Electrochemical C-H phosphorylation of 2-phenylpyridine in the presence of palladium salts

Article abstract of DOI:10.1007/s11172-014-0792-3

A new approach was developed to the introduction of the phosphonate group into arylpyridines using 2-phenylpyridine as an example. The approach is the electrochemical oxidation of a mixture of 2-phenylpyridine, diethyl phosphite, and palladium acetate at room temperature. An intermediate dipalladium cyclic complex was isolated that is formed by the ortho-palladation of 2-phenylpyridine and substitution of acetate ions by phosphonate ions. The preparative oxidation of this complex selectively results in the product of the phosphorylation of the C-H bond in 2-phenylpyridine.

Full text of DOI:10.1007/s11172-014-0792-3

Russian Chemical Bulletin, International Edition, Vol. 63, No. 12, pp. 2641—2646, December, 2014
2641
Electrochemical С—Н phosphorylation of 2ꢀphenylpyridine
in the presence of palladium salts
Yu. B. Dudkina, T. V. Gryaznova, O. N. Kataeva, Yu. H. Budnikova, and O. G. Sinyashin
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Еꢀmail: tatyanag@iopc.ru
A new approach was developed to the introduction of the phosphonate group into arylꢀ
pyridines using 2ꢀphenylpyridine as an example. The approach is the electrochemical oxidation
of a mixture of 2ꢀphenylpyridine, diethyl phosphite, and palladium acetate at room temperaꢀ
ture. An intermediate dipalladium cyclic complex was isolated that is formed by the orthoꢀ
palladation of 2ꢀphenylpyridine and substitution of acetate ions by phosphonate ions. The
preparative oxidation of this complex selectively results in the product of the phosphorylation
of the C—H bond in 2ꢀphenylpyridine.
Key words: С—Н phosphorylation, Hꢀphosphonate, electrooxidation, 2ꢀphenylpyridine,
palladium complexes.
Direct functionalization of compounds containing
C—H bonds provides the most efficient route of transꢀ
formation of molecules, which attracts vast attention to
the problem.1 Although a wide set of such reactions, inꢀ
cluding those catalyzed by transition metals, was accomꢀ
plished to the present time, examples of С—Р bond forꢀ
mation are very restricted, most likely, due to the strong
coordinating influence of phosphorus reagents.2 Chemiꢀ
cal and electrochemical methods of hydrogen atom subꢀ
stitution by phosphorusꢀcontaining nucleophiles are few.
Successful examples are mainly described only for the funcꢀ
tionalization of nitroaromatic substrates.3 The routes for
С—Р bond formation remain to be an urgent field of studꢀ
ies. Special attention is given to the synthesis of phosꢀ
phonic acid derivatives, since the phosphonate group is in
the composition of many natural molecules variable in
structure and involved in biological processes. Many poꢀ
tential drugs, which exhibit anticancer or antibacterial
properties or act as antiꢀAIDS agents, also contain phosꢀ
phonic acid fragments. There are numerous methods in
synthetic chemistry for introducing phosphorus groups into
various structures, and enantioselective results were obꢀ
tained in some cases. However, the first catalytic methods
that are especially important due to requirements of green
chemistry have been developed quite recently, and there
are only few successful examples.4,5
all, of nucleophile, which necessarily affects the result of
the reaction. For the Hꢀadduct and other intermediates it
is very difficult (and sometimes impossible) to estimate
the oxidation potential as a measure of the ability of the
substance to donate electrons. Therefore, one has to select
the oxidant guiding by experience, intuition, and some
empirical rules that make it possible to judge only tentꢀ
atively about the efficiency of the oxidant.
Another problem is that the used cooxidants are exꢀ
pensive (for example, salts of metals of the platinum
and silver groups) and organic oxidants with a high moꢀ
lecular weight are hardly separable from the reaction mixꢀ
ture. In addition, all of them are often insufficiently
selective.1f,6,7
Several different strategies are applied for the solution
of the problem of selective С—Н functionalization. The
most popular strategies assume the use of substrates conꢀ
taining coordinating ligands. These ligands (often named
"directing groups") are bound to the metal center and seꢀ
lectively direct the catalyst to the nearest С—Н bond.
Many transition metals, including Pd, enter into ligandꢀ
directed reactions of C—H bond activation (also known as
cyclometallation reactions).
The successful examples of the phosphorylation of the
C—H bond of the aromatic substrate with the directing
pyridyl or other heterocyclic group to the orthoꢀpalladꢀ
ation reaction have recently been described.4,5 The method
used4 makes it possible to obtain the product of phosꢀ
phorylation of 2ꢀphenylpyridine bearing the (EtO)2P(O)
group in 66% yield (Scheme 1) and with the (PriO)2P(O)
group in 78% yield.
One of the most difficult problems of performing
С—Н substitution, including that with participation of
Рꢀnucleophiles, is the necessary presence of an oxidant.
Each pair of substrates needs preliminary experiments with
allowance for the ability of reactants to oxidation, first of
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2641—2646, December, 2014.
1066ꢀ5285/14/6312ꢀ2641 © 2014 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014
Dudkina et al.
We have previously shown9 the possibility of electroꢀ
chemical С—Н acetoxylation and perfluoroalkylation unꢀ
der mild conditions. The purpose of this study is to estabꢀ
lish the possibility of the С—Н phosphorylation of
2ꢀphenylpyridine under the conditions of electrochemical
oxidation involving Pd(OAc)2 and diethyl phosphite as an
accessible phosphorus precursor. The application of the
electrochemical method would make it possible to carry
out the reaction without a specially added oxidant at
a controlled potential under milder conditions and to study
individual stages of the reaction.
Scheme 1
Reagents and conditions: tertꢀС5Н11ОН, 120 С, 13 h.
Catalyst Pd(OAc)2 (10 mol.%), base NaOAc (2 equiv.), oxidant
AgOAc, benzoquinone for the facilitation of the reductive elimiꢀ
nation stage.
Results and Discussion
The electrochemical oxidation of a mixture of 2ꢀphenꢀ
ylpyridine, diethylphosphorous acid (phosphorous acid
diethyl ester) (ratio 1.0 : 1.1), and Pd(OAc)2 (10 mol.%)
in a divided electrolyzer gives not only phosphorylated
2ꢀphenylpyridine 1 (Scheme 3) but also a series of other
products.
The method described5 is performed under similar conꢀ
ditions (Scheme 2).
Scheme 2
Scheme 3
Reagents and conditions: ButOH, 120 С, 48 h. Catalyst Pd(OAc)2
(10 mol.%), base K2HPO4 (4.5 equiv.), oxidant AgOAc
(2.5 equiv.), 1ꢀmethylꢀ1Нꢀpyrroleꢀ2,5ꢀdione (40 mol.%) for the
facilitation of the reductive elimination stage.
According to the 31Р NMR spectrum of the reaction
mixture, the electrolysis affords the dipalladium complex
containing phosphonate ligands with Р 96.1, phosphorylꢀ
ated 2ꢀphenylpyridine with Р 18.1, and probably phosꢀ
phonium salts (Р 27.2) and phosphorous acids. To optiꢀ
mize the electrosynthesis, we carried out experiments unꢀ
der different conditions in the presence of bases and some
additives favoring the occurrence of the reductive eliminꢀ
ation stage (1ꢀmethylꢀ1Нꢀpyrroleꢀ2,5ꢀdione (NMMI),
benzoquinone (BQ), bipyridine (bpy)). In the course of
the synthesis, diethylphosphorous acid was permanently
added dropwise. The results of experiments are presented
in Table 1.
It is seen that the target product of С—Н phosphorylꢀ
ation 1 is formed under the electrochemical oxidation conꢀ
ditions in satisfactory (in the case of entry 6, fairly good)
yield at both room temperature and 70 С even in the
absence of additives (NMMI or BQ). The best result (see
Table 1) was obtained when the electrolysis was carried
out in the presence of sodium acetate as a base and benzoꢀ
quinone facilitating the reductive elimination stage.
