Oxidative metal-free cross-coupling of secondary phosphine chalcogenides and benzenediols: Synthesis of phosphinochalcogenoic O-diesters

Article abstract of DOI:10.1002/hc.21020

Benzenediols react with 2 equiv of secondary phosphine chalcogenides in the CCl₄-Et₃N system under mild conditions (50-52°C, 1.5-13 h) to give phosphinochalcogenoic O-diesters in 62-91% isolated yields.

Full text of DOI:10.1002/hc.21020

Heteroatom Chemistry
Volume 00, Number 0, 2012
Oxidative Metal-Free Cross-Coupling of
Secondary Phosphine Chalcogenides and
Benzenediols: Synthesis of
Phosphinochalcogenoic O-Diesters
Nina K. Gusarova, Pavel A. Volkov, Nina I. Ivanova,
Ludmila I. Larina, and Boris A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of
Sciences, 664033 Irkutsk, Russian Federation
Received 28 October 2011; revised 8 February 2012
form new C C [3a–g,i] and C-heteroatom [2,3h,j]
ABSTRACT: Benzenediols react with 2 equiv of sec-
bonds. For instance, an efficient metal-free Sono-
gashira coupling between phenylacetylene and dif-
ferent electron-deficient aryl halides catalyzed by 1,
4-diazabicyclo[2.2.2]octane (DABCO) has been re-
alized [3i]. Microwave-promoted Suzuki-type cou-
pling of 4-bromoacetophenone and phenylboronic
acid in water has been developed [3b]. Recently,
ondary phosphine chalcogenides in the CCl4–Et3N sys-
tem under mild conditions (50–52◦C, 1.5–13 h) to give
phosphinochalcogenoic O-diesters in 62–91% isolated
ꢀ
C
yields. 2012 Wiley Periodicals, Inc. Heteroatom Chem
00:1–7, 2012; View this article online at wileyonlineli-
brary.com. DOI 10.1002/hc.21020
original and effective transition-metal-free cross-
coupling between halogenoacetylenes and pyrroles
INTRODUCTION
or indoles on Al2O3, BaO, and K2CO3 has been
proposed [4]. It has been reported as a metal-
free coupling reaction of 1,3-diarylpropenes or 1,3-
diarylpropynes with alcohols promoted by 2,3-
dichloro-5,6-dicyanobenzoquinone (DDQ) to form
the C O bonds [2,3h].
Most recently, we have published results on ox-
idative transition-metal-free cross-coupling between
secondary phosphine chalcogenides and amines [5],
alcohols and phenols [6] to furnish the P N and
P O bonds, correspondingly. These reactions pro-
ceed under mild conditions in the system CCl4–
Et3N to give amides [5] and O-esters [6] of phos-
phinochalcogenoic acids, which are widely used for
the design of practically important compounds and
materials [7].
Transition metal-catalyzed cross-coupling reactions
have been established as one of the powerful tools
for the formation of the C C and C X bonds
[1]. However, transition metal–based protocols usu-
ally have some inherent limitations, such as costly
metal catalysts, environmental toxicity, and mois-
ture sensitivity [2]. With the prevalence of “green
chemistry,” the cross-coupling reactions without
any metal catalysts have attracted great interest
[3]. Now these reactions are successfully used to
Correspondence to: Boris A. Trofimov; e-mail: boris trofimov@
irioch.irk.ru.
Contract grant sponsor: President of the Russian Federation
(program for the support of leading scientific schools).
Contract grant number: NSh-3230.2010.3.
Contract grant sponsor: President of the Russian Federation
(program for the support of young Russian scientists).
The objective of this paper is the development
of a one-pot and convenient method for prepa-
ration of phosphinochalcogenoic O-diesters, and
the chemistry of which is being developed very
Contract grant number: MK-629.2010.3.
2012 Wiley Periodicals, Inc.
c
ꢀ
1

2
Gusarova et al.
