New functionalized derivatives of mono- and diphosphonic acids substituted with five-membered nitrogen heterocycles

Article abstract of DOI:10.1007/s11172-017-1737-4

New types of (hydroxymethyl)phosphonic and (methylene)diphosphonic acids bearing heterocyclic fragments were synthesized by addition of tris(trimethylsilyl) phosphite to N-formyl derivatives of five-membered nitrogen heterocycles.

Full text of DOI:10.1007/s11172-017-1737-4

Russian Chemical Bulletin, International Edition, Vol. 66, No. 2, pp. 342—345, February, 2017
342
New functionalized derivatives of monoꢀ and diphosphonic acids
substituted with fiveꢀmembered nitrogen heterocycles
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I. Livantsova, R. S. Alekseyev, V. I. Terenin, and V. S. Petrosyan
Department of Chemistry, M. V. Lomonosov Moscow State University,
3 Build., 1 Leninskie Gory, 119991 Moscow, Russian Federation.
Eꢀmail: aprishchenko@yandex.ru
New types of (hydroxymethyl)phosphonic and (methylene)diphosphonic acids bearing
heterocyclic fragments were synthesized by addition of tris(trimethylsilyl) phosphite to Nꢀformyl
derivatives of fiveꢀmembered nitrogen heterocycles.
Key words: tris(trimethylsilyl) phosphite, fiveꢀmembered nitrogen heterocycles, Nꢀformylꢀ
substituted heterocycles, trimethylsilyl triflate.
Scheme 1
Functionalized phosphonic and (methylene)diphosꢀ
phonic acids and their derivatives bearing fragments of
nitrogen heterocycles are well known biomimetics of
hydroxy(amino) acids and natural pyrophosphates. Some
of these compounds, for instance, zoledronic, risedronic,
and minodronic acids, are widely applied in medicine as
the therapeutic agents for disorders of bone and calcium
metabolism. They are also of interest as promising plant
growth regulators and efficient polydentate ligands.1—3
Earlier, we have described convenient synthetic proceꢀ
dures to access a series of aminomethylenediphosphoric
acids and their derivatives from highly reactive synthones,
i.e., trimethylsilyl esters of trivalent phosphorus acids.4—7
The aim of the present work is to study the addition of
excess tris(trimethylsilyl) phosphite to readily available
Nꢀformylꢀsubstituted fiveꢀmembered rings with two or
three nitrogen heteroatoms. The heterocyclic compounds
were generated in situ using formic acid and N,N´ꢀdiꢀ
cyclohexylcarbodiimide as earlier described.8 It was found
that phosphite adds to the carbonyl group of Nꢀformyl
heterocycle only in the presence of the catalyst, trimethylꢀ
silyl triflate (cf. Refs 5 and 9). The reaction proceeds under
mild conditions and produces mixtures of phosphonates 1
and diphosphonates 2 in the ratios depending on the strucꢀ
ture of the starting Nꢀformyl heterocycle. For instance,
Nꢀformylꢀ3,5ꢀdimethylꢀ1Hꢀpyrazole gives predominantly
phosphonate 1c and Nꢀformylimidazole produces diphosꢀ
phonate 2a in high yield (Scheme 1). Owing to unusual
variability, this reaction allows simultaneous synthesis of
two types of the target products and, therefore, advantaꢀ
geously differs from the similar reaction between formaꢀ
mides and tris(trimethylsilyl) phosphite always giving only
aminomethylene diphosphonates.5
1, 2
Yield (%)
1
2
HetN =
(a),
(c),
(b),
(d)
a
b
c
d
19
30
86
59
83
62
17
30
Reagents and conditions: i. HCOOH, (cycloꢀC6H11N=)2C,
—(cycloꢀC6H11NH)2CO, 20 °C; ii. P(OSiMe3)3 (3 equiv.),
CF3SO3SiMe3 (0.26 equiv.), 40 °C.
phosphite proceeds similarly to the reactions of formaꢀ
mides of simple structure.5 The role of trimethylsilyl triꢀ
flate as a catalyst is to favor the formation of highly reacꢀ
tive intermediate iminium salts (Scheme 2). The absence
of further conversion of substituted trimethylsilyloxymeꢀ
thyl phosphonates 1 during the reaction is apparently can
be rationalized in terms of the bulkiness of the heteroꢀ
cyclic fragment impeding substitution of the C(1) triꢀ
methylsilyloxy group of phosphonates 1.