In order to establish the mechanism of the process, we
synthesized intermediate sixꢀmembered binuclear palladꢀ
ium complex 3 similar to [(PhPy)Pd(BuO)2P(O)]2 deꢀ
In this case, the orthoꢀС—Н bond in 2ꢀphenylpyridine
was subjected to phosphorylation by dibutyl phosphite with
the yield of the product only 12%. The best results were
achieved5 when dialkyl phosphite was replaced by the speꢀ
cially prepared ꢀhydroxyalkyl phosphonate. In this work,
we used commercially accessible dialkyl phosphites as
phosphorylating agents.
In spite of obvious success of aromatic substrates in
С—Н phosphorylation,4,5 many factors (high temperaꢀ
tures, excess of expensive silverꢀcontaining oxidant AgOAc
and additional agents for the facilitation of the reductive
elimination stage, not always satisfactory yields and reacꢀ
tion time) indicate that the search for new simpler and
more efficient solutions is important and promising.
The advantages of electrochemical metal complex caꢀ
talysis are (1) the possibility of controlled synthesis of
active forms of catalysts, i.e., metal complexes with differꢀ
ent oxidation states, (2) mild reaction conditions, and (3)
the possibility to carry out the reaction in an almost closed
system using a minimum amount of the reusable catalyst.
It is known that electrochemical processes are ecologicalꢀ
ly safe and their control can easily be automated.8

C—H phosphorylation of 2ꢀphenylpyridine
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014 2643
Table 1. Optimization of the electrochemical C—H phosphorylation of 2ꢀphenylpyridine in the presence of 10 mol.%
palladium acetate
Entry
Base
Additional
reagents
Electrolysis
conditions
Yield
of product 1 (%)
1
2
Na2HPO4
(excess)
(EtO)2PONa
acid/salt = 1 : 2
—
МеCN, 20 С
20
35
Maleic anhydride (2 equiv.)
and BQ (2 equiv.)
МеCN, 20 С.
Additional reagents were added
after electrolysis, 6 h, 80 С
МеCN, 70 С
3
(EtO)2PONa
acid/salt = 1 : 1,
Na2HPO4
BQ
43
4
5
6
Na2HPO4
(excess)
(EtO)2PONa
acid/salt = 1 : 1
NaOAc (2 equiv.)
NMMI (40%)
—
МеCN, 70 С
42
15
68
Amyl alcohol,
80 С, 4.5 h
МеCN, 20 С
BQ (2 equiv.)
After electrolysis the mixture
was heated at 80 С for 1 h
МеCN, 20 С, Q = 3 Ф
МеCN, 20 С
7*
8
Lutidine (2 equiv.)
Lutidine (2 equiv.)
bpy (1 equiv.)
bpy (1 equiv.)
52
48
* The equimolar amount of palladium acetate was used.
scribed earlier.5 For this purpose, we performed the reacꢀ
tion of the acetate dimer of phenylpyridylpalladium 2,
which was obtained using a described procedure,10 with
diethyl phosphite (1 : 2) in acetonitrile (Scheme 4).
2.2 equiv. K2HPO4. Evidently, the ligand exchange is
much easy when diethyl phosphite is used.
The binuclear structure was ascribed to complex 3 by
analogy to the previously5 studied relative compound
[(PhPy)Pd(BuO)2P(O)]2.
Then, complex 3 was oxidized at the Pt electrode in
МеCN at 20 C under argon at the potential of the first
oxidation peak with the complete conversion to the single
product of orthoꢀphosphorylation of 2ꢀphenylpyridine
(compound 1) (Scheme 5) in an almost quantitative yield
(the 31Р NMR spectrum of the reaction mixture contains
the single signal with Р 18).
Scheme 4
Scheme 5
The electrochemical characteristics of complex 3 were
studied by cyclic voltammetry. The cyclic voltammogram
of complex 3 (Fig. 1) exhibits two peaks of irreversible
oxidation, and their potentials are in a more positive reꢀ
The reaction occurs readily at 20 С. Complex 3 in
90% yield precipitates from the reaction mixture in 24 h.
Earlier,5 when synthesizing the palladium dibutyl phosꢀ
phonate complex [(PhPy)Pd(BuO)2P(O)]2 from ꢀhydrꢀ
oxybutyl phosphonate and [(PhPy)Pd(OAc)]2, the mixꢀ
ture was heated in dioxane at 120 С in the presence of
gion compared to the potentials of complex
([(PhPy)Pd(OAc)]2).
2
The electrochemical behavior of complex 2 has been
studied previously.9b It was shown that complex 2 is oxiꢀ

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Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014
Dudkina et al.
I/A
Thus, the electrochemical oxidation favors the reducꢀ
tive elimination of intermediate 3 to occur much more
efficiently.
1
25 A
According to the oxidation potentials of the key interꢀ
mediates complexes [(PhPy)Pd(ꢀOAc)]2
2
and
[(PhPy)Pd(EtO)2P(O)]2 3, phosphorus complex 3 is more
difficultly oxidized than acetate complex 2. A comparison
of the chemical (AgOAc as an oxidant (see Refs 4 and 5))
and electrochemical oxidations shows that the acetate
complex would be oxidized first. The latter undesirable
reaction results in the orthoꢀacetoxylation of 2ꢀphenylꢀ
pyridine.9b To obtain target product 1 in good yield,
it is necessary to provide conditions for the predomiꢀ
nant oxidation of the phosphorus complex, i.e., to perꢀ
form electrolysis at the oxidation potential of complex 3.
The presumable scheme of the electrochemical С—Н
phosphorylation of 2ꢀphenylpyridine can be presented as
Scheme 6.
[(PhPy)Pd(ꢀOAc)]2
0.62
1.56
2
[(PhPy)Pd(EtO)2P(O)]2
1.18
1.69
1.92
1.35
0.77
0.20 E/V (vs Ag/AgNO3)
Fig. 1. Cyclic votammograms of 0.005 М solutions of complexes
[(PhPy)Pd(ꢀOAc)]2 (2) (curve 1) and [(PhPy)Pd(EtO)2P(O)]2
(3) (curve 2) in МеCN. The concentration of the complexes is
Scheme 6
5•10–3 mol L–1, and the potential sweep is 100 mV s–1
.
dized in two stages with the transfer of two electrons at
each stage. The first peak characterizes the reversible oxidꢀ
ation and is due to the metalꢀcentered electron transfer
and conversion PdII  PdIII. Two electrons are also transꢀ
ferred at the second stage, but the oxidation PdIII  PdIV is
irreversible. The formation of intermediate PdIII was earliꢀ
er detected in the oxidation of compound 2, whereas no
paramagnetic intermediates were observed in the case of
complex 3. However, two oxidation stages (two peaks but
at more positive potentials) are also observed for this
complex.
Thus, the substitution of hydrogen in the orthoꢀposiꢀ
tion of 2ꢀphenylpyridine by the phosphonate group proꢀ
ceeds selectively under the electrochemical oxidation conꢀ
ditions and does not require additional reagents (NMMI,
BQ, PPh3, etc.) promoting the reductive elimination stage,
which are always present in all earlier published works.4,5
It can be assumed that in the chemical variant of С—Н
phosphorylation the role of AgOAc as an oxidant was not
only to participate in the regeneration of the palladium
catalyst by the oxidation of presumably formed Pd0 to
PdII, as it is suggested by the authors.4,5 Perhaps, Ag+ can
act as an oxidant of the intermediately formed phosꢀ
phorusꢀcontaining diphenylpyridinepalladium complex
[(PhPy)Pd(BuO)2P(O)]2 affording the target product
PhPy(BuO)2P(O).
Electrolysis at the oxidation potential of phosphorus
complex 3 favors the catalytic process and increases the
yield. The addition of other substances (BQ, NMMI,
PPh3), which facilitate, as a rule, reductive elimination,
can probably shift the oxidation potentials of complexes 2
and 3 to different extents, which increases the yield of the
target product. As can be seen from Table 1, the best result
was achieved upon the addition of benzoquinone.
Thus, the new approach was developed to the introꢀ
duction of the phosphonate group into arylpyridines using
2ꢀphenylpyridine as an example. The approach is based
on the electrochemical oxidation of a mixture of 2ꢀphenylꢀ
pyridine and diethyl phosphite at room temperature in the
presence of palladium acetate. The intermediate sixꢀmemꢀ
bered binuclear palladium cycle linked to the phosphoꢀ
nate ligand through the oxygen and phosphorus atoms
[(PhPy)Pd(EtO)2P(O)]2 (3) was isolated, and its redox
properties were determined. The preparative oxidation of
complex 3 selectively gives the target product of C—H
bond phosphorylation in quantitative yield.
We reproduced the reductive eliminations stage5 by
heating complex 3 in МеCN (at the temperature of the
bath 120 С) in the presence of 2 equiv. NMMI for 4 h.
However, only half an initial complex decomposed to the
product of orthoꢀphosphorylation of 2ꢀphenylpyridine 1.

C—H phosphorylation of 2ꢀphenylpyridine
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014 2645
matographic column packed with silica gel (hexane—dichloroꢀ
methane (1 : 3) as an eluent). 2ꢀ(Pyridinꢀ2´ꢀyl)phenyldiethyl
phosphonate (1) was obtained (see Table 1, entry 6) in a yield of
When considering the mechanism of С—Н phosꢀ
phorylation, one should take into account the dual role of
the metal salt (in particular, AgOAg) introduced into the
reaction mixture as a regenerator of the active form of the
catalyst and an oxidant of the key intermediate of the
reactions.
1.4 g (68%). 1Н NMR (CDСl3), : 8.81 (d, 1 Н, H(6), Py, 3JH,H
= 5.85 Hz); 8.10 (dt, 1 Н, H(3´), Ph, 3JH,H = 7.98 Hz, 4JH,H
=
=
1.25 Hz); 7.86 (d, 2 Н, H(3), Py and H(6´), Ph, 3JH,H = 7.28 Hz);
7.65 (d, 1 Н, H(5´), Ph, 3JH,H = 7.54 Hz); 7.42 (t, 2 Н, H(4), Py
and H(4´), Ph, 3JH,H = 7.89 Hz); 7.34 (m, 1 Н, H(5), Py); 4.05
(dq, 4 Н, CH2CH3, 3JH,H = 7.09 Hz, 3JP,H = 7.95 Hz); 1.23 (t, 6 Н,
Experimental
3
CH2CH3, JH,H = 7.01 Hz). 31Р NMR (CDСl3), : 18.1.
Found (%): C, 60.93; H, 5.81; N, 4.63; Р, 10.34. C15H18NO3Р.
Calculated (%): C, 61.85; H, 6.18; N, 4.81; Р, 10.65.
Acetonitrile was distilled over Р2О5 and KMnO4 and then
over molecular sieves. Benzene was distilled over sodium. After
purification, the solvents were kept under dry argon. Supporting
salt Et4NBF4 was recrystallized from ethanol and dried in
a vacuum desiccator at 100 С for 48 h. Diethylphosphorous acid
was obtained by an earlier described procedure.11 The palladium
complexes were synthesized according to known procedures.12,13
2ꢀPhenylpyridine (Acros) was used. All syntheses were carried
out under dry argon.
Preparative electrolysis was carried out using a B5ꢀ49 conꢀ
stant current source in a 40ꢀmL threeꢀelectrode cell with divided
anodic and cathodic spaces in the presence of Et4NBF4 as
a supporting electrolyte. The potential of the working electrode
was measured with a V7ꢀ27 constant current voltmeter relative
to the reference electrode Ag/0.01 М AgNO3 in acetonitrile.
The working surface of the platinum cylindrical cathode used as
a working electrode was 20.0 cm2. A ceramic plate with a pore
size of 900 nm served as a membrane. The anode was a platinum
wire, and the catholyte was a saturated solution of PyHBF4 in
МеCN. The electrolyte was magnetically stirred at a permanent
argon flow passing through the drying system.
NMR spectra were recorded on Bruker AVANCEꢀ400 multiꢀ
nuclear spectrometers (400.1 (1Н) and 162.0 MHz (31Р)). The
1Н chemical shifts were detected relative to the signal of the
deuterated solvent used as an internal standard, and the 31Р shifts
were measured relative to the signal of phosphoric acid as an
external standard.
