C-P bond formation via selective electrocatalytic C-H phosphorylation

Article abstract of DOI:10.1080/10426507.2018.1555538

A new approach to phosphorylation of 2-phenylpyridine was proposed. It is possible to obtain the product of diethyl (2-(pyridin-2-yl)phenyl)phosphonate product in good yield (72%) by this method.

Full text of DOI:10.1080/10426507.2018.1555538

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
C-P bond formation via selective electrocatalytic C-
H phosphorylation
M. N. Khrizanforov, S. O. Strekalova, V. V. Grinenko, A. I. Kononov, E. L.
Dolengovski & Y. H. Budnikova
To cite this article: M. N. Khrizanforov, S. O. Strekalova, V. V. Grinenko, A. I. Kononov, E.
L. Dolengovski & Y. H. Budnikova (2019): C-P bond formation via selective electrocatalytic
C-H phosphorylation, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2018.1555538
To link to this article: https://doi.org/10.1080/10426507.2018.1555538
Published online: 09 Jan 2019.
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1555538
SHORT COMMUNICATION
C-P bond formation via selective electrocatalytic C-H phosphorylation
M. N. Khrizanforov , S. O. Strekalova , V. V. Grinenko , A. I. Kononov , E. L. Dolengovski , and Y. H.
Budnikova
Arbuzov Institute of Organic and Physical Chemistry of FRC Kazan Scientific Center of RAS, Kazan, Russia
ABSTRACT
ARTICLE HISTORY
Received 28 September 2018
Accepted 29 November 2018
A new approach to phosphorylation of 2-phenylpyridine was proposed. It is possible to obtain the
product of diethyl (2-(pyridin-2-yl)phenyl)phosphonate product in good yield (72%) by this method.
KEYWORDS
GRAPHICAL ABSTRACT
Phosphorylation; electrosyn-
thesis; electrocatalysis;
CH-substitution
Table 1. Electrochemical phosphorylation of 2-phenylpyridine by
(CH3)2C(OH)P(O)(OC2H5)2 (1:1.1 ratio).
Introduction
C-P bond containing organophosphorus compounds are widely
used in medical chemistry, biochemistry, materials, phosphine-
containing ligands for catalysis, and organic synthesis.[1–5] There
are only few electrochemical approach for the C-H substitution
with phosphorus-containing nucleophiles.[1] Successful examples
of electrochemical reactions have been mainly known so far only
for functionalization of nitroaromatic substrates.[5]
E of anode, V vs.
Ag/AgCl
Amount of
electricity
Product
yield (%)
Solvent:
DMF
1.0
1.0
1.0
1.5
1.5
1.5
2F
1F
2F
2F
1F
2F
0
0
20
0
8
72
CH3CN
CH3CN
DMF
CH3CN
CH3CN
Results and discussion
We used our accumulated experience in electrochemical
C–H-substitution[6–9] to develop a ligand-directed C-H-
phosphorylation method by electrochemical oxidation under
mild conditions involving Pd(OAc)2 as the catalyst and
(CH3)2C(OH)P(O)(OC2H5)2 as the accessible phosphorus
precursor. The use of the electrochemical method allowed
the conduction of the reaction at room temperature without
the addition of the oxidant with a controlled potential it was
possible to analyze the reaction steps particularly.
The electrochemical oxidation of 2-phenylpyridine and
(CH3)2C(OH)P(O)(OC2H5)2 (ratio 1:1.1, dropwise addition
of phosphorus agent during the whole electrolysis) in the
presence of 10 mol% of palladium acetate gives the ortho-
phosphorylation product in a yield of 72% in optimal pro-
cess conditions (Table 1).
Conditions: Room temperature, Pd(OAc)2 catalyst (10% based on 2-Ph-Py).
Isolated yields of diethyl-(2-pyridin-2-yl)phenyl)phosphonate.
Ag/AgCl) leads to the formation of diethyl-(2-pyridin-2-yl)
phenyl)phosphonate.
Experimental
The solution for electrolysis was prepared by mixing of 2-phe-
nylpyridine (1.4 mmol, 0.22g,), (CH3)2C(OH)P(O)(OC2H5)2
(1.6 mmol, 0.31g) and Pd(OAc)2 (0.14 mmol, 0.03g) in
CH3CN (30 mL). Electrolysis was carried out in undivided
electro-chemical cell at ambient temperature under argon
atmosphere at the potential of working electrode correspond-
ing to oxidation potential of the Pd(OAc)2 (1.5 V vs. Ag/
AgCl). The amount of electricity passed through the electro-
lyte were 2 F per one mole of (CH3)2C(OH)P(O)(OC2H5)2
Conclusions
The interaction of 2-phenylpyridine with (CH3)2C(OH)
P(O)(OC2H5)2 in the presence of Pd(OAc)2 at 1.5 V (vs. (75 mA ꢀ hꢁ1). After completing the electrolysis, the solution
CONTACT M. N. Khrizanforov
ß 2018 Taylor & Francis Group, LLC
khrizanforov@gmail.com

