Electrochemical phosphorylation of arenes catalyzed by cobalt under oxidative and reductive conditions

Article abstract of DOI:10.1080/10426507.2018.1540488

Catalyst capable to operate in cathode and anode spaces simultaneously was found. Electrochemical regeneration of active form of catalyst Co²⁺bpy (1%) under oxidative as well as reductive conditions allows the C–H/P–H coupling of dialkyl-H-phos

Full text of DOI:10.1080/10426507.2018.1540488

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
Electrochemical phosphorylation of arenes
catalyzed by cobalt under oxidative and reductive
conditions
S. O. Strekalova, V. V. Grinenko, T. V. Gryaznova, A. I. Kononov, E. L.
Dolengovski & Y. H. Budnikova
To cite this article: S. O. Strekalova, V. V. Grinenko, T. V. Gryaznova, A. I. Kononov, E. L.
Dolengovski & Y. H. Budnikova (2018): Electrochemical phosphorylation of arenes catalyzed by
cobalt under oxidative and reductive conditions, Phosphorus, Sulfur, and Silicon and the Related
Elements, DOI: 10.1080/10426507.2018.1540488
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1540488
Electrochemical phosphorylation of arenes catalyzed by cobalt under oxidative
and reductive conditions
S. O. Strekalova , V. V. Grinenko , T. V. Gryaznova , A. I. Kononov
E. L. Dolengovski , and Y. H. Budnikova
,
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Kazan, Russia
ABSTRACT
ARTICLE HISTORY
Catalyst capable to operate in cathode and anode spaces simultaneously was found.
Received 29 September 2018
Accepted 23 October 2018
2þ
Electrochemical regeneration of active form of catalyst Co bpy (1%) under oxidative as well as
reductive conditions allows the C–H/P–H coupling of dialkyl-H-phosphonate and various aromatic
or heteroaromatic compounds.
KEYWORDS
Phosphorylation; cobalt;
electrocatalysis;
CH-substitution
GRAPHICAL ABSTRACT
[
10–13]
[14–18]
1
. Introduction
electrooxidative
and electroreduction
reactions
have been developed. In comparison with direct electrolysis,
indirect processes in which redox mediators (catalysts) are
used have more opportunities and advantages both in terms
for synthesis and research of the mechanisms of proc-
Organophosphorus compounds are important class of sub-
stances which are widely used in various areas of human
activity. Typical methods for the preparation of arylphospho-
nates are multi-stage and long-term processes requiring high
[
19]
[1–5]
esses.
For example, indirect organic electrosynthesis often
temperature and the use of additional expensive reagents.
demonstrates a higher selectivity of the reaction, since elec-
trolysis is carried out at lower potentials than the oxidation-
reduction potentials of the initial reagents.
Organic electrosynthesis is considered as a methodology
for the environmentally friendly preparation of organic com-
pounds, since dangerous and toxic redox agents, which may
be necessary and commonly used in classical reactions, are
replaced by a reaction at the electrode under an influence of
2. Results and discussion
[6–8]
electric current.
Traditional electrochemical methods in
organic synthesis have been considered in many mono- C–H bond activation reactions catalyzed by transition metals
[
5, 9]
graphs and reviews.
applications of
In recent years new strategies and are considered as a powerful tool for the functionalization
the
implementation
of
organic and production of organic molecules possessing huge
CONTACT V. V. Grinenko
grinenkovaleriya@gmail.com
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS,
Kazan, Russia.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
ß 2018 Taylor & Francis Group, LLC