Cyclic voltammograms were detected on a BASi Epsilon
potentiostat at a linear potential sweep of 100 mV s–1. The glassy
carbon stationary disc electrode with the working surface area
8 mm2 was used as a working electrode. The Ag/0.01 М AgNO3
system in МеCN served as reference electrode, and an auxiliary
electrode was a platinum wire with a diameter of 1 mm and
a length of 10 mm. The measurements were performed in a temꢀ
peratureꢀcontrolled (25 С) cell in argon. The cyclic voltammoꢀ
grams of the complexes were detected in МеCN at a concentraꢀ
tion of the substrate of 5•10–3 mol L–1 in a 0.01 М solution of
Bu4NBF4.
Synthesis of the dimer of phenylpyridylpalladium diethyl phosꢀ
phonate (3). Diethylphosphorous acid (2 mmol, 0.28 g) was addꢀ
ed to [PhPyPdOAc]2 (2) (1 mmol, 0.64 g) in MeCN (15 mL).
The reaction mixture was stirred for 24 h at 20 С. Precipitated
transparent crystals were filtered off and dried, and complex 3
1
was obtained in a yield of 0.71 g (90%). Н NMR (CDСl3), :
8.98 and 8.97 (both d, 2 Н, H(6), H(12), Py, 3JH,H = 4.57 Hz);
7.91 (m, 2 Н, H(3´), H(9´), Ph); 7.86 and 7.84 (both dd, 2 Н,
3
4
3
H(6´), H(12´), Ph, JH,H = 7.48 Hz, JH,H = 1.75 Hz, JH,H
=
4
= 7.44 Hz, JH,H = 1.73 Hz); 7.76 (br.d, 2 Н, H(3), H(9), Py,
3JH,H = 7.93 Hz); 7.57 (m, 2 Н, H(5´), H(11´), Py); 7.28 (t, 2 Н,
H(4), H(10), Py, 3JH,H = 6.40 Hz); 7.12 (m, 4 Н, H(5), H(11),
Py and H(4), H(10), Ph); 4.33 (dq, 8 Н, CH2CH3, 3JH,H = 7.52 Hz,
3JH,H = 14.65 Hz); 1.26 (t, 12 Н, CH2CH3, JH,H = 7.03 Hz).
31Р NMR (CDСl3), : 97.5.
3
Electrochemical oxidation of complex 3. Dipalladium comꢀ
plex 3 (0.5 mmol, 0.40 g) in MeCN (30 mL) was placed in an
electrochemical cell. Electrolysis was carried out with divided
anodic and cathodic spaces in the supporting electrolyte
Et4NBF4. Electricity (2 F) was passed through the electrolyte
based on 1 mole of the initial complex (268.0 mA h–1). After the
end of electrolysis, the reaction mixture was evaporated on
a rotary evaporator, washed with a saturated aqueous solution of
ammonium chloride (350 mL), and extracted with benzene
(340 mL). The organic layer was dried over MgSO4 for 24 h,
and the solvent was removed. The residue was purified by passꢀ
ing through a chromatographic column packed with silica gel
(hexane—dichloromethane (1 : 3) as an eluent). 2ꢀ(Pyridinꢀ2´ꢀ
yl)phenyl diethyl phosphonate (1) was obtained in a yield of 0.23 g
(79%). 31Р NMR (CDСl3), : 18.1.
This work was financially supported by the Russian
Science Foundation (Project No. 14ꢀ23ꢀ00016).
References
General procedure of electrolysis. The electrochemical cell
was loaded with palladium acetate (0.7 mmol, 0.16 g), 2ꢀphenylꢀ
pyridine (7 mmol, 1.104 g), and the corresponding base in acetoꢀ
nitrile (30 mL). Electricity (2 F) was passed through the electroꢀ
lyte based on 1 mole of the initial 2ꢀphenylpyridine (375.5 mA h–1).
Electrolysis was carried out at the potential Ер = 1.2 V. Diethylꢀ
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Received September 16, 2014;
in revised form October 27, 2014