with
CHCl3. The combined organic phase was dried over Na2SO4, evaporated and
purified by chromatography on SiO2 (petroleum ether/CHCl3=8:1). The purified
products were identified by 1H NMR spectra.
Acknowledgments
The contribution of the Center for molecule composition studies of INEOS RAS
is gratefully acknowledged.
Supplementary material

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CCDC 1826817 (for 5) and 1826818 (for 9) contain the supplementary
crystallographic data. These data can be obtained free of charge from the
Cambridge
Crystallographic
Data
Center
via
www.ccdc.cam.ac.uk/data_request/cif.
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•
•
•
Two 5,6-membered bicyclic CNN pincer palladium complexes have been synthesized
The molecular structures were confirmed by X-ray diffraction analysis in single crystal
The complexes demonstrate good catalytic activity in the Suzuki reaction