Reaction of elemental phosphorus with α-methylstyrenes: One-pot synthesis of secondary and tertiary phosphines, prospective bulky ligands for Pd(II) catalysts

Article abstract of DOI:10.1016/j.tet.2015.11.009

α-Methylstyrene and 4-chloro-α-methylstyrene react readily with elemental (red) phosphorus under microwave-irradiation in the superbase KOH/DMSO suspension to afford, depending on the reactant ratio and reaction time, either corresponding bis(2-arylpropyl

Full text of DOI:10.1016/j.tet.2015.11.009

Tetrahedron 72 (2016) 443e450
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Reaction of elemental phosphorus with -methylstyrenes: one-pot
a
synthesis of secondary and tertiary phosphines, prospective bulky
ligands for Pd(II) catalysts
a
a
a
Alexander V. Artem’ev , Svetlana F. Malysheva , Nina K. