Catalyst- A nd Solvent-Free Hydrophosphorylation of Ketones with Secondary Phosphine Oxides: Green Synthesis of Tertiary α-Hydroxyphosphine Oxides

Article abstract of DOI:10.1055/s-0040-1707945

Tertiary α-hydroxyphosphine oxides have been synthesized via the catalyst- A nd solvent-free reaction between available secondary phosphine oxides and aliphatic, aromatic and heteroaromatic ketones at 20-62? °C in near to 96-98percent yield. The developed method meets the requirements of green chemistry and the PASE (pot, atom, step economy) paradigm. According to quantum-chemical calculations at the B3LYP/6-311++G(d,p) level, the synthesized hydroxyphosphine oxides feature a weak (≈3 kcal·mol ^-1) O-H···O=P intramolecular hydrogen bond.

Full text of DOI:10.1055/s-0040-1707945

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2020, 52, A–I
paper
A
en
N. K. Gusarova et al.
Paper
Synthesis
Catalyst- and Solvent-Free Hydrophosphorylation of Ketones
with Secondary Phosphine Oxides: Green Synthesis of Tertiary
-Hydroxyphosphine Oxides
Nina K. Gusarova
R1
R1
R1
R1
O
H
O
O
20–62 °C, 0.25–24 h
R2
R3
+
R2
P
13 examples
96–98%
P
Nina I. Ivanova
R3
no catalyst and solvent
Kseniya O. Khrapova
Pavel A. Volkov
HO
R1 = Ph, Ph(CH2)2, 4-ClC6H4(CH2)2
R2 = CH2C(=O)OEt, c-C6H11, 4-ClC6H4, 4-NO2C6H4, Ph
R2 - R3 = (CH2)4, (CH2)5; R3 = Me, CH2Cl, 2-Py
Anton A. Telezhkin
Lyudmila I. Larina
Andrei V. Afonin
Dmitry V. Pavlov
Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian
Branch of the Russian Academy of Sciences, 1 Favorsky Str.,
664033 Irkutsk, Russian Federation
boris_trofimov@irioch.irk.ru
Received: 14.02.2020
Accepted after revision: 06.04.2020
Published online: 22.04.2020
Among the known and expedient methods for the syn-
thesis of tertiary -hydroxyphosphine oxides, the addition
of secondary phosphine oxides to aldehydes, easily pro-
ceeding under non-catalytic conditions and extensively
studied over the last two decades,8 should be mentioned.
Most of these known reactions have been carried out in
organic solvents,8a–e and only in one work catalyst- and
solvent-free rapid addition of secondary phosphine chalco-
genides to aldehydes is described.8f
At the same time, similar addition of secondary phos-
phine oxides to ketones is much less investigated. It was re-
ported that dialkyl- and diarylphosphine oxides react with
aliphatic and aromatic ketones in the presence of a basic
catalyst (alkali metals and alkali metal hydroxides, triethyl-
amine)9 to form the corresponding tertiary -hydroxyphos-
phine oxides. A similar non-catalytic reaction of secondary
phosphine oxides took place only for activated ketones con-
taining a trifluoromethyl group,10a,b as well as for phenyl-
ethynyl alkyl ketones.10c
It should be emphasized that all known approaches to
ketone phosphorylation by secondary phosphine chalco-
genides were implemented in an organic solvent medium.
Meanwhile, in recent years, special attention has been paid
to the development of addition reactions of P–H com-
pounds to multiple bonds, which occur without catalyst
and solvent.8f,11 Such reactions meet the ecological require-
ments of the green and click chemistry. But perhaps more
important is that the above catalyst- and solvent-free
methodologies often start up the processes unrealizable
under conventional conditions.11a,d Sometimes, without
solvent, the reactions take completely a different direc-
tion.11d
DOI: 10.1055/s-0040-1707945; Art ID: ss-2020-z0088-op
Abstract Tertiary -hydroxyphosphine oxides have been synthesized
via the catalyst- and solvent-free reaction between available secondary
phosphine oxides and aliphatic, aromatic and heteroaromatic ketones
at 20–62 °C in near to 96–98% yield. The developed method meets the
requirements of green chemistry and the PASE (pot, atom, step econo-
my) paradigm. According to quantum-chemical calculations at the
B3LYP/6-311++G(d,p) level, the synthesized hydroxyphosphine oxides
feature a weak (≈3 kcal·mol–1) O−H···O=P intramolecular hydrogen
bond.
Key words ketones, secondary phosphine oxides, catalyst- and
solvent-free addition, -hydroxyphosphine oxides
Tertiary phosphine oxides refer to an important class of
organophosphorus compounds, which are widely used as
ligands for the preparation of metal complex catalysts,1 ex-
tractive agents of heavy and noble metals, as well as trans-
uranic elements,2 stabilizing solvents for the design of con-
ductive nanomaterials,3 flame retardants,4 cellulose bleach-
es,5 prospective objects for medicine, and reactive building
blocks for organic synthesis.6 A particular attention is
drawn to tertiary phosphine oxides containing reactive
functional groups capable of further modification.7 For ex-
ample, tertiary phosphine oxides with a hydroxyl function,
imparting hydrophilic properties to the molecule, can be
further employed for design of metal complex phase-
transfer catalysts.7a Besides, tertiary phosphine oxides with
the -hydroxy group easily react with electron-deficient
acetylenes to afford acrylates, attractive monomers for the
production of non-combustible polymeric materials.7c,d
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–I
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
N. K. Gusarova et al.
Paper
Synthesis
In this paper, we report on a convenient approach to the
catalyst- and solvent-free synthesis of new representatives
of tertiary -hydroxyphosphine oxides from secondary
phosphine oxides 1–3 and ketones 4–12. The only known of
products, synthesized by us, -hydroxyphosphine oxide
13a, was prepared earlier9d by the reaction of diphenyl-
phosphine oxide (1) and acetophenone (4) in the system
Et3N/THF, the yield being 65%. At room temperature, the
above reaction almost does not occur (Scheme 1). However,
we have found that the hydrophosphorylation of ketone 4
with phosphine oxide 1 proceeds easily at room tempera-
ture under non-catalytic conditions without a solvent to
give -hydroxyphosphine oxide 13a in almost quantitative
yield (Scheme 1).
Previous work9d
reflux
This work
O
Ph
Ph
without catalyst
and solvent
13a, 65%
P
Me
Ph
Ph
O
H
O
Et3N/THF
C
Ph
P
+
r.t.
HO
r.t.
Me
13a
not
formed
Ph
13a, 98%
4
1
Scheme 1 Reaction of diphenylphosphine oxide with acetophenone
aliphatic, aromatic, and heteroaromatic substituents, with-
out catalyst and solvent to form tertiary -hydroxyphos-
phine oxides 13a–m. The addition is realized at room tem-
perature (or slight heating) and almost quantitatively (Table
1) that corresponds to the PASE paradigm.13
Our experiments have shown that not only phosphine
oxide 1, but also bis(2-arylethyl)phosphine oxides 2 and 3
(easily prepared from red phosphorus and styrenes12) are
capable of reacting with various ketones 4–12, containing
The reaction was monitored by 31P NMR spectroscopy
until the complete disappearance of signals of phosphine
oxides 1–3 (range P = 21–30) and the appearance of signals
of the final adducts 13a–m (range P = 29–53).