Trimethylsilyl esters 1 and 2 readily react with excess
methanol under mild conditions to give functionalized
monoꢀ and diphosphonic acids 3 and 4, respectively
(Scheme 3).
Thus, the addition of Nꢀformyl derivatives of fiveꢀ
membered nitrogen heterocycles to tris(trimethylesilyl)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0342—0345, February, 2017.
1066ꢀ5285/17/6602ꢀ0342 © 2017 Springer Science+Business Media, Inc.

Functionalized monoꢀ and diphosphonic acids
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 2, February, 2017
343
Scheme 2
phosphonic acids bearing fragments of fiveꢀmembered
nitrogen heterocycles via the unique reaction of trisꢀ
(trimethylsilyl) phosphite with Nꢀformylꢀsubstituted
heterocycles.
Experimental
1
H, 13C{1H}, and 31P{1H} NMR spectra were recorded with
a Bruker Avance 400 spectrometer at working frequencies of
400, 100, and 162 MHz, respectively. The chemical shifts are
given in the δ scale relative to Me4Si (1H, 13C{1H}) and a 85%
solution of H3PO4 in D2O (31P{1H}). All reactions were carried
out in anhydrous solvents under dry argon. The starting trimethylꢀ
silyl esters of trivalent phosphorus acids14,15 were synthesized by
the known procedures.
Scheme 3
Bis(trimethylsilyl) (1Hꢀimidazolꢀ1ꢀyl)(trimethylsilyloxy)ꢀ
methylphosphonate (1a) and tetrakis(trimethylsilyl) (1Hꢀimidazolꢀ
1ꢀyl)methylenediphosphonate (2a). To a stirred mixture of imidꢀ
azole (3.4 g, 0.05 mol) and formic acid (2.8 g, 0.06 mol) in
dichloromethane (50 mL), a solution of N,N´ꢀdicyclohexylcarboꢀ
diimide (14.4 g, 0.07 mol) in dichloromethane (20 mL) was
added. The mixture was stirred for 6 h and then kept for 12 h.
The precipitate was filtered off and the filtrate was successively
treated with tris(trimethylsilyl) phosphite (44.8 g, 0.15 mol) and
a solution of trimethylsilyl triflate (2.9 g, 0.013 mol) in dichloroꢀ
methane (10 mL). The mixture was heated in a boiling water
bath with simultaneous distillation off of the lowꢀboiling compoꢀ
nents. Vacuum distillation of the residue afforded 1.8 g (9%) of
phosphonate 1a, b.p. 102 °C (1 Torr), and 22.0 g (83%) of diphosꢀ
phonate 2a, b.p. 126 °C (1 Torr).
Phosphonate 1a. Found (%): C, 39.42; H, 7.83. C13H31N2O4PSi3.
Calculated (%): C, 39.57; H, 7.92. 1H NMR (CDCl3), δ: –0.38
(s, Me3SiO); –0.24 (s, 2 Me3Si); 5.22 (d, C(1)H, 2JP,H = 4.8 Hz);
6.57 and 7.15 (both s, CHHet). 13C{1H} NMR (CDCl3), δ: 1.62
(s, Me3Si); –0.25 and 0.05 (both s, 2 Me3Si); 76.47 (d, C(1),
1JP,C = 213.2 Hz); 106.61, 139.80, 146.52 (all s, CHet). 31P{1H}
NMR (CDCl3), δ: –4.02 (s).
The synthesized compounds 1—4 can found applicaꢀ
tions in the synthesis of new types of organophosphorus
compounds bearing both heterocyclic and phosphonic
moieties. These compounds are promising precursors for
pharmaceuticals for multifunctional targeted therapy,
plant growth regulating agents, and efficient polydentate
ligands to access new complexes of different (including
biogenic) metals with monoꢀ and diphosphorusꢀcontainꢀ
ing ligands.
It should be emphasized that in contrast to formamide
diethyl acetals reacting with esters of phosphorous acids
to give aminomethylene diphosphonates,10 reactions of
readily available Nꢀdiethoxymethyl derivatives of fiveꢀ
membered nitrogen heterocycles11—13 with tris(trimethylꢀ
silyl) phosphite involve the nitrogen—carbon bond cleavꢀ
age and produce diethoxymethyl phosphonates 5 in high
yields (Scheme 4).
Diphosphonate 2a. Found (%): C, 36.12; H, 7.52.
C16H40N2O6P2Si4. Calculated (%): C, 36.21; H, 7.60. 1H NMR
(CDCl3), δ: –0.15 (s, 2 Me3Si); –0.14 (s, 2 Me3Si); 3.55
(t, C(1)H, 2JP,H = 17.2 Hz); 6.57 and 7.15 (both s, CHHet). 13C{1H}
1
NMR (CDCl3), δ: 0.47 (s, 4 Me3Si); 67.80 (t, C(1), JP,C
=
= 168.2 Hz); 121.00 and 134.69 (both s, CHet). 31P{1H} NMR
(CDCl3), δ: –0.32 (s).
Scheme 4
Phosphonates 1b—d and diphosphonates 2b—d were syntheꢀ
sized similarly.
Bis(trimethylsilyl) (1Hꢀbenzimidazolꢀ1ꢀyl)(trimethylsilyloxy)ꢀ
methylphosphonate (1b). Yield 30%, b.p. 110 °C (1 Torr).
Found (%): C, 45.81; H, 7.40. C17H33N2O4PSi3. Calculated (%):
C, 45.92; H, 7.48. 1H NMR (CDCl3), δ: –0.44 (s, Me3Si); –0.25
2
(s, 2 Me3Si); 5.58 (d, C(1)H, JP,H = 4.4 Hz); 6.70—7.45
(m, CHHet). 13C{1H} NMR (CDCl3), δ: –0.22 (s, Me3Si); 1.11
(s, 2 Me3Si); 75.50 (d, C(1), 1JP,C = 214.1 Hz); 110.40, 120.23,
122.51, 123.19, 139.62, 143.28, 145.74 (all s, CHet). 31P{1H} NMR
(CDCl3), δ: –3.47 (s).
HetN =
,
; X = Me3Si (a), Et (b)
Tetra(trimethylsilyl) (1Hꢀbenzimidazolꢀ1ꢀyl)methylenediꢀ
phosponate (2b). Yield 62%, b.p. 139 °C (1 Torr). Found (%):
C, 41.26; H, 7.20. C20H42N2O6P2Si4. Calculated (%): C, 41.36;
H, 7.29. 1H NMR (CDCl3), δ: –0.38 and –0.31 (both s, 2 Me3Si);
Reagents and conditions: i. (XO)2POSiMe3, Me3SiCl, CH2Cl2,
40 °C.
In summary, we elaborated convenient procedures to
synthesize new functional derivatives of monoꢀ and diꢀ
2
–0.16 (s, Me3Si); 3.55 (t, C(1)H, JP,H = 16.8 Hz); 6.65—7.55

344
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 2, February, 2017
Prishchenko et al.
2
(m, CHHet). 13C{1H} NMR (CDCl3), δ: 1.10 (s, 4 Me3Si); 68.11
(d, C(1), JP,C = 167.3 Hz); 112.46, 119.92, 122.13, 122.75,
139.71, 141.75, 145.46 (all s, CHet). 31P{1H} NMR (CDCl3), δ:
–0.58 (s).
1H NMR (D2O—C5D5N), δ: 5.15 (d, C(1)H, JP,H = 6.4 Hz);
1
3
4
3
7.17 (dd, JH,H = 16.0 Hz, JH,H = 3.2 Hz); 7.47 (dd, JH,H =
= 16.0 Hz, JH,H = 3.2 Hz); 7.57 (s) (CHHet). 13C{1H} NMR
4
1
(D2O—C5D5N), δ: 78.85 (d, C(1), JP,C = 170.0 Hz); 114.16,
Bis(trimethylsilyl) (3,5ꢀdimethylꢀ1Hꢀpyrazolꢀ1ꢀyl)(trimethylꢀ
silyloxy)methylphosphonate (1c). Yield 86%, b.p. 106 °C (1 Torr).
Found (%): C, 42.49; H, 8.28. C15H35N2O4PSi3. Calculated (%):
C, 42.62; H, 8.35. 1H NMR (CDCl3), δ: –0.38 and –0.31 (both
s, 2 Me3Si); –0.16 (s, Me3Si); 1.71 and 1.99 (both s, 2 Me); 5.36
125.86, 129.74, 138.52 (all s, CHet). 31P{1H} NMR (D2O—C5D5N),
δ: 6.88 (s).