2
S. O. STREKALOVA ET AL.
2þ
Scheme 1. Phosphorylation of arenes catalyzed by Co. Conditions: rt, Q ¼ 2F per mol of diethyl-H-phosphonate, [Co bpy] (1%), CH
3
CN.
importance for the pharmaceutical industry and material sci- Electrochemical reactions are easily scaled, which also
[20, 21]
ence.
Methods of direct functionalization of C–H bonds applies to their advantages and can be realized in the future.
can be considered as atom-economical approaches. Over the
past decades, the strategy for activating of C–H bonds has
been successfully implemented mainly using 4d- and 5d-tran-
sition metals (Pd, Pt, Ag, etc.). The use of more cost-effective
alternative systems based on more common metals such as
cobalt to activate C–H bonds seemed impossible until
recently, despite the predominance of such metals in the
active center of different enzymes, and as a rule harsh reac-
tion conditions were often required to achieve their reactivity.
We assumed that the phosphorylation of aromatic com-
pounds can be realized in one stage and at room tempera-
ture taking advantage of the electrochemical metal complex
4
. Experimental
4
.1. NMR experiments
NMR spectras were recorded with multi-nuclear spectrom-
1
eter Bruker AVANCE-400 (400.1 MHz ( H), 100.6 MHz
1
3
31
(
C) and 162.0 MHz ( P)). Chemical shifts are given in
parts per million relative to SiMe (1H, internal solvent) and
4
31
8
5% H PO ( P, external). The spectroscopic data for 1-7
3 4
[
6]
matched that reported in the literature.
[22–28]
catalysis.
4
.1.1. Diethyl phenylphosphonate (1)
We carried out a series of experiments to obtain phos-
phorylated aromatic compounds (benzene and its derivatives,
31
1
Colorless oil. P NMR (162 MHz, CDCl ) 18.3. H NMR
3
(400 MHz, CDCl ) 7.82–7.73 (m, 2H), 7.55–7.47 (m, 1H),
3
coumarins) using CoCl bpy as a catalyst and commercially
2
7
¼
.43–7.38 (m, 2H), 4.16–3.87 (m, 4H), 1.31 (t, JH-H
7.0 Hz, 6H).
available inexpensive and stable diethyl-H-phosphonate as
phosphorylating reagent. The distinctive feature of the process
is an equimolar ratio of arene:phosphorylation reagent (1:1)
and the room temperature. It was found that Co is capable to 4.1.2. Diethyl 4-cyanophenylphosphonate (2)
ꢁ
31
catalyze the phosphorylation reaction of arenes under both the White solid; mp ¼31–33 C. P NMR (162 MHz, CDCl3)
1
electrooxidation and electroreduction conditions (Scheme 1).
15.5. H NMR (400 MHz, CDCl ) 7.92 (dd, J ¼ 13.4 Hz,
3
P-H
The maximum yields of the products are achievable after 2H), 7.78–7.72 (m, 2H), 4.23–4.07 (m, 4H), 1.34 (t, JH-H
keeping the reaction mixture prior to electrolysis for some
¼
7.3 Hz, 6H).
[
6]
time necessary for the formation of cobalt phosphonate.
00% conversion of diethyl-H-phosphonate was achieved
1
4
.1.3. Diethyl 3-(dimethylamino)phenylphosphonate (3)
during the synthesis; it did not remain in the reaction mix-
ture after passing 2 F of electricity. The phosphorylation
product was not formed in the absence of the catalyst.
ꢁ
31
Yellow solid; mp ¼55–58 C. P NMR (162 MHz, CDCl3)
1
1
9.2. H NMR (400 MHz, CDCl ) 7.59–7.50 (m, 2H),
3
7
.35–7.29 (m, 3H), 4.21–4.01 (m, 4H), 2.98 (s, 6H), 1.27 (t,
JH-H ¼ 7.1 Hz, 6H).
.1.4. Diethyl 4-nitrophenylphosphonate (4)
3
. Conclusions
Thus, a cobalt catalyst which is able to work in cathode and
anode spaces simultaneously was found. It has been estab-
lished that the electrochemical regeneration of active form
of catalyst (1%) based on unsaturated complex Co bpy
under oxidative as well as reductive conditions allows the
C–H/P–H coupling of dialkyl-H-phosphonate and various
aromatic or heteroaromatic compounds with yields up to
4
31
Colorless viscous oil. P NMR (162 MHz, CDCl ) 13.2. 1H
3
NMR (400 MHz, CDCl ) 8.33 (dd, J ¼ 6.9 Hz, 2H), 7.97 (dd,
3
2
þ
J ¼ 12.7 Hz, 2H), 4.21–4.11 (m, 4H), 1.71–1.66 (m, 4H), 1.37
(t, J ¼ 7.2 Hz, 6H).
8
0% in reductive conditions and up to 68% in oxidative 4.1.5. Diethyl 2-oxo-2H-chromen-3-ylphosphonate (5)
ꢁ
31
conditions. The use of a cobalt complex in electroreductive White solid; mp ¼65–66 C. P NMR (162 MHz, CDCl
)
3
1
3
conditions leads to a better yield of arylphosphonates as the 10.37. H NMR (400 MHz, CDCl
): 8.53 (d, JPH ¼ 17.2 Hz,
3
þ
reaction proceeds without overpotential (ꢀ0.3 V vs Fc /Fc). 1H, C -H), 7.66–7.60 (m, 2H, ArH), 7.37–7.33 (m, 2H,
4

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Table 1. Electrochemical phosphorylation of arenes by diethyl-H-phosphonates (0.01 M, NaCl) reference electrode that had two sections
(
ratio 1:1). Conditions: room temperature, Q ¼ 2F per mol of diethyl-H-
2þ
separated with Vycor, the second one containing a saturated
phosphonate, galvanostatic mode, (1%) [Co bpy], isolated yields.
solution of the background salt in CH CN. The surface area
ꢂ
3
Yield (%)
of the working platinum (Pt) U-shaped electrode amounted
Reduction
condition
Oxidation
condition
2
to 48.00 cm . A ceramic plate with a pore size of 10 lm was
Number
Product
used as a membrane. During the preparative synthesis, the
electrolyte was continuously stirred using a magnetic stirrer
with a continuous inflow of an inert gas that was run
through a purification system to remove oxygen and other
impurity gases. A platinum grid served as a cathode, and
the catholyte was a saturated solution of Et NBF supporting
1
56
80
78
31
48
44
P(O)(OEt)2
2
3
NC
P(O)(OEt)2
4
4
electrolyte in the corresponding solvent.
P(O)(OEt)2
Me N
Acknowledgements
2
4
5
76
59
50
52
The authors gratefully acknowledge the Russian Science Foundation
No 14-23-00016 for financial support.
O N
P(O)(OEt)2
2
P(O)(OEt)2
ORCID
O
O
S. O. Strekalova
V. V. Grinenko
T. V. Gryaznova
A. I. Kononov
http://orcid.org/0000-0002-7940-7895
http://orcid.org/0000-0001-9235-3089
http://orcid.org/0000-0002-8076-8540
http://orcid.org/0000-0002-2038-537X
http://orcid.org/0000-0001-5745-3738
6
7
P(O)(OEt)2
70
73
68
65
O
O
O
E. L. Dolengovski
P(O)(OEt)2
O
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