Table 1 Synthesis of Tertiary Hydroxyphosphine Oxides 13a–ma
R1
R1
O
C
R1
R1
O
H
R2
R3
P
O
20–62 °C, 0.25–24 h
R2
P
+
R3
HO
no catalyst and solvent
4–12
13a–m
1–3
Entry
Phosphine oxides 1–3
Ketones 4–12
Temp (°C) (Time, h)
20–25 (24)
Products 13a–m
Isolated yield (%)b
Me
C
O
P
O
O
P
H
1
98
Me
OH
4
5
6
1
1
13a
O
Me
MeCCH2COEt
P
C
CH2CO2Et
2
3
20–25 (19)
97
96
O
O
OH
13b
O
P
C
O
1
1
60–62 (4)
OH
13c
O
P
C
O
4
60–62 (3)
98
OH
7
13d
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–I

C
N. K. Gusarova et al.
Paper
Synthesis
Table 1
Entry
Phosphine oxides 1–3
Ketones 4–12
Temp (°C) (Time, h)
60–62 (8)
Products 13a–m
Isolated yield (%)b
Me
C
O
P
O
5
6
1
97
Me
OH
8
4
13e
O
O
Me
P
P
60–62 (24)
96
H
HO
2
1
13f
O
P
Cl
O
7
60–62 (3)
97
Cl
OH
9
9
13g
O
P
8
9
2
1
60–62 (14)
98
96
Cl
HO
13h
Me
C
O
P
O
Me
Cl
Cl
60–62 (3)
OH
10
13i
Me
O
P
NO2
C
O
O2N
10
11
12
1
2
1
60–62 (7)
98
97
97
Me
OH
11
13j
O
Me
P
11
60–62 (23)
HO
NO2
13k
O
P
Ph
C
N
N
O
Ph
60–62 (0.25)
OH
12
13l
Thieme. All rights reserved. Synthesis 2020, 52, A–I

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N. K. Gusarova et al.
Paper
Synthesis
Table 1
Entry
13
Phosphine oxides 1–3
Ketones 4–12
Temp (°C) (Time, h)
20–25 (2)
Products 13a–m
Isolated yield (%)b
98
1
12
13l
Cl
Cl
O
O
P
P
14
12
60–62 (8)
96
N
H
HO
Ph
Cl
Cl
13m
3
a Reaction conditions: phosphine oxides 1–3 (1 mmol), ketones 4–12 (1.05 mmol), 20–62 °C, 0.25–24 h, argon.
b Conversion of phosphine oxides 1–3 are quantitative (data according to 31P NMR analysis).
As seen from Table 1, the addition of diphenylphosphine
oxide (1) to the C=O group is completed by 3–5 times faster
than that in the case of phosphine oxides 2 and 3 (compare
Table 1, entries 7 and 8, as well as 12 and 14). It follows that
secondary phosphine oxide 1 with aromatic substituents is
more reactive in the studied reaction as compared with
bis(arylethyl)phosphine oxides 2 and 3. Among the studied
ketones, the most active was 2-pyridylphenylketone 12 (en-
tries 12, 13). The ketones with aromatic (heteroaromatic)
substituents react with secondary phosphine oxides faster
than the ketones bearing aliphatic or cycloaliphatic substit-
uents.
It can be assumed that this catalyst- and solvent-free
addition of secondary phosphine oxides to ketones is real-
ized via the molecular mechanism in four-membered tran-
sition states A involving concerted electron pair (or a single
electron) transfer without preliminary formation of ions or
radicals (Scheme 2).
Table 2 Reaction of Diphenylphosphine Oxide with Acetophenone in
Solventsa
O
C
Ph
Ph
O
H
Ph
Ph
O
solvent
+
P
Me
Ph
P
Ph
r.t., 24 h
Me
HO
1
4
13a
Entry Solvent
Gutmann acceptor number (AN) Yield of 13a (%)b
1
2
3
4
5
6
none
PhMe
THF
–
3.3
≈100
48c
8.0
23c
1,4-dioxane
MeCN
10.8
18.9
20.4
19
traces
not formed
CH2Cl2
a Reaction conditions: 1 (0.5 mmol), ketone 4 (0.53 mmol), solvent (1.7
mL), r.t., 24 h (argon).
b Data from 31P NMR analysis.
c A small amount of Ph2P(O)OH is also formed in these experiments.
R1
R1
R1
P
R1
R2
O
R1
R1
R2
R3
O
H
P
O
The fact that the reaction proceeds much faster and
cleaner without solvent is likely associated with a special
mutual affinity of the reactants (the secondary phosphine
oxides and ketones), which secures a specific enzyme-like
intermolecular recognition and thereby concerted hydro-
phosphorylation of the C=O bond. The driving force here is,
on the one hand, the ability of the phosphorus atom to ex-
tend its coordination sphere and, on the other hand, the re-
sponsive polarizability of ketones. In such reversibly form-
ing complexes (either intermediates or transition states),
the phosphorus atom behaves as organizing center, thus re-
sembling the coordination catalysis. The slowing down of
the reactions by solvents is assumingly due to insertion of
the solvent molecules into ketone/phosphine oxide com-
plexes as well as to the decrease of the reactants concentra-
tion. This assumption is supported by the approximate re-
ciprocal correlation between the yield of adduct 13a and
Gutmann AN14 of the solvents.
R2
O
P
H
+
OH
13
R3
O
R3
A
Scheme 2 A plausible mechanism for 13 formation
The fact that diphenylphosphine oxide (1) is more reac-
tive than bis(arylalkyl)phosphine oxides 2 and 3 as well as
higher reactivity of ketone 12 are consistent with the pro-
posed mechanism. In the first case, electron-withdrawing
phenyl substituents in oxide 1 promote the cleavage of the
P–H bond, just as the aryl and hetaryl substituents in the
ketone facilitate the attack of phosphorus atom on the C=O
group.
Using the reaction of diphenylphosphine oxide (1) with
acetophenone (4) as an example, we found that in the pres-
ence of organic solvents (toluene, THF, 1,4-dioxane, MeCN,
CH2Cl2, r.t., 24 h) the studied phosphorylation proceeds less
efficiently (Table 2, compare entries 2–4 and entry 1) or
does not occur at all (Table 2, entries 5, 6).
As shown by quantum-chemical calculations for gas
phase, the O–H···O=P intramolecular hydrogen bond in the
Thieme. All rights reserved. Synthesis 2020, 52, A–I

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N. K. Gusarova et al.