3,5ꢀDimethylꢀ1Hꢀpyrazolꢀ1ꢀyl(hydroxy)methylphosphonic
acid (3c). Yield 97%, m.p. 357—359 °C (decomp.). Found (%):
C, 34.78; H, 5.30. C6H11N2O4P. Calculated (%): C, 34.96;
H, 5.38. 1H NMR ((CD3)2SO—C5D5N), δ: 1.86 and 2.20 (both s,
2 Me); 4.92 (d, C(1)H, 2JP,H = 6.0 Hz); 5.64 (s, CHHet). 13C{1H}
NMR ((CD3)2SO—C5D5N), δ: 10.47 and 12.44 (both s, 2 Me);
88.18 (d, C(1), 1JP,C = 191.4 Hz); 103.71, 144.05 (both s, CHet).
31P{1H} NMR ((CD3)2SO—C5D5N), δ: 10.42 (s).
2
(s, CHHet); 5.40 (d, C(1)H, JP,H = 7.2 Hz). 13C{1H} NMR
(CDCl3), δ: –1.62 (s, Me3Si); –0.25 and 0.05 (both s, 2 Me3Si);
10.77 and 12.36 (both s, 2 Me); 81.19 (d, C(1), 1JP,C = 214.1 Hz);
106.61, 139.80, 146.52 (all s, CHet). 31P{1H} NMR (CDCl3), δ:
–3.35 (s).
Tetrakis(trimethylsilyl) (3,5ꢀdimethylꢀ1Hꢀpyrazolꢀ1ꢀyl)methꢀ
ylenediphosphonate (2c). Yield 7%, b.p. 129 °C (1 Torr).
Found (%): C, 38.52; H, 7.86. C18H44N2O6P2Si4. Calculated (%):
1HꢀBenzotriazolꢀ1ꢀyl(hydroxy)methylphosphonic acid (3d).
Yield 95%. m.p. 105—107 °C (decomp.). Found (%): C, 36.55;
H, 3.48. C7H8N3O4P. Calculated (%): C, 36.70; H, 3.52. 1H NMR
2
C, 38.69; H, 7.94. 1H NMR (CDCl3), δ: –0.12 and –0.16 (both s,
((CD3)2SO), δ: 6.43 (d, C(1)H, JP,H = 7.2 Hz); 7.41 (dd,
2
4
3
4 Me3Si); 1.80 and 2.01 (both s, 2 Me); 3.58 (t, C(1)H, JP,H
=
3JH,H = 6.4 Hz, JH,H = 3.2 Hz); 7.89 (dd, JH,H = 6.4 Hz,
= 17.2 Hz); 5.36 (s, CHHet). 13C{1H} NMR (CDCl3), δ: 0.35
(s, 4 Me3Si); 10.80 and 12.40 (both s, 2 Me); 68.09 (t, C(1),
1JP,C = 168.2 Hz); 106.68, 139.86, 146.57 (all s, CHet). 31P{1H}
NMR (CDCl3), δ: –0.30 (s).
4JH,H = 3.2 Hz) (CHHet). 13C{1H} NMR ((CD3)2SO), δ: 79.96
(d, C(1), JP,C = 187.7 Hz); 114.92, 118.84, 125.42, 126.86,
1
131.87, 145.86 (all s, CHet). 31P{1H} NMR ((CD3)2SO), δ: 10.62 (s).
1HꢀBenzimidazolꢀ1ꢀylmethylenediphosphonic acid (4b). Yield
98%. m.p. 348—350 °C (decomp.). Found (%): C, 32.74; H, 3.40.
C8H10N2O6P2. Calculated (%): C, 32.89; H, 3.45. 1H NMR
Bis(trimethylsilyl) (1Hꢀbenzotriazolꢀ1ꢀyl)(trimethylsilyloxy)ꢀ
methylphosphonate (1d). Yield 59%, b.p. 108 °C (1 Torr).
Found (%): C, 43.03; H, 7.16. C16H32N3O4PSi3. Calculated (%):
C, 43.12; H, 7.24. 1H NMR (CDCl3), δ: –0.36 (s, Me3Si); –0.05
2
((CD3)2SO), δ: 4.18 (t, C(1)H, JP,H = 16.0 Hz); 7.18 (dd,
4
3
3JH,H = 6.0 Hz, JH,H = 3.2 Hz); 7.46 (dd, JH,H = 6.0 Hz,
2
(s, 2 Me3Si); 6.26 (d, C(1)H, JP,H = 6.4 Hz); 6.99—7.76
4JH,H = 3.2 Hz); 7.56 (s) (CHHet). 13C{1H} NMR ((CD3)2SO),
δ: 66.86 (d, C(1), JP,C = 142.1 Hz); 113.79, 125.73, 129.59,
(m, C6H4). 13C{1H} NMR (CDCl3), δ: –0.93 (s, Me3Si); –0.75
1
1
(s, Me3Si); –0.43 (s, Me3Si); 80.73 (d, C(1), JP,C = 13.2 Hz);
138.88 (all s, CHet). 31P{1H} NMR ((CD3)2SO), δ: 15.63 (s).
3,5ꢀDimethylꢀ1Hꢀpyrazolꢀ1ꢀylmethylenediphosphonic acid
(4c). Yield 98%. m.p. 357—359 °C (decomp.). Found (%): C, 26.49;
H, 4.52. C6H12N2O6P2. Calculated (%): C, 26.68; H, 4.48.
1H NMR ((CD3)2SO—C5D5N), δ: 1.82 and 2.14 (both s, 2 Me);
3.97 (t, C(1)H, 2JP,H = 15.6 Hz); 5.60 (s, CHHet). 13C{1H} NMR
((CD3)2SO—C5D5N), δ: 10.44 and 12.34 (both s, 2 Me); 55.57
(t, C(1), 1JP,C = 181.7 Hz); 105.63, 140.83 (both s, CHet). 31P{1H}
NMR ((CD3)2SO—C5D5N), δ: 15.03 (s).
113.37, 119.20, 124.17, 127.30, 131.84, 146.45 (all s, CHet).
31P{1H} NMR (CDCl3), δ: –4.81 (s).
Tetrakis(trimethylsilyl) (1Hꢀbenzotriazolꢀ1ꢀyl)methylenediꢀ
phosphonate (2d). Yield 30%, b.p. 133 °C (1 Torr). Found (%):
C, 39.03; H, 7.01. C19H41N3O6P2Si4. Calculated (%): C, 39.22;
H, 7.10. 1H NMR (CDCl3), δ: –0.11 (s, 4 Me3Si); 3.75 (t, C(1)H,
2JP,H = 16.8 Hz); 7.17—7.83 (m, C6H4). 13C{1H} NMR (CDCl3),
1
δ: 0.01 (s, 4 Me3Si); 67.71 (t, C(1), JP,C = 168.2 Hz); 110.50,
114.55, 119.44, 126.22, 129.93, 140.27 (all s, CHet). 31P{1H} NMR
(CDCl3), δ: –0.47 (s).
1HꢀBenzotriazolꢀ1ꢀylmethylenediphosphonic acid (4d). Yield
96%. m.p. 355—357 °C (decomp.). Found (%): C, 28.56; H, 3.14.
C7H9N3O6P2. Calculated (%): C, 28.68; H, 3.09. 1H NMR
((CD3)2SO—C5D5N), δ: 3.88 (t, C(1)H, 2JP,H = 17.2 Hz); 8.01
(1HꢀImidazolꢀ1ꢀyl)methylenediphosphonic acid (4a). A soluꢀ
tion of diphosphonate 2a (10.6 g, 0.02 mol) in diethyl ether
(15 mL) was added to methanol (40 mL) at 10 °C under continuꢀ
ous stirring. The mixture was heated to reflux and concentrated.
The white crystals were dried in vacuo (1 Torr) for 1 h to give
4.7 g (98%) of acid 4a, m.p. 174—176 °C. Found (%): C, 19.69;
H, 3.28. C4H8N2O6P2. Calculated (%): C, 19.85; H, 3.33.
3
3
(d, JH,H = 8.2 Hz); 8.95 (d, JH,H = 8.2 Hz). 13C{1H} NMR
1
((CD3)2SO—C5D5N), δ: 65.28 (t, C(1), JP,C = 150.2 Hz);
113.61, 118.64, 124.03, 125.42, 126.86, 138.69 (all s, CHet).
31P{1H} NMR ((CD3)2SO—C5D5N), δ: 16.41 (s).