(I)
(II)
intensively during the recent decades [8–14]. These
compounds are employed as ligands for metal
complexes [8] (including supramolecular complexes
[8c]), extractants [9], and flame retardants [10] (in-
cluding “green, halogen-free” ones [10b]). Phos-
phinic O-diesters, which are structural analogs of
myleran, possess antineoplastic activity [11]. Func-
tional diesters of diphenylphosphinic acid are highly
selective, sensitive, cell-permeable, red fluorescent
probes for detecting of O2C•− in biological systems
[12], whereas their seleno-containing congeners are
applied as effective chemosensors for mercury ions
in biological systems and drinking water [12c]. Bis-
phosphinates are employed as the building blocks
[13] to design, for example, an effective catalyst for
enantioselective ethylation of aldehydes [13a].
At the same time, the conventional syntheses
of phosphinochalcogenoic O-diesters are multistep,
laborious, and involve utilizing moisture- and air-
sensitive phosphorus halides [8–13, 14b–g].
R
R
X
H
Et3N
CCl4
- e-
R
R
R
R
P
X
X
P
+
CCl4
P
_ Et3HN
A
B
C
X
P
Cl
D
(III)
R
R
B
+
+
CCl3
C
(IV)
CCl3
+
+
Et3N
+
CHCl3
Et3HN
(V)
R
X
X
X
R
Et3N
R
HOR2OH
[Et3NH]Cl
+
2
P
P
P
R
O R2
O
Cl
R
R
D
X = O, S, Se
SCHEME 1 A tentative mechanism for the formation of
phosphinochalcogenoic O-diesters 9a–i.
Here, we report for the first time on the reaction
of oxidative metal-free cross-coupling of secondary
phosphine chalcogenides with benzenediols using
the system CCl4–Et3N. Also, the paper deals with
the development of a one-pot method for the prepa-
ration of phosphinochalcogenoic O-diesters basing
on the above reaction. Initial secondary phosphine
oxides, sulfides, and selenides are easily prepared
by the “halogen-free” method from red phosphorus,
styrenes, and elemental chalcogens [15].
However, the main product of the cross-coupling in
this case remained O-diester 9g (yield 57%).
The reactivity of the starting secondary phos-
phine chalcogenides in oxidative cross-coupling
with benzenediols meets the following order: phos-
phine selenide > phosphine sulfide > phosphine ox-
ide (Table 1, cf. entries 1, 4, 7) that corresponds to
the decrease of P H acidity in the above series of
phosphine chalcogenides [16].
The lower reactivity of 1,2-benzenediol 5 as com-
pared to compounds 6,7 (Table 1, cf. entries 5–7) is
likely due to steric hindrances imposed by two hy-
droxyl groups in the orthoposition.
RESULTS AND DISCUSSION
We showed that bis(2-phenylalkyl)phosphine
chalcogenides 1–4 reacted with 1,2-, 1,3-, 1,4-
benzenediols 5–7, and 4,4ꢁ-isopropylidenebisphenol
8 in the system CCl4–Et3N under mild conditions
(50–52◦C, 1.5–13 h, molar ratio 1–4:5–8 = 1:0.4–0.5)
to afford bis(2-phenylalkyl)phosphinochalcogenoic
O-diesters 9a–i in 62–91% isolated yields (Table 1).
The products of monocondensation, phos-
phinochalcogenoic O-(hydroxyphenyl) esters, were
not detected in the resulting reaction mixture ob-
tained under the above conditions. At the same
time, on the example of phosphine selenide 3 and
1,4-benzenediol 7, it was shown that, when the
molar ratio of the starting reagents was 1:1, di(2-
phenethyl)phosphinoselenoic O-(4-hydroxyphenyl)
ester 10 was formed in significant amount (30%).
The experimental results obtained are in good
agreement with the reaction mechanism (Scheme 1),
which we have proposed earlier for the cross-
coupling of secondary phosphine chalcogenides
with alcohols and phenols [6]. The deprotona-
tion of a secondary phosphine chalcogenide by
triethylamine (which proceeds easier in the case
of more acidic secondary phosphine selenides and
then phosphine sulfides) produces P,X-ambident
chalcogenophosphinite-anion A (Step I). The latter
participates in the one-electron transfer toward CCl4
(oxidizer) to give free radical of secondary phos-
phine chacogenide B and anion radical C (Step II).
Then the interconversion of the species B and C
affords phosphinochalcogenoic chloride D and the
−CCl3 carbanion (Step III). The latter is protonated
by a triethylammonium cation that leads to regen-
eration of triethylamine and formation of chloro-
form (Step IV). The reaction between chloride D
and benzenediol in the presence of triethylamine
results in the final product, phosphinochalcogenoic
Se
P
O
OH
10
Heteroatom Chemistry DOI 10.1002/hc

Oxidative Metal-Free Cross-Coupling of Secondary Phosphine Chalcogenides and Benzenediols
3
TABLE 1 Synthesis of Phosphinochalcogenoic O-diesters 9a–ia
R1
R1
R1
R1
X
X
X
CCl4/Et3N
2
HO
OH
+
R2
P
P
P
50–52oC
O O
R2
H
R1
R1
5–8
9a–i
1–4
Yield (%)
b
c
Entry Phosphine Chalcogenides 1–4 R1
X
HOR2OH 5–8
R 2
Time (h) Product
1
2
1
2
H
H
O
S
7
5
9.5
13
9a
9b
76
66
72
63
3
4
2
2
H
H
S
S
6
7
5
6
9c
9d
79
81
73
75
5
3
H
Se
5
11
9e
65
62
6
7
3
3
H
H
Se
Se
6
7
1.5
4.5
9f
91
93
84
89
9g
8
9
3
4
H
Se
8
7
3
9h
9i
94
93
91
90
Me Se
9.5
aThe reagents 1–4 (1 mmol), Et3N (1 mmol) and 5 (0.42 mmol) or 6–8 (0.5 mmol), and CCl4 (4 mL) were used.
bYield was calculated from the 31P NMR spectra of the crude products. Bis(diorganochalcogenophosphoryl)oxides were identified as side
organophosphorus compounds (13C and 31P NMR).
cIsolated yield.
O-diester, and triethylammonium chloride (Step V).
In support of this mechanism, triethylammonium
chloride is always isolated from the reaction mix-
ture (by filtration) and CHCl3 is identified by gas
chromatography–mass spectrometry.
The formation of bis(diorganochalcogenophos-
phoryl)oxides as by-products is also in agreement
with the mechanism proposed (Scheme 2). Phos-
phinochalcogenoic chloride D generated at Stage III
apparently undergoes the hydrolysis owing to the
presence of trace water in the system to give dior-
ganylphosphinochalcogenoic O-acid E, which fur-
ther reacts with chloride D in the presence of Et3N
to form bis(diorganylchalcogenophosphoryl)oxides.
On the example of phosphine sulfide 2 and
phosphine selenide 3, it was shown that secondary
phosphine chalcogenides did react readily (r.t., 4
h) with water in the system CCl4–Et3N to de-
liver bis(diphenethylchalcogenophosphoryl)oxides
11, 12 in almost quantitative yields (Scheme 3).
In summary, the oxidative transition-metal-
free cross-coupling of secondary phosphine chalco-
genides and benzenediols using the CCl4–Et3N sys-
tem under mild conditions affords hitherto essen-
tially unknown phosphinochalcogenoic O-diesters
9a–i in high yields. The compounds synthesized
are prospective ligands for the preparation of metal
R
R
X
X
R
R
X
X
R
R
D/Et3N
R
R
H2O/Et3N
P
P
P
P
Cl
OH
O
D
E
SCHEME 2 A tentative mechanism for the formation of
bis(diorganylchalcogenophosphoryl)oxides.
Heteroatom Chemistry DOI 10.1002/hc

4
Gusarova et al.
precipitated white solid (triethylammonium chlo-
ride) was filtered, and 1,4-dioxane was evaporated
under vacuum. The residue obtained was washed
with Et2O (2 × 1 mL) and was dried in vacuum to
give diesters 9a–i.
X
X
X
CCl4/Et3N
+
H2O
P
P
P
2
- 2[Et3NH]Cl
- 2CHCl3
O
H
11, 12
2, 3
X = S (2, 11), Se (3, 12)
4-[(Diphenethylphosphoryl)oxy]phenyldipheneth-
ylphosphinate (9a). White powder, yield 0.224 g
(72%), mp 116–118◦C (hexane). IR (KBr) (cm−1):
1194 (P O C), 1172 (P O). 1H NMR (CDCl3) δ:
2.02–2.18 (m, 8H, CH2P), 2.82–2.98 (m, 8H, PhCH2),
7.12–7.13, 7.19–7.21, 7.23–7.28 (m, 24H, Ph, C6H4).
13C NMR (CDCl3) δ: 28.00 (PhCH2), 30.05 (d, CH2P,
1 JPC 86.7 Hz), 121.93 (C-2,3,5,6, C6H4), 126.60 (Cp),
128.09 (Co), 128.73 (Cm), 140.36 (d, Ci, 3 JPC 14.4 Hz),
147.64 (m, C-1,4, C6H4). 31P NMR (CDCl3) δ: 56.8.
Anal. Calcd for C38H40O4P2: C, 73.30; H, 6.47; P,
9.95. Found: C, 73.21; H, 6.50; P, 9.89.
SCHEME 3 Synthesis of bis(diphenethylchalcogenophos-
phoryl)oxides 11, 12.
complexes, extractants, flame retardants, and pre-
cursors for the design of biologically active com-
pounds.
EXPERIMENTAL
All experiments were carried out under argon. CCl4
were purified according to standard procedures [17].
Secondary phosphine chalcogenides 1–4 was pre-
pared from styrene or α-methylstyrene and elemen-
tal phosphorus and elemental chalcogenes as re-
ported [15]. The reaction was monitored using 31P
NMR spectra by the disappearance of peaks of the
initial secondary phosphine chalcogenides 1–4 and
appearance of new peaks corresponding to phos-
phinechalcogenoic O-diesters 9a–i. The 1H, 13C, 31P,
and 77Se NMR spectra were recorded in CDCl3 solu-
tions on a Bruker DPX 400 and Bruker AV-400 spec-
trometer (Bruker, Germany; 400.13, 100.62, 161.98,
and 76.31 MHz, respectively) and referenced to
TMS (1H NMR, 13C NMR), H3PO4 (31P NMR), and
Me2Se (77Se NMR). IR spectra were run on a Bruker
IFS 25 instrument. Mass spectra of electron ioniza-
tion (70 eV) were obtained on a Shimadzu GCMS–
QP5050 A (quadruple mass analyzer, the range of de-
tected mass was from 34 to 650 Da); capillary column
SPB–5ms (60 m × 0.25 mm × 0.25 μm), gas carrier
helium, flow rate 0.7 mL min−1, temperature of injec-
tor and ion source 250◦C, pressure 100 kPa; temper-
ature programming from 50 to 250◦C, 10 deg min−1.
Melting points were recorded on a Stuart melting
point apparatus and are uncorrected.
O-{2-[(Diphenethylphosphorothioyl)oxy]phenyl}
diphenethylphosphinothioate (9b). Light gray pow-
der, yield 0.173 g (63%), mp 107–109◦C (hexane).
IR (KBr) (cm−1): 1181 (P O C), 617 (P S). 1H
NMR (CDCl3) δ: 2.34–2.46 (m, 8H, CH2P), 2.87–3.06
(m, 8H, PhCH2), 7.08–7.10, 7.15–7.24 (m, 22H,
Ph, H-4,5, C6H4), 7.51 (m, 2H, H-3,6, C6H4). 13C
NMR (CDCl3) δ: 29.00 (PhCH2), 36.58 (d, CH2P, 1 JPC
65.6 Hz), 123.60 (C-3,6, C6H4), 125.38 (C-4,5, C6H4),
126.58 (Cp), 128.15 (Co), 128.72 (Cm), 140.12 (d, Ci,
2
3 JPC 16.1 Hz), 142.49 (dd, C-1,2, C6H4, JPC 9.9 Hz,
3 JPC 4.4 Hz). 31P NMR (CDCl3) δ: 107.0. Anal. Calcd
for C38H40O2P2S2: C, 69.70; H, 6.16; P, 9.46; S, 9.79.
Found: C, 69.72; H, 6.16; P, 9.39; S, 9.73.
O-{3-[(Diphenethylphosphorothioyl)oxy]phenyl}
diphenethylphosphinothioate (9c). White powder,
yield 0.239 g (73%), mp 74–76◦C (hexane). IR (KBr)
(cm−1): 1124 (P O C), 629 (P S). 1H NMR (CDCl3)
δ: 2.32–2.49 (m, 8H, CH2P), 2.92–3.09 (m, 8H,
3
PhCH2), 7.04 (d, 2H, H-4,6, C6H4, JHH 8.2 Hz),
7.16–7.24, 7.26–7.32 (m, 22H, Ph, H-2,5, C6H4). 13C
NMR (CDCl3) δ: 29.02 (d, PhCH2, 2 JPC 2.4 Hz), 36.46
1
3
(d, CH2P, JPC 65.9 Hz), 115.88 (t, C-2, C6H4, JPC
3
4.6 Hz), 118.50 (d, C-4,6, C6H4, JPC 3.6 Hz), 126.70
(Cp), 128.42 (Co), 128.84 (Cm), 129.99 (C-5, C6H4),
Phosphinechalcogenoic O-Diesters (9a–i)
3
130.37 (d, Ci, JPC 15.6 Hz), 151.20 (d, C-1,3, C6H4,
(General Procedure)
2 JPC 10.0 Hz). 31P NMR (CDCl3) δ: 105.2. Anal. Calcd
for C38H40O2P2S2: C, 69.70; H, 6.16; P, 9.46; S, 9.79.
Found: C, 69.64; H, 6.14; P, 9.37; S, 9.73.
A solution of secondary phosphine chalcogenides
1–4 (1.0 mmol) and Et3N (1.0 mmol) in 4 mL of CCl4
was stirred at 20–22◦C for 10 min. The benzenedi-
ols 6–8 (0.5 mmol) or 1,2-benzenediol 5 (0.42 mmol)
were added in the reaction mixture. The reaction
mixture was stirred at 50–52◦C for 1.5-13 h (see also
Table 1). The solvent was removed under the reduced
pressure, and 1,4-dioxane (3 mL) was added. The
O-{4-[(Diphenethylphosphorothioyl)oxy]phenyl}
diphenethylphosphinothioate (9d). White powder,
yield 0.246 g (75%), mp 69–70◦C (hexane). IR
1
(KBr) (cm−1): 1175 (P O C), 603 (P S). H NMR
(CDCl3) δ: 2.31–2.48 (m, 8H, CH2P), 2.92-3.10
Heteroatom Chemistry DOI 10.1002/hc

Oxidative Metal-Free Cross-Coupling of Secondary Phosphine Chalcogenides and Benzenediols
5
(m, 8H, PhCH2), 7.15–7.33 (m, 24H, Ph, C6H4). 13C
NMR (CDCl3) δ: 29.09 (PhCH2), 36.49 (d, CH2P,
1 JPC 65.9 Hz), 122.82 (C-2,3,5,6, C6H4), 126.77 (Cp),
128.44 (Co), 128.91 (Cm), 140.43 (d, Ci, 3 JPC 15.6 Hz),
147.63 (d, C-1,4, C6H4, 2 JPC 8.8 Hz). 31P NMR (CDCl3)
δ: 104.3. Anal. Calcd for C38H40O2P2S2: C, 69.70; H,
6.16; P, 9.46; S, 9.79. Found: C, 69.67; H, 6.15; P,
9.39; S, 9.73.
803.4 Hz). Anal. Calcd for C38H40O2P2Se2: C, 60.97;
H, 5.39; P, 8.28; Se, 21.10. Found: C, 61.01; H, 5.35;
P, 8.21; Se, 21.02.
O-[4-(1-{4-[(Diphenethylphosphoroselenoyl)oxy]
phenyl}-1-methylethyl)phenyl]diphenethylphosphino-
selenoate (9h). White powder, yield 0.394 g (91%),
mp 97–98◦C (hexane). IR (KBr) (cm−1): 1170
1
(P O C), 575 (P Se). H NMR (CDCl3) δ: 1.69 (s,
6H, Me), 2.51–2.60 (m, 8H, PhCH2), 2.98–3.11 (m,
8H, CH2P), 7.04 (d, 4H, H-2,6, C6H4, JHH 7.3 Hz)
O-{2-[(Diphenethylphosphoroselenoyl)oxy]phenyl}
diphenethylphosphinoselenoate (9e). White pow-
der, yield 0.195 g (62%), mp 109–111◦C (hexane).
IR (KBr) (cm−1): 1175 (P O C), 572 (P Se). 1H
NMR (CDCl3) δ: 2.46–2.61 (m, 8H, CH2P), 2.90–3.09
(m, 8H, PhCH2), 7.10–7.12, 7.20-7.27 (m, 22H, Ph,
H-4,5, C6H4), 7.53 (m, 2H, H-3,6, C6H4). 13C NMR
3
7.12–7.14 (m, 12H, Ph, Ho, Hp), 7.18 (d, 4H, H-3,5,
C6H4, 3 JHH 7.3 Hz), 7.25 (dd, 8H, Hm, Ph, 3 JHH 8.1 Hz,
3 JHH 7.3 Hz,). 13C NMR (CDCl3) δ: 29.41 (PhCH2),
1
30.93 (Me), 37.62 (d, CH2P, JPC 56.3 Hz), 42.38
3
(CMe), 121.16 (d, C-2,6, C6H4, JPC 3.4 Hz), 126.60
1
(C-3,5, C6H4), 127.88 (Cp), 128.31 (Co), 128.73 (Cm),
(CDCl3) δ: 29.47 (PhCH2), 37.89 (d, CH2P, JPC
3
140.12 (d, Ci, JPC 15.6 Hz), 147.26 (C-4, C6H4),
55.3 Hz), 123.52 (C-3,6, C6H4), 125.44 (C-4,5, C6H4),
126.66 (Cp), 128.22 (Co), 128.77 (Cm), 139.87 (d, Ci,
148.72 (d, C-1, C6H4, 2 JPC 10.0 Hz). 31P NMR (CDCl3)
1
δ: 104.5 (+d satellite, JPSe 799.6 Hz). 77Se NMR
2
3 JPC 16.6 Hz), 142.72 (dd, C-1,2, C6H4, JPC 10.3 Hz,
(CDCl3) δ: −248.7 (d, 1 JPSe 800.9 Hz). Anal. Calcd for
C47H50O2P2Se2: C, 65.13; H, 5.81; P, 7.15; Se, 18.22.
Found: C, 65.08; H, 5.79; P, 7.08; Se, 18.18.
3 JPC 4.8 Hz). 31P NMR (CDCl3) δ: 108.6 (+d satellite,
1 JPSe 811.1 Hz). 77Se NMR (CDCl3) δ: −239.9 (d, 1 JPSe
811.1 Hz). Anal. Calcd for C38H40O2P2Se2: C, 60.97;
H, 5.39; P, 8.28; Se, 21.10. Found: C, 60.89; H, 5.36;
P, 8.21; Se, 20.98.
O-(4-{[Bis(2-phenylpropyl)phosphoroselenoyl]
oxy}phenyl)bis(2-phenylpropyl)phosphinoselenoate
(9i). Waxy product, yield 0.362 g (90%). IR (neat)
O-{3-[(Diphenethylphosphoroselenoyl)oxy]phenyl}
diphenethylphosphinoselenoate (9f). Waxy product,
yield 0.314 g (84%). IR (neat) (cm−1): 1123 (P O C),
1
(cm−1): 1170 (P O C); 550, 575 (P Se). H NMR
(CDCl3) δ: 1.22, 1.28, 1.31, and 1.37 (4d, 12H, MeCH,
3 JPH 7.0 Hz, JPH 7.1 Hz, JPH 7.1 Hz, JPH 7.1 Hz,
respectively), 1.72–1.80, 2.05–2.48 (m, 8H, CH2P),
3.21–3.31, 3.34–3.49 (m, 4H, PhCH), 6.53, 6.57–6.61,
6.69–6.77, 6.85–6.92 (m, 4H, C6H4), 7.09–7.19,
7.22–7.25, 7.27–7.33 (m, 20H, Ph). 13C NMR (CDCl3)
1
3
3
3
582 (P Se). H NMR (CDCl3) δ: 2.46–2.61 (m, 8H,
CH2P), 2.90–3.09 (m, 8H, PhCH2), 7.04 (d, 2H,
3
H-4,6, C6H4, JHH 8.1 Hz), 7.20–7.33 (m, 22H, Ph,
H-2,5, C6H4). 13C NMR (CDCl3) δ: 29.47 (PhCH2),
1
3
37.89 (d, CH2P, JPC 55.6 Hz), 115.82 (t, C-2, JPC
3
3
4.6 Hz), 118.56 (d, C-4,6, JPC 3.5 Hz), 126.60 (Cp),
δ: 23.58 (d, MeCH, JPC 11.6 Hz), 23.89 (d, MeCH,
3
128.32 (Co), 128.69 (Cm), 129.77 (C-5, C6H4), 139.91
3 JPC 12.7 Hz), 24.29 (d, MeCH, JPC 12.4 Hz), 24.42
3
2
3
(d, Ci, JPC 15.3 Hz), 151.15 (d, C-1,3, C6H4, JPC
(d, MeCH, JPC 12.7 Hz), 35.36, 35.40, 35.61, 35.82
(4s, PhCH), 43.95 (d, CH2P, JPC 55.1 Hz), 44.13 (d,
CH2P, JPC 56.3 Hz), 44.30 (d, CH2P, JPC 55.1 Hz),
44.94 (d, CH2P, JPC 55.5 Hz), 122.00–122.23 (m,
1
9.8 Hz). 31P NMR (CDCl3) δ: 108.6 (+d satellite, 1 JPSe
1
1
1
811.1 Hz). 77Se NMR (CDCl3) δ: −239.9 (d, JPSe
1
811.1 Hz). Anal. Calcd for C38H40O2P2Se2: C, 60.97;
H, 5.39; P, 8.28; Se, 21.10. Found: C, 60.89; H, 5.36;
P, 8.21; Se, 20.98.
C-2,3,5,6, C6H4), 126.48–126.79, 127.02–127.28,
128.51–128.67 (m, Co, Cm, Cp), 145.46–145.61,
145.75–145.90 (m, Ci), 147.09–147.29 (m, C-1,4,
C6H4). 31P NMR (CDCl3) δ: 103.55–103.64, 106.04–
106.18, 106.94–107.14 (m). 77Se NMR (CDCl3) δ:
−(223.3–223.5), −232.0, −(232.6–233.1), −(233.7–
233.9), −242.5, −(243.1÷243.5) (m). Anal. Calcd for
C42H48O2P2Se2: C, 62.69; H, 6.01; P, 7.70; Se, 19.62.
Found: C, 62.65; H, 5.97; P, 7.63; Se, 19.57.
O-{4-[(Diphenethylphosphoroselenoyl)oxy]phenyl}
diphenethylphosphinoselenoate (9g). Light gray
powder, yield 0.333 g (89%), mp 148–149◦C (hex-
ane). IR (KBr) (cm−1): 1181 (P O C), 578 (P Se).
1H NMR (CDCl3) δ: 2.45–2.53 (m, 8H, CH2P),
2.89–3.08 (m, 8H, PhCH2), 7.16–7.23, 7.27–7.30 (m,
24H, Ph, C6H4). 13C NMR (CDCl3) δ: 29.55 (PhCH2),
1
37.80 (d, CH2P, JPC 56.0 Hz), 122.83 (C-2,3,5,6,
Phosphinochalcogenoic O-ester (10)
C6H4), 126.80 (Cp), 128.46 (Co), 128.91 (Cm), 140.14
3
2
(d, Ci, JPC 15.6 Hz), 147.96 (d, C-1,4, C6H4, JPC
A solution of secondary phosphine selenide 3
(1.0 mmol) and Et3N (1.0 mmol) in 4 mL of
CCl4 was stirred at 20–22◦C for 10 min. The
9.4 Hz). 31P NMR (CDCl3) δ: 109.4 (+d satellite, 1 JPSe
803.4 Hz). 77Se NMR (CDCl3) δ: −250.2 (d, JPSe
1
Heteroatom Chemistry DOI 10.1002/hc

6
Gusarova et al.
benzenediol 7 (1.0 mmol) was added in the re-
action mixture. The reaction mixture was stirred
at 50–52◦C for 3 h. The solvent was removed un-
der the reduced pressure, and 1,4-dioxane (3 mL)
was added. The precipitated white solid (triethy-
lammonium chloride) was filtered, and 1,4-dioxane
was evaporated under vacuum. The residue ob-
tained was consecutively washed with hexane (2
× 1 mL) and Et2O (3 × 1 mL). The residue was
dried in vacuum to give diester 9g (yield 0.213 g,
57%). Hexane solution was evaporated in vacuum
to afford bis(diphenethylselenophosphoryl)oxide 12
(yield 0.02 g, 6%). The ether solution was evap-
orated in vacuum to give 0.13 g (30%) of O-(4-
hydroxyphenyl)diphenethylphosphinoselenoate 10
as a waxy product. IR (KBr) (cm−1): 3326 (OH), 1192
(P O C), 581 (P Se). 1H NMR (CDCl3) δ: 2.47–2.54
(m, 4H, CH2P), 2.94-3.04 (m, 4H, PhCH2), 6.76 (d,
Bis(diphenethylselenophosphoryl)oxide
(12).
White powder, yield 0.325 g (99%), mp 81–82◦C
(hexane). IR (KBr) (cm−1): 956 (P O P), 574 (P Se).
1H NMR (CDCl3) δ: 2.47–2.68 (m, 8H, CH2P), 2.96–
3.03 (m, 8H, PhCH2), 7.21–7.25, 7.27–7.33 (m, 20H,
Ph). 13C NMR (CDCl3) δ: 29.64 (PhCH2), 39.14 (m,
CH2P), 126.84 (Cp), 128.58 (Co), 128.90 (Cm), 139.88,
3
139.96 (2 d, Ci, JPC 7.7 Hz). 31P NMR (CDCl3) δ:
1
2
102.9 (+dd satellites, JPSe 817.5 Hz, JP P 37.9 Hz).
77Se NMR (CDCl3): δ = −181.3 (d, JPSe 817.5 Hz).
1
Anal. Calcd for C32H36OP2Se2: C, 58.54; H, 5.53; P,
9.44; Se, 24.06. Found: C, 58.48; H, 5.55; P, 9.38; Se,
23.98.
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3
3
H-3.5, JHH 8.8 Hz), 6.99 (dd, H-2,6, JHH 8.8 Hz,
4 JPH 1.6 Hz), 7.20 (m, 6H, Ho, Hp, Ph), 7.30 (dd, 3 JHH
8.0 Hz, 3 JHH 7.7 Hz, 4H, Hm, Ph). 13C NMR (CDCl3) δ:
29.57 (PhCH2), 38.95 (d, CH2P, 1 JPC 56.7 Hz), 116.10
3
(C-3,5, C6H4), 122.83 (d, JPC 4.0 Hz, C-2,6, C6H4),
126.66 (Cp), 128.45 (Cm), 128.78 (Co), 140.12 (d, Ci,
2
3 JPC 15.6 Hz), 143.96 (d, C-1, JPC 10.0 Hz), 153.30
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792.3 Hz). Anal. Calcd for C22H23O2PSe: C, 61.54; H,
5.40; P, 7.21; Se, 18.39. Found: C, 61.50; H, 5.39; P,
7.18; Se, 18.37.
Bis(diphenethylchalcogenophosphoryl)oxides
(11, 12)
To a solution of phosphine chalcogenides 2, 3
(1.0 mmol) in 4 mL of CCl4 was added to a so-
lution of Et3N (1.0 mmol) and H2O (0.5 mmol)
in 1 mL of 1,4-dioxane, and the reaction mix-
ture was stirred at 20–22◦C for 4 h. The solvent
was removed under the reduced pressure, and 1,4-
dioxane (3 mL) was added. The precipitated white
solid (triethylammonium chloride) was filtered, and
1,4-dioxane was evaporated under vacuum to give
bis(diorganochalcogenophosphoryl)oxides 11, 12.
Bis(diphenethylthiophosphoryl)oxide(11). White
powder, yield 0.280 g (99%), mp 91–92◦C (hexane).
1
IR (KBr) (cm−1): 958 (P O P), 615 (P S). H NMR
(CDCl3) δ: 2.36–2.56 (m, 8H, CH2P), 2.97–3.04 (m,
8H, PhCH2), 7.21–7.27, 7.28–7.30 (m, 20H, Ph). 13C
NMR (CDCl3) δ: 28.66 (PhCH2), 37.43 (m, CH2P),
126.26 (Cp), 127.99 (Co), 128.36 (Cm), 139.91 (2d, Ci,
3 JPC 7.7 Hz). Anal. Calcd for C32H36OP2S2: C, 68.30;
H, 6.45; P, 11.01; S, 11.40. Found: C, 68.34; H, 6.43;
P, 10.89; S, 11.36.
Heteroatom Chemistry DOI 10.1002/hc

Oxidative Metal-Free Cross-Coupling of Secondary Phosphine Chalcogenides and Benzenediols
7
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Heteroatom Chemistry DOI 10.1002/hc