Paper
Synthesis
studied hydroxyphosphine oxides is rather weak (no more
than 3 kcal·mol–1). This conclusion is based on the values of
the electron density at the critical point of the O–H···O=P
hydrogen bond (not more than 0.025 a.u.) calculated in the
framework of the quantum theory ‘Atoms in Molecules’15a
and the equations relating this electron density to energy of
the intramolecular hydrogen bond.15b At the same time, the
intermolecular O−H···O=P hydrogen bond bridges have
been recognized16 to form ring and chain motifs in the crys-
tal structure of similar hydroxyphosphine oxides.
In summary, a convenient, environmentally friendly,
and highly efficient method for the green, click, atom-eco-
nomic synthesis of functional tertiary -hydroxyphosphine
oxides has been developed via the catalyst- and solvent-free
reaction of secondary phosphine oxides with ketones. The
synthesized compounds are promising ligands in the transi-
tion metal catalysis, flame retardants for polymeric materi-
als, and reactive building blocks for organic synthesis.
To determine the melting point, the phosphine oxides 13a–m were
re-precipitated from CНСl3/hexane (Table 1).
IR (KBr): 3093br s, 3031sh, 2867, 2813, 2781, 1971, 1829, 1677, 1593,
1484sh, 1410sh, 1314sh, 1158 (P=O), 1117, 1075, 1027, 997sh, 920,
816, 751, 697, 551, 501 cm–1
.
1H NMR (400.13 MHz, DMSO-d6):  = 8.09 (dd, 3JPН = 10.1 Hz, 3JHН = 8.3
3
3
Hz, 2 H, Ho, PhP), 7.72 (dd, JPН = 10.1 Hz, JHН = 8.3 Hz, 2 H, Ho, PhP),
7.58–7.52 (m, 2 H, Hm, PhР; 1 H, Hp, PhР), 7.47 (d, 3JHН = 7.6 Hz, 2 H, Ho,
PhC), 7.39 (t, 3JHН = 7.3 Hz, 1 H, Hp, PhC), 7.34–7.30 (m, 2 H, Hm, PhC),
7.19 (dd, 3JHН = 8.3 Hz, 3JHН = 7.3 Hz, 2 H, Hm, PhP), 7.14 (t, 3JHН = 7.2 Hz,
1 H, Hp, PhP), 6.38 (d, 3JPН = 18.9 Hz, 1 H, OH), 1.67 (d, 3JPН = 14.0 Hz, 3
H, CH3).
13C NMR (100.61 MHz, DMSO-d6):  = 143.5 (d, 2JPC = 3.2 Hz, Cipso, PhC),
2
1
133.0 (d, JPC = 7.7 Hz, Co, PhP), 132.0 (d, JPC = 89.5 Hz, Cipso, PhP),
4
1
131.9 (d, JPC = 2.2 Hz, Cp, PhP), 131.8 (d, JPC = 91.6 Hz, Cipso, PhP),
131.6 (d, 4JPC = 2.5 Hz, Cp, PhP), 128.6 (d, 3JPC = 10.6 Hz, Cm, PhP), 128.1
(d, 3JPC = 10.9 Hz, Cm, PhP), 127.6 (d, 4JPC = 1.7 Hz, Cm, PhC), 127.1 (d, 5JPC
3
1
= 2.1 Hz, Cp, PhC), 126.4 (d, JPC = 3.3 Hz, Co, PhC), 75.6 (d, JPC = 89.6
Hz, СOH), 25.9 (d, 2JPC = 3.9 Hz, CH3).
31P NMR (161.98 MHz, DMSO-d6):  = 30.4.
Anal. Calcd for C20H19O2P: С, 74.52; Н, 5.94; P, 9.61. Found: С, 74.41;
Н, 5.86; P, 9.49.
All reactions were carried out under an argon atmosphere. Diphenyl-
phosphine oxide (1) was a commercial product (Aldrich, 2014). Sec-
ondary phosphine oxides 2 and 3 were prepared from styrenes and
elemental phosphorus as previously reported.12 The reaction was
monitored using 31P NMR spectra by the disappearance of peaks of
the initial secondary phosphine oxides 1–3 (P ≈ 21–30) and the ap-
pearance of new peaks corresponding to -hydroxyphosphine oxides
13a–m (P ≈ 29–53). The 1H, 13C, 15N, and 31P NMR spectra were re-
corded on a Bruker DPX 400 and Bruker AV-400 spectrometers
(400.13, 100.61, 40.56, 161.98 MHz, respectively) in CDCl3 and
DMSO-d6 solutions and referenced to HMDS (1H NMR, 13C NMR),
CH3NO2 (15N NMR), and H3PO4 (31P NMR). The values of the  15N were
measured through the 2D 1H-15N HMBC experiment. Coupling con-
stants are given in hertz (Hz). All 2D NMR spectra were recorded by
using a standard gradient Bruker pulse programs. HSQC spectra were
recorded via double INEPT transfer in the phase sensitive TPPI mode
with GARP decoupling during acquisition.17a HMBC spectra were ob-
tained with the inverse technique and processed in the magnitude
mode.17b IR spectra were run on a Bruker Vertex 70 instrument. Melt-
ing points were recorded on a Stuart melting point apparatus and are
uncorrected. The microanalyses were performed on a Flash EA 1112
Series elemental analyzer. Quantum-chemical calculations of the ge-
ometry of molecules under study were carried out with a Gaussian 09
software package.18 The B3LYP functional19a with the 6-311++G(d,p)
basis set19b was applied at this calculations. The B3LYP/6-311++G(d,p)
protocol was also used in the calculations of topological parameters
of hydrogen bonds in terms of QTAIM, which were performed with
the AIMAll program.20
Ethyl 3-(Diphenylphosphoryl)-3-hydroxybutanoate (13b)
Yield: 322 mg (97%); white solid; mp 86–87 °C.
IR (film): 3208, 3062sh, 2983, 2934sh, 1730, 1652sh, 1438, 1371,
1321, 1179 (P=O), 1114, 1085, 1029, 950, 845, 751sh, 701, 621sh, 530
cm–1
.
1H NMR (400.13 MHz, CDCl3):  = 8.18–8.06 (m, 4 H, Ho, Ph), 7.54–
3
7.46 (m, 6 H, Hm,p, Ph), 4.09–3.96 (m, 2 H, CH2Me), 2.78 (d, JPН = 8.0
Hz, 2 H, CH2C=O), 1.53 (d, 3JPН = 13.6 Hz, 3 H, CH3COH), 1.22 (t, 3JHH
7.1 Hz, 3 Н, CH2CH3).
=
13C NMR (100.61 MHz, CDCl3):  = 172.4 (d, 3JPC = 14.9 Hz, C=O), 132.5
2
2
4
(d, JPC = 8.2 Hz, Co, Ph), 132.3 (d, JPC = 8.3 Hz, Co, Ph), 131.8 (d, JPC
=
2.3 Hz, Cp, Ph), 130.1 (d, 1JPC = 94.6 Hz, Cipso, Ph), 130.06 (d, 1JPC = 94.5
Hz, Cipso, Ph), 128.31 (d, JPC = 3.8 Hz, Cm, Ph), 128.28 (d, JPC = 3.6 Hz,
3
3
1
2
Cm, Ph), 72.9 (d, JPC = 92.6 Hz, СOH), 61.0 (CH2Me), 39.3 (d, JPC = 6.2
Hz, CH2C=O), 22.7 (d, 2JPC = 5.0 Hz, CH3СOH), 13.9 (CH2CH3).