Bis(trimethylsilyl) diethoxymethylphosphonate (5a). A soluꢀ
tion of Nꢀdiethoxymethylimidazole (4 g, 0.024 mol), tris(triꢀ
methylsilyl) phosphite (18 g, 0.06 mol), and chlorotrimethylꢀ
silane (5 g, 0.046 mol) in dichloromethane (20 mL) was refluxed
for 1 h and then the solvent was carefully distilled off upon
heating in a boiling water bath. Vacuum distillation of the resiꢀ
2
1H NMR (D2O—C5D5N), δ: 3.33 (t, C(1)H, JP,H = 16.0 Hz);
6.55 and 7.85 (both s, CHHet). 13C{1H} NMR (D2O—C5D5N),
1
δ: 66.26 (t, C(1), JP,C = 139.9 Hz); 117.83 and 132.43 (both s,
CHet). 31P{1H} NMR (D2O—C5D5N), δ: 14.66 (s).
Acids 3a—d and 4b—d were synthesized similarly.
1HꢀImidazolꢀ1ꢀyl(hydroxy)methylphosphonic acid (3a). Yield
96%, m.p. 144—145 °C (decomp.). Found (%): C, 26.86;
H, 3.88. C4H7N2O4P. Calculated (%): C, 26.98; H, 3.96. 1H NMR
due afforded 5.8 g (74%) of compound 5a, b.p. 104 °C (2 Torr).
3
1H NMR (CDCl3), δ: 0.03 (s, Me3Si); 0.97 (t, 2 CH3, JH,H
=
= 6.8 Hz); 3.38—3.55 (m, 2 CH2O); 4.34 (d, C(1)H, 2JP,H = 5.2 Hz).
2
(D2O—C5D5N), δ: 6.81 (d, C(1)H, JP,H = 4.2 Hz); 6.57 and
13C{1H} NMR (CDCl3), δ: 0.67 (s, 2 Me3Si); 14.85 (s, 2 Me);
7.92 (both s, CHHet). 13C{1H} NMR (D2O—C5D5N), δ: 78.81
63.97 and 64.08 (both s, 2 CH2O); 98.97 (d, C(1)H, JP,C
=
1
1
(d, C(1), JP,C = 180.4 Hz); 117.96 and 132.86 (both s, CHet).
= 216.0 Hz). 31P{1H} NMR (CDCl3), δ: –3.58 (s) (cf. Ref. 16).
Phosphonate 5b was synthesized similarly.
31P{1H} NMR (D2O—C5D5N), δ: 7.47 (s).
1HꢀBenzimidazolꢀ1ꢀyl(hydroxy)methylphosphonic acid (3b).
Yield 94%, m.p. 157—159 °C (decomp.). Found (%): C, 41.97;
H, 3.91. C8H9N2O4P. Calculated (%): C, 42.12; H, 3.98.
Diethyl (diethoxymethyl)phosphonate (5b). Yield 78%,
b.p. 93 °C (2 Torr). 1H NMR (CDCl3), δ: 0.81 (t, 2 CH3, 3JH,H
=
3
= 6.8 Hz); 0.91 (t, 2 CH3, JH,H = 7.2 Hz); 3.10—3.50

Functionalized monoꢀ and diphosphonic acids
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 2, February, 2017
345
(m, 2 CH2O); 3.60—3.80 (m, 2 CH2O); 4.32 (d, C(1)H, 2JP,H
=
6. A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
= 4.8 Hz). 13C{1H} NMR (CDCl3), δ: 14.62 (s, 2 Me); 15.93
(d, Me, 3JP,C = 5.5 Hz); 62.41 (d, CH2O, 3JP,C = 6.5 Hz); 63.99
(d, CH2O, 2JP,C = 10.1 Hz); 98.59 (d, C(1)H, 1JP,C = 207.7 Hz).
31P{1H} NMR (CDCl3), δ: 13.63 (s) (cf. Ref. 17).
Livantsova, I. S. Ershov, V. S. Petrosyan, Heteroat. Chem.,
2015, 26, 101.
7. A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
Livantsova, G. M. Averochkin, V. S. Petrosyan, Heteroat.
Chem., 2015, 26, 405.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 14ꢀ03ꢀ00001,
15ꢀ03ꢀ00002, and 17ꢀ03ꢀ00169).
8. A. R. Katriztky, H.ꢀX. Chang, B. Yang, Synthesis, 1995, 503.
9. A. D. Dilman, S. L. Ioffe, Chem. Rev., 2003, 103, 733.
10. A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
Livantsova, V. S. Petrosyan, Heteroat. Chem., 2009, 20, 352.
11. N. J. Curtius, R. S. Brown, J. Org. Chem., 1980, 45, 4038.
12. A. R. Katriztky, J. J. Slawinski, F. Brunner, S. Gorun,
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Received June 23, 2016;
in revised form October 12, 2016