2
M. N. KHRIZANFOROV ET AL.
Phosphorus Sulfur Silicon Relat. Elem. 2016, 191, 1660–1661. DOI:
10.1080/10426507.2016.1225062.
was washed with distilled water (100 ml) and extracted with
CHCl3 (3 ꢀ 100 mL). The organic layer was dried over magne-
sium sulfate and filtered. The residual solution was concen-
trated. The reaction mixture was filtered through a plug of
silica (eluated with 5% EtOAc: 95% hexane). The filtrate was
concentrated, and the diethyl-(2-pyridin-2-yl)phenyl)phosph-
onate was isolated (0.29 g, 72%, colorless oil). 1H NMR
(400 MHz, C6D6) d: 8.83 (d,J ¼ 5.93 Hz, 1H); 8.13 (dt, J ¼ 7.99;
1.25 Hz, 1H); 7.88 (d,J ¼ 7.29 Hz, 2H); 7.66 (d, J ¼ 7.54 Hz,
1H); 7.42 (t, J ¼ 7.89 Hz,2H); 7.34 (m, 1H); 4.05 (dq, J ¼ 7.09;
7.95 Hz, 4H); 1.22 (t,J ¼ 7.01 Hz, 6H). 31hNMR (162 MHz,
C6D6): d 16.6. ESI-HRMS (þve): [C15H18NO3P]þ: found
293.66. Anal Calcd: C, 61.85; H, 6.23; N, 4.81; O, 16.48; P,
10.63 for C15H18NO3P. Found: C, 61.57; H, 6.17; P, 10.55.
[2] Khrizanforova, V. V.; Khrizanforov, M. N.; Gryaznova, T. V.;
Budnikova, Y. H. Electrochemical Pathway to CH/PH
Functionalization of Diphenylphosphine Oxide. Phosphorus
Sulfur Silicon Relat. Elem. 2016, 191, 1602–1603. DOI: 10.1080/
10426507.2016.1216430.
[3] Khrizanforov, M. N.; Strekalova, S. O.; Kholin, K. V.;
Khrizanforova, V. V.; Kadirov, M. K.; Gryaznova, T. V.;
Budnikova, Y. H. Novel Approach to Metal-induced Oxidative
Phosphorylation of Aromatic Compounds. Cat. Today. 2017,
279, 133–144. DOI: 10.1016/j.cattod.2016.06.001.
[4] Budnikova, Y. H; Gryaznova, T.V.; Grinenko, V.V.;
Khrizanforov, M.N. Eco-efficient Electrocatalytic C–P Bond
Formation. Pure. App. Chem. 2017, 89, 311–330.
[5] Khrizanforov, M.; Strekalova, S.; Kholin, K.; Khrizanforova, V.;
Grinenko, V.; Gryaznova, T.; Budnikova, Y. One-stage
Synthesis of FcP(O)(OC 2 H
5 ) 2 from Ferrocene and
a-Hydroxyethylphosphonate. RSC Adv. 2016, 6, 42701–42707.
DOI: 10.1039/C6RA04480H.
Acknowledgments
[6] Khrizanforov, M. N.; Strekalova, S. O.; Gryaznova, T. V.;
Khrizanforova, V. V.; Budnikova, Y. H. New Method of Metal-
induced Oxidative Phosphorylation of Benzene. Russ. Chem.
Bull. 2015, 64, 1926–1932. DOI: 10.1007/s11172-015-1095-z.
[7] Strekalova, S. O.; Khrizanforov, M. N.; Gryaznova, T. V.;
Khrizanforova, V. V.; Budnikova, Y. H. Electrochemical
Phosphorylation of Coumarins Catalyzed by Transition Metal
Complexes (Ni—Mn, Co—Mn). Russ. Chem. Bull. 2016, 65,
1295–1298. DOI: 10.1007/s11172-016-1451-7.
The authors gratefully acknowledge the Russian Science Foundation
No 14-23-00016 for financial support and CSF-SAC FRC KSC RAS for
the registration of spectra (NMR, ESI, Raman, etc.).
ORCID
M. N. Khrizanforov
S. O. Strekalova
V. V. Grinenko
A. I. Kononov
E. L. Dolengovski
Y. H. Budnikova
http://orcid.org/0000-0003-4714-4143
http://orcid.org/0000-0002-7940-7895
http://orcid.org/0000-0001-9235-3089
http://orcid.org/0000-0001-9125-5209
http://orcid.org/0000-0001-5745-3738
http://orcid.org/0000-0001-9497-4006
[8] Khrizanforov, M.; Khrizanforova, V.; Mamedov, V.; Zhukova,
N.; Strekalova, S.; Grinenko, V.; Gryaznova, T.; Sinyashin, O.;
Budnikova,
Y.
Single-stage
Synthetic
Route
to
Perfluoroalkylated Arenes via Electrocatalytic Cross-coupling of
Organic Halides Using Co and Ni Complexes. J. Organomet.
Chem. 2016, 820, 82–88. DOI: 10.1016/j.jorganchem.
2016.08.003.
[9] Khrizanforov, M.; Fedorenko, S.; Strekalova, S.; Kholin, K.;
Mustafina, A.; Zhilkin, M.; Khrizanforova, V.; Osin, Y.;
Salnikov, V.; Gryaznova, T.; Budnikova, Y. H. A Ni( iii ) com-
plex Stabilized by Silica Nanoparticles as an Efficient
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