31P NMR (161.98 MHz, CDCl3):  = 31.5.
Anal. Calcd for C18H21O4P: С, 65.05; Н, 6.37; P, 9.32. Found: С, 64.94;
Н, 6.29; P, 9.19.
1-(Diphenylphosphoryl)cyclopentanol (13c)
Yield: 275 mg (96%); white solid; mp 148–149 °C.
IR (KBr): 3213, 3060sh, 2955, 2870, 2778, 1479sh, 1437, 1387, 1304
sh, 1163, 1111, 1009, 963, 914, 856, 722sh, 698, 541, 498sh cm–1
.
1H NMR (400.13 MHz, CDCl3):  = 8.00–7.95 (m, 4 H, Ho, Ph), 7.56–
7.52 (m, 2 H, Hp, Ph), 7.49–7.44 (m, 4 H, Hm, Ph), 2.30–2.21 and 1.89–
1.82 (m, 4 H, H2,5, cyclopentanol), 1.74–1.64 (m, 4 H, H3,4, cyclopenta-
nol).
-Hydroxyphosphine Oxides 13a–m; 1-(Diphenylphosphoryl)-1-
phenylethanol (13a);9d Typical Procedure
A mixture of diphenylphosphine oxide (1; 202 mg, 1.0 mmol) and ac-
etophenone (4; 126 mg, 1.05 mmol) was rubbed with a spatula in a
round-bottomed flask (20–25 °C, 15 min, argon atmosphere) and
then stirred under the same conditions for ≈ 24 h to give a solid prod-
uct. The latter was washed with Et2O (2 × 0.3 mL) and dried in vacu-
um to afford -hydroxyphosphine oxide 13a; yield: 316 mg (98%);
white solid; mp 133–134 °C (Lit.9d mp 132–137 °C).
13C NMR (100.61 MHz, CDCl3):  = 132.2 (d, 2JPC = 8.5 Hz, Co, Ph), 131.7
(Cp, Ph), 131.0 (d, JPC = 92.7 Hz, Cipso, Ph), 128.2 (d, JPC = 11.1 Hz, Cm,
Ph), 81.8 (d, 1JPC = 90.3 Hz, COH), 36.7 (d, 2JPC = 8.5 Hz, C2,5, cyclopenta-
nol), 24.4 (d, 3JPC = 9.9 Hz, C3,4, cyclopentanol).
1
3
31P NMR (161.98 MHz, CDCl3):  = 33.7.
Anal. Calcd for C17H19O2P: C, 71.32; H, 6.69; P, 10.82. Found: C, 71.19;
H, 6.61; P, 10.67.
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–I

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N. K. Gusarova et al.
Paper
Synthesis
1
2
1-(Diphenylphosphoryl)cyclohexanol (13d)
PhCOH), 73.9 (d, JPC = 80.1 Hz, COH), 28.2 (d, JPC = 3.2 Hz, PhCH2),
2
1
27.7 (d, JPC = 3.3 Hz, PhCH2), 26.4 (d, JPC = 58.2 Hz, CH2P), 25.1 (d,
Yield: 294 mg (98%); white solid; mp 140–142 °C.
2JPC = 3.9 Hz, CH3).
IR (film): 3093br s, 2867, 2813, 2781, 1971, 1903, 1829, 1667, 1593,
1484sh, 1436, 1416sh, 1314, 1213sh, 1158 (P=O), 1117, 1075, 1027sh,
31P NMR (161.98 MHz, DMSO-d6):  = 51.0.
997sh, 920, 816, 751, 697, 551, 501 cm–1
.
Anal. Calcd for С24Н27O2P: С, 76.17; Н, 7.19; P, 8.18. Found: С, 76.06;
Н, 7.11; P, 8.03.
1H NMR (400.13 MHz, CDCl3):  = 8.04 (dd, 3JHН = 8.5 Hz, 3JPН = 9.5 Hz,
4 H, Ho, Ph), 7.55–7.45 (m, 6 H, Hm,p, Ph), 2.35–2.28 (br s, 1 H, OH),
1.92–1.85 (m, 2 H, cyclohexanol), 1.70–1.58 (m, 7 H, cyclohexanol),
1.27–1.20 (m, 1 H, cyclohexanol).
2-Chloro-1-(diphenylphosphoryl)-1-phenylethanol (13g)
Yield: 346 mg (97%); white solid; mp 139–140 °C.
13C NMR (100.61 MHz, CDCl3):  = 132.5 (d, 2JPC = 8.0 Hz, Co, Ph), 131.7
IR (KBr): 3123sh, 3060, 3007sh, 2688, 1964, 1904, 1819, 1627sh,
1596, 1488, 1436, 1343, 1242, 1172 (P=O), 1108, 1033, 996, 936, 897,
4
1
(d, JPC = 2.2 Hz, Cp, Ph), 129.9 (d, JPC = 90.3 Hz, Cipso, Ph), 128.3 (d,
3JPC = 11.0 Hz, Cm, Ph), 73.8 (d, JPC = 88.6 Hz, COH), 31.0 (d, JPC = 4.3
1
2
859, 751, 693, 576, 539, 516sh, 454 cm–1
.
3
Hz, C2,6, cyclohexanol), 25.1 (C4, cyclohexanol), 20.2 (d, JPC = 9.5 Hz,
1H NMR (400.13 MHz, DMSO-d6):  = 8.06 (dd, 3JHН = 8.8 Hz, 3JPН = 10.4
Hz, 2 H, Ho, PhP), 7.67–7.55 (m, 4 H, Ho,m, PhP; 1 H, Hp, PhP), 7.44–7.40
(m, 1 H, Hp, PhP; 2 H, Ho, PhC), 7.34–7.30 (m, 2 H, Hm, PhP), 7.22–7.16
C
3,5, cyclohexanol).
31P NMR (161.98 MHz, CDCl3):  = 33.6.
3
2
(m, 3 H, Hm,p, PhC), 6.89 (d, JPН = 17.1 Hz, 1 H, OH), 4.61 (dd, JHН
=
Anal. Calcd for C18H21O2P: C, 71.98; H, 7.05; P, 10.31. Found: C, 71.84;
H, 6.96; P, 10.18.
11.5 Hz, 3JPН = 2.7 Hz, 1 H, CH2Cl), 3.88 (dd, 2JHН = 11.5 Hz, 3JPН = 4.3 Hz,
1 H, CH2Cl).
1-Cyclohexyl-1-(diphenylphosphoryl)ethanol (13e)
13C NMR (100.61 MHz, DMSO-d6):  = 138.3 (Cipso, PhC), 133.2 (d, 2JPC
8.0 Hz, Co, PhP), 132.5 (d, 4JPC = 2.5 Hz, Cp, PhP), 132.14 (d, 2JPC = 8.0 Hz,
Co, PhP), 132.12 (d, 4JPC = 2.5 Hz, Cp, PhP), 131.2 (d, 1JPC = 90.1 Hz, Cipso
=
Yield: 319 mg (97%); white solid; mp 111–113 °C.
,
IR (KBr): 3247, 3059, 2931, 2858, 1734, 1629, 1462sh, 1437, 1369,
1166 (P=O), 1115, 1077, 1034sh, 952sh, 843, 751sh, 717sh, 700, 544
1
3
PhP), 130.9 (d, JPC = 95.4 Hz, Cipso, PhP), 129.0 (d, JPC = 11.3 Hz, Cm,
PhP), 128.4 (d, 3JPC = 11.3 Hz, Cm, PhP), 127.8 (Cm,p, PhC), 127.5 (d, 3JPC
3.3 Hz, Co, PhC), 79.1 (d, JPC = 83.0 Hz, COH), 51.5 (d, JPC = 18.6 Hz,
=
cm–1
.
1
2
1H NMR (400.13 MHz, DMSO-d6):  = 8.03–7.95 (m, 4 H, Ho, Ph), 7.55–
7.48 (m, 6 H, Hm,p, Ph), 5.53 (d, 3JPН = 11.1 Hz, 1 H, OH), 1.67–1.63 and
1.46–1.43 (m, 2 H, H2, cyclohexyl), 1.36–1.33 (m, 2 H, H6, cyclohexyl),
1.24 (br s, 1 H, H1, cyclohexyl), 1.21 (br s, 2 H, H4, cyclohexyl), 1.19–
CH2Cl).
31P NMR (161.98 MHz, DMSO-d6):  = 29.0.
Anal. Calcd for С20Н18ClO2P: С, 67.33; Н, 5.09; Cl, 9.94; P, 8.68. Found:
С, 67.21; Н, 5.01; Cl, 9.81; P, 8.57.
3
1.13 (m, 4 H, H3,5, cyclohexyl), 0.81 and 0.79 (2 d, JPН = 7.0 Hz, 3 H,
CH3).
1-[Bis(2-phenylethyl)phosphoryl]-2-chloro-1-phenylethanol
(13h)
13C NMR (100.61 MHz, DMSO-d6):  = 132.9 (d, 1JPC = 88.9 Hz, Cipso, Ph),
2
1
132.55 and 132.47 (2 d, JPC = 7.5 Hz, Co, Ph), 132.4 (d, JPC = 88.0 Hz,
C
ipso, Ph), 131.8 and 131.7 (2 d, 4JPC = 2.5 Hz, Cp, Ph), 128.6 and 128.5 (2
Yield: 405 mg (98%); white solid; mp 128–130 °C.
d, 3JPC = 10.6 Hz, Cm, Ph), 73.6 (d, 1JPC = 91.7 Hz, COH), 37.1 (d, 3JPC = 6.9
Hz, C2 or C6, cyclohexyl), 31.6 and 29.6 (C3,5, cyclohexyl), 22.4 (C4, cy-
clohexyl), 22.3 (d, 3JPC = 7.6 Hz, C2 or C6, cyclohexyl), 21.8 (d, 2JPC = 6.0
Hz, C1, cyclohexyl), 14.3 (CH3).
IR (KBr): 3064sh, 3027, 2957sh, 2908sh, 2868sh, 1955, 1878, 1814,
1755, 1629sh, 1601, 1490, 1447, 1390, 1373sh, 1328sh, 1281, 1210,
1145 (P=O), 1070sh, 997, 938, 903sh, 866sh, 833sh, 777, 740, 700,
574, 493, 441 cm–1
.
31P NMR (161.98 MHz, DMSO-d6):  = 34.6.
3
1H NMR (400.13 MHz, DMSO-d6):  = 7.62 (d, JHН = 7.8 Hz, 2 H, Ho,
3
3
PhCOH), 7.42 (dd, JHН = 7.8 Hz, JHН = 7.4 Hz, 2 H, Hm, PhCOH), 7.36–
7.32 (m, 1 H, Hp, PhCOH), 7.30–7.29 (m, 4 H, Ho,m, PhCH2), 7.21–7.16
Anal. Calcd for C20H25O2P: C, 73.15; H, 7.67; P, 9.43. Found: C, 73.03;
H, 7.58; P, 9.31.
3
(m, 2 H, Hm, PhCH2; 1 H, Hp, PhCH2), 7.10 (t, JHН = 7.3 Hz, 1 H, Hp,
PhCH2), 6.89 (d, 3JHН = 7.6 Hz, 2 H, Ho, PhCH2), 6.55 (d, 3JPН = 9.2 Hz, 1 H,
1-[Bis(2-phenylethyl)phosphoryl]-1-phenylethanol (13f)
2
3
OH), 4.52 and 4.34 (2 dd, JHН = 12.0 Hz, JPН = 3.5 Hz, 2 H, CH2Cl),
2.92–2.84 (m, 2 H, PhCH2), 2.46–2.32 (m, 2 H, CH2P), 2.20–2.08 (m, 1
H, CH2P), 1.89–1.79 (m, 1 H, CH2P), 1.72–1.63 (m, 2 H, PhCH2).
3
Yield: 363 mg (96%); white solid; mp 137–138 °C.
IR (film): 3090br s, 3031sh, 2966, 2926, 2863, 2785, 1984, 1959, 1812,
1662sh, 1601, 1491, 1448, 1399, 1364sh, 1274, 1213, 1148 (P=O),
13C NMR (100.61 MHz, DMSO-d6):  = 142.3 (d, JPC = 13.1 Hz, Cipso
,
1087, 1023sh, 996sh, 934, 917sh, 856, 819, 750, 701, 555, 510 cm–1
.
3
PhCH2), 142.0 (d, JPC = 14.8 Hz, Cipso, PhCH2), 139.0 (Cipso, PhCOH),
3
1H NMR (400.13 MHz, DMSO-d6):  = 7.61 (d, JHН = 8.1 Hz, 2 H, Hо,
4
129.0 (Cm, PhCH2), 128.9 (Co, PhCH2), 128.5 (d, JPC = 1.4 Hz, Cm,
3
3
PhCOH), 128.3 (Co, PhCH2), 128.0 (d, 5JPC = 1.6 Hz, Cp, PhCOH), 126.9 (d,
3JPC = 2.8 Hz, Co, PhCOH), 126.6 (Cp, PhCH2), 126.5 (Cp, PhCH2), 77.3 (d,
PhCOH), 7.39 (dd, JHН = 8.1 Hz, JHН = 7.3 Hz, 2 H, Hm, PhCOH), 7.30–
7.27 (m, 2 H, Ho, PhCH2; 2 H, Hm, PhCH2; 1 H, Hp, PhCOH), 7.22–7.17
3
2
2
1JPC = 73.1 Hz, COH), 51.1 (d, JPC = 17.2 Hz, CH2Cl), 28.0 (d, JPC = 3.2
Hz, PhCH2), 27.5 (d, 2JPC = 3.5 Hz, PhCH2), 27.4 (d, 1JPC = 49.4 Hz, CH2P),
26.9 (d, 1JPC = 47.8 Hz, CH2P).
(m, 2 H, Hm, PhCH2; 1 H, Hp, PhCH2), 7.11 (t, JHН = 6.9 Hz, 1 H, Hp,
PhCH2), 6.94 (d, 3JHН = 7.3 Hz, 2 H, Ho, PhCH2), 6.08 (d, 3JPН = 11.8 Hz, 1
H, OH), 2.91–2.85 and 2.25–1.86 (m, 2 H, CH2P; 4 H, PhCH2), 1.74 (d,
3JPН = 12.3 Hz, 3 H, CH3), 1.68–1.60 (m, 2 H, CH2P).
2
31P NMR (161.98 MHz, DMSO-d6):  = 53.5.
13C NMR (100.61 MHz, DMSO-d6):  = 143.9 (d, JPC = 2.5 Hz, Cipso
,
Anal. Calcd for С24Н26ClO2P: С, 69.82; Н, 6.35; Cl, 8.59; P, 7.50. Found:
С, 69.68; Н, 6.26; Cl, 8.48; P, 7.37.
PhCOH), 142.6 (d, 3JPC = 17.6 Hz, Cipso, PhCH2), 142.4 (d, 3JPC = 17.9 Hz,
C
ipso, PhCH2), 128.9 (Co, PhCH2), 128.8 (Cm, PhCH2), 128.7 (Cm, PhCH2),
5
128.29–128.25 (Co, PhCH2; Cm, PhCOH), 127.3 (d, JPC = 1.7 Hz, Cp,
1-(4-Chlorophenyl)-1-(diphenylphosphoryl)ethanol (13i)
PhCOH), 126.5 (Cp, PhCH2), 126.3 (Cp, PhCH2), 126.2 (d, 3JPC = 2.7 Hz, Co,
Yield: 343 mg (96%); white solid; mp 115–117 °C.
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–I

G
N. K. Gusarova et al.
Paper
Synthesis
IR (KBr): 3126sh, 3058, 2985sh, 2924sh, 2750sh, 1967, 1911, 1824sh,
1773sh, 1736sh, 1649, 1615, 1592, 1483, 1437, 1393, 1366, 1170
(P=O), 1104sh, 1074, 1009, 963sh, 920, 837, 720, 695, 598sh, 545,
(m, 2 H, CH2P), 2.69–2.59 (m, 1 H, CH2P), 2.43–2.32 (m, 1 H, CH2P),
2.26–2.14 (m, 2 H, PhCH2), 1.88 (d, 3JPН = 12.3 Hz, 3 H, CH3), 1.82–1.73
(m, 2 H, PhCH2).
516, 458 cm–1
.
2
13C NMR (100.61 MHz, CDCl3 + DMSO-d6):  = 150.9 (d, JPC = 2.0 Hz,
1H NMR (400.13 MHz, DMSO-d6):  = 8.06 (dd, 3JPН = 10.3 Hz, 3JHН = 8.6
С1, 4-NO2C6H4), 146.9 (С4, 4-NO2C6H4), 141.4 (d, JPC =12.9 Hz, Cipso
,
3
3
3
3
Hz, 2 H, Ho, Ph), 7.72 (dd, JPН = 10.6 Hz, JHН = 8.6 Hz, 2 H, Ho, Ph),
Ph), 141.1 (d, JPC = 13.3 Hz, Cipso, Ph), 128.5 (Cm, Ph), 128.4 (Cm, Ph),
7.60–7.55 (m, 2 H, Hm, Ph; 1 H, Hp, Ph), 7.46–7.41 (m, 1 H, Hp, Ph; 2 H,
128.1 (Co, Ph), 127.8 (Co, Ph), 126.8 (C2,6, 4-NO2C6H4), 126.3 (Cp, Ph),
3
1
H
H
2,6, 4-ClC6H4), 7.36–7.33 (m, 2 H, Hm, Ph), 7.25 (d, 2 H, JНН = 8.5 Hz,
126.1 (Cp, Ph), 123.0 (C3,5, 4-NO2C6H4), 74.1 (d, JPC = 79.4 Hz, COH),
3,5, 4-ClC6H4), 6.52 (d, 3JPН = 18.4 Hz, 1 H, OH), 1.63 (d, 3JPН = 13.9 Hz,
27.8 (d, JPC = 47.3 Hz, CH2P), 27.6 (d, JPC = 47.0 Hz, CH2P), 26.5
1
1
3 H, CH3).
13C NMR (100.61 MHz, DMSO-d6):  = 142.6 (d, JPC = 3.3 Hz, C1, 4-
(PhCH2), 25.9 (PhCH2), 25.0 (d, 2JPC = 2.4 Hz, CH3).
2
15N NMR (40.56 MHz, CDCl3 + DMSO-d6):  = –9.3.
31P NMR (161.98 MHz, CDCl3 + DMSO-d6):  = 53.2.
2
2
ClC6H4), 133.0 (d, JPC = 7.8 Hz, Co, Ph), 132.2 (d, JPC = 7.9 Hz, Co, Ph),
4
5
132.1 (d, JPC = 2.7 Hz, Cp, Ph), 132.0 (d, JPC = 2.7 Hz, С4, 4-ClC6H4),
131.9 (d, 4JPC = 2.7 Hz, Cp, Ph), 131.7 (d, 1JPC = 90.4 Hz, Cipso, Ph), 131.4
(d, 1JPC = 92.1 Hz, Cipso, Ph), 128.67 (d, 3JPC = 10.5 Hz, Cm, Ph), 128.65 (d,
3JPC = 3.6 Hz, C2,6, 4-ClC6H4), 128.3 (d, 3JPC = 10.4 Hz, Cm, Ph), 127.7 (d,
Anal. Calcd for С24Н26NO4P: С, 68.08; Н, 6.19; N, 3.31; P, 7.31. Found:
С, 67.96; Н, 6.08; N, 3.26; P, 7.17.
4JPC = 2.0 Hz, C3,5, 4-ClC6H4), 75.4 (d, 1JPC = 89.5 Hz, COH), 25.7 (d, 2JPC
=
(Diphenylphosphoryl)(phenyl)pyridine-2-ylmethanol (13l)
3.8 Hz, CH3).
Yield 374 mg (97%); white solid; mp 139–140 °C.
31P NMR (161.98 MHz, DMSO-d6):  = 31.6.
IR (KBr): 3228, 3059sh, 1967, 1832, 1642, 1585, 1468sh, 1432, 1383,
1252sh, 1185 (P=O), 1105, 1038, 999sh, 933, 886, 750, 694, 551, 520
Anal. Calcd for С20Н18ClO2P: С, 67.33; Н, 5.09; Cl, 9.94; P, 8.68. Found:
С, 67.21; Н, 5.02; Cl, 9.91; P, 8.59.
cm–1
.
3
1H NMR (400.13 MHz, CDCl3):  = 8.21 (d, JHН = 4.7 Hz, 1 H, H6, Py),
3
8.17 (d, JHН = 8.4 Hz, 1 H, H3, Py), 8.08–8.03 (m, 4 H, Ho, PhP), 7.71
1-(Diphenylphosphoryl)-1-(4-nitrophenyl)ethanol (13j)
3
3
5
(ddd, JHН = 8.4 Hz, JHН = 7.6 Hz, JPН = 1.8 Hz, 1 H, H4, Py), 7.50–7.46
(m, 2 H, Hm, PhC), 7.42–7.33 and 7.29–7.25 (m, 4 H, Hm, PhP; 2 H, Ho,
PhC), 7.24–7.18 (m, 2 H, Hp, PhP; 1 H, Hp, PhC), 7.14 (dd, 3JHН = 7.6 Hz,
3JHН = 4.7 Hz, 1 H, H5, Py), 7.08 (br s, 1 H, OH).
Yield: 360 mg (98%); white solid; mp 141–143 °C.
IR (KBr): 3105sh, 3056, 2987sh, 2963sh, 1966, 1817, 1689, 1595,
1517, 1485sh, 1439, 1345, 1170 (P=O), 1106, 1071, 1046sh, 918, 856,
816sh, 748sh, 716sh, 693, 589sh, 542, 520sh, 449 cm–1
.
13C NMR (100.61 MHz, CDCl3):  = 156.3 (d, 2JPC = 1.5 Hz, C2, Py), 146.1
1H NMR (400.13 MHz, CDCl3 + DMSO-d6):  = 7.98 (dd, JHН = 8.8 Hz,
3JPН = 10.5 Hz, 2 H, Ho, Ph), 7.83 (d, 5JPН = 8.6 Hz, 2 H, H3,5, 4-NO2C6H4),
7.61–7.56 (m, 2 H, H2,6, 4-NO2C6H4; 2 H, Ho, Ph), 7.40–7.36 (m, 1 H, Hp,
Ph), 7.34–7.27 (m, 2 H, Hm, Ph), 7.20 (t, 3JHН = 7.4 Hz, 1 H, Hp, Ph), 7.11–
7.07 (m, 2 H, Hm, Ph), 5.96 (br s, 1 H, OH), 1.64 (d, 3JPН = 13.8 Hz, 3 H,
CH3).
3
4
2
(d, JPC = 1.6 Hz, C6, Py), 141.3 (d, JPC = 5.2 Hz, Cipsо, PhC), 136.9 (d,
4JPC = 2.0 Hz, C4, Py), 132.8 (Cm, PhC), 132.7 (d, JPC = 5.1 Hz, Co, PhP),
2
132.5 (Cm, PhС), 131.5 (d, 3JPC = 2.8 Hz, Co, PhC), 131.3 (d, 3JPC = 2.8 Hz,
1
1
Co, PhC), 130.5 (d, JPC = 95.9 Hz, Cipso, PhP), 130.4 (d, JPC = 98.6 Hz,
C
ipso, PhP), 128.2 (Cp, PhP), 128.0 (d, 3JPC = 11.5 Hz, Cm, PhP), 127.43 (d,
5JPC = 2.8 Hz, Cp, PhC), 127.42 (d, 3JPC = 11.2 Hz, Cm, PhP), 126.6 (d, 2JPC
=
13C NMR (100.61 MHz, CDCl3 + DMSO-d6):  = 150.8 (d, JPC = 3.4 Hz,
4.4 Hz, Co, PhP), 123.8 (C3, Py), 122.6 (C5, Py), 77.8 (d, JPC = 87.1 Hz,
2
1
5
2
C1, 4-NO2C6H4), 146.7 (d, JPC = 2.8 Hz, C4, 4-NO2C6H4), 133.0 (d, JPC
=
COH).
8.0 Hz, Co, Ph), 132.1 (d, 2JPC = 8.4 Hz, Co, Ph), 131.8 (d, 4JPC = 2.7 Hz, Cp,
15N NMR (40.56 MHz, DMSO-d6):  = –89.6.
31P NMR (161.98 MHz, DMSO-d6):  = 34.4.
4
1
Ph), 131.6 (d, JPC = 2.7 Hz, Cp, Ph), 130.3 (d, JPC = 92.9 Hz, Cipso, Ph),
129.9 (d, 1JPC = 94.5 Hz, Cipso, Ph), 128.2 (d, 3JPC = 11.1 Hz, Cm, Ph), 127.8
(d, 3JPC = 11.5 Hz, Cm, Ph), 127.5 (d, 3JPC = 3.1 Hz, C2,6, 4-NO2C6H4), 122.5
(d, 4JPC = 2.0 Hz, C3,5, 4-NO2C6H4), 76.1 (d, 1JPC = 87.6 Hz, COH), 25.4 (d,
2JPC = 3.1 Hz, CH3).
Anal. Calcd for С24Н20NO2P: С, 74.80; Н, 5.23; N, 3.63; P, 8.04. Found:
С, 74.73; Н, 5.12; N, 3.57; P, 7.91.
15N NMR (40.56 MHz, CDCl3 + DMSO-d6):  = –8.5.
31P NMR (161.98 MHz, CDCl3 + DMSO-d6):  = 31.1.
{Bis[2-(4-chlorophenyl)ethyl]phosphoryl}(phenyl)pyridin-2-yl-
methanol (13m)
Yield: 490 mg (96%); white solid; mp 130–131 °C.
Anal. Calcd for С20Н18NO4P: С, 65.39; Н, 4.94; N, 3.81; P, 8.43. Found:
С, 65.21; Н, 4.89; N, 3.65; P, 8.32.
IR (KBr): 3094, 3062sh, 2915, 2861sh, 2740, 1894, 1629sh, 1586,
1489, 1445sh, 1409sh, 1377sh, 1276, 1223sh, 1167 (P=O), 1090, 1050,
1013, 947, 916sh, 870, 845, 806, 759, 706sh, 644, 545sh, 515, 477 cm–1
.
1-[Bis(2-phenylethyl)phosphoryl]-1-(4-nitrophenyl)ethanol (13k)
3
1H NMR (400.13 MHz, DMSO-d6):  = 8.60 (d, JHН = 4.8 Hz, 1 H, H6,
Py), 7.91–7.89 (m, 2 H, H3,4, Py; 2 H, Ho, Ph), 7.42–7.36 (m, 1 H, H5, Py;
2 H, Hm, Ph), 7.31–7.25 (m, 4 H, H2,6, 4-ClC6H4; 1 H, Hp, Ph), 7.06–7.01
(m, 4 H, H3,5, 4-ClC6H4), 2.70–2.50 (m, 2 H, CH2CH2P), 2.40–2.30 (m, 1
H, CH2P), 2.19–2.10 (m, 1 H, CH2P), 2.05–1.96 (m, 2 H, CH2P), 1.95–
1.84 (m, 2 H, CH2CH2P).
Yield: 410 mg (97%); white solid; mp 149–150 °C.
IR (KBr): 3196br s, 3068sh, 3028, 2937sh, 2865sh, 2787sh, 2629,
1949, 1806, 1598, 1513, 1451, 1410, 1345, 1205, 1127 (P=O), 1095,
1035, 1008sh, 927, 859, 751, 701, 555, 510 cm–1
.
1H NMR (400.13 MHz, CDCl3 + DMSO-d6):  = 8.19 (d, 3JHН = 8.8 Hz, 2
3
4
H, H3,5, 4-NO2C6H4), 7.89 (dd, JHН = 8.8 Hz, JPН = 1.7 Hz, 2 H, H2,6, 4-
NO2C6H4), 7.28 (dd, 3JHН = 7.3 Hz, 3JHН = 7.2 Hz, 2 H, Hm, Ph), 7.24–7.17
(m, 2 H, Ho, Ph; 2 H, Hm, Ph; 1 H, Hp, Ph), 7.12 (t, 3JHН = 7.3 Hz, 1 H, Hp,
Ph), 6.92 (d, 3JHН = 7.2 Hz, 2 H, Ho, Ph), 6.15 (br s, 1 H, OH), 3.08–2.90
2
13C NMR (100.61 MHz, DMSO-d6):  = 158.9 (d, JPC = 1.6 Hz, C2, Py),
2
3
148.0 (C6, Py), 141.6 (d, JPC = 2.9 Hz, Cipso, Ph), 141.3 (d, JPC = 3.1 Hz,
C1, 4-ClC6H4), 141.1 (d, 3JPC = 3.3 Hz, C1, 4-ClC6H4), 138.1 (C4, Py), 131.2
(C4, 4-ClC6H4), 130.3 (d, JPC = 3.5 Hz, C3,5, 4-ClC6H4), 128.84 and
128.82 (C2,6, 4-ClC6H4), 128.6 (Cm, Ph), 128.1 (Cp, Ph), 126.9 (d, JPC
5
3
=
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–I

H
N. K. Gusarova et al.
Paper
Synthesis
3
3.2 Hz, Co, Ph), 123.9 (C5, Py), 123.1 (d, JPC = 2.1 Hz, C3, Py), 77.7 (d,
(5) Moiseev, D. V.; James, B. R.; Hu, T. Q. Phosphorus, Sulfur Silicon
Relat. Elem. 2012, 187, 433.
1JPC = 78.6 Hz, COH), 27.9 (d, JPC = 60.0 Hz, CH2P), 27.2 (d, JPC = 61.1
1
1
Hz, CH2P), 26.9 (d, 2JPC = 3.5 Hz, CH2CH2P).
(6) (a) Cristau, H. J.; Brahic, C.; Pirat, J. L. Tetrahedron 2001, 57,
9149. (b) Nawrot, B.; Michalak, O.; Clercq, E. D.; Stec, W. J. Anti-
vir. Chem. Chemother. 2004, 15, 319. (c) Stroman, D. W.;
Chowhan, M. A.; Schneider, L. W.; Bartell, J. G.; Han, W. W.
Patent PCT Int. Appl. WO 2010091280 A1, 2010. (d) Alexandre,
F.-R.; Amador, A.; Bot, S.; Caillet, C.; Convard, T.; Jakubik, J.;
Musiu, C.; Poddesu, B.; Vargiu, L.; Liuzzi, M.; Roland, A.; Seifer,
M.; Standring, D.; Storer, R.; Dousson, C. B. J. Med. Chem. 2011,
54, 392. (e) Olsson, R. I.; Jacobson, I.; Boström, J.; Fex, T.; Björe,
A.; Olsson, C.; Sundell, J.; Gran, U.; Öhrn, A.; Nordin, A.; Gyll, J.;
Thorstensson, M.; Hayen, A.; Aplander, K.; Hidestal, O.; Jiang, F.;
Linhardt, G.; Forsström, E.; Collins, T.; Sundqvist, M.; Lindhardt,
E.; Astrand, A.; Löfberg, B. Bioorg. Med. Chem. Lett. 2013, 23, 706.
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Stelzer, O. Catal. Todаy 1998, 42, 413. (b) Gusarova, N. K.;
Ivanova, N. I.; Volkov, P. A.; Larina, L. I. Synthesis 2008, 3525.
(c) Ivanova, N. I.; Volkov, P. A.; Khrapova, K. O.; Larina, L. I.;
Bagryanskaya, I. Yu.; Gusarova, N. K.; Trofimov, B. A. Russ. J. Org.
Chem. 2016, 52, 772. (d) Jia, K.; Li, J.; Chen, Y. Chem. Eur. J. 2018,
24, 3174.
15N NMR (40.56 MHz, DMSO-d6):  = –80.4.
31P NMR (161.98 MHz, DMSO-d6):  = 53.2.
Anal. Calcd for С28Н26Cl2NO2P: С, 65.89; Н, 5.13; Cl, 13.89; N, 2.74; P,
6.07. Found: С, 65.78; Н, 5.06; Cl, 13.86; N, 2.67; P, 5.98.
Funding Information
This work has been approved by plans for research projects at the IPC
RAS State, Registration No. AAAA-A16-116112510005-7.
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Acknowledgment
The spectral data were obtained using the equipment of Baikal Ana-
lytical Center for Collective Use of the Siberian Branch of the Russian
Academy of Sciences.
(8) (a) Gusarova, N. K.; Reutskaya, A. M.; Ivanova, N. I.; Medvedeva,
A. S.; Demina, M. M.; Novopashin, P. S.; Afonin, A. V.; Albanov, A.
I.; Trofimov, B. A. J. Organomet. Chem. 2002, 659, 172.
(b) Ivanova, N. I.; Gusarova, N. K.; Nikitina, E. A.; Albanov, A. I.;
Sinegovskaya, L. M.; Nikitin, M. V.; Konovalova, N. A.; Trofimov,
B. A. Phosphorus, Sulfur Silicon Relat. Elem. 2004, 179, 7.
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24, 1641. (d) Yuan, X.-L.; Liu, W.-Y.; Huo, P.; Mei, G.-O. Acta
Crystallogr., Ser. E 2010, 66, 2331. (e) Keglevich, G.; Tóth, V. R.;
Drahos, L. Heteroat. Chem. 2011, 22, 15. (f) Gusarova, N. K.;
Ivanova, N. I.; Volkov, P. A.; Khrapova, K. O.; Larina, L. I.;
Smirnov, V. I.; Borodina, T. N.; Trofimov, B. A. Synthesis 2015, 47,
1611.
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(b) Goerlich, J. R.; Schmutzler, R. Phosphorus, Sulfur Silicon Relat.
Elem. 1995, 101, 213. (c) Odinets, I. L.; Matveeva, E. V. Curr. Org.
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Zhao, Yu. Phosphorus, Sulfur Silicon Relat. Elem. 2013, 188, 1080.
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Keglevich, G. Heteroat. Chem. 2016, 27, 260. (g) Keglevich, G.;
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0040-1707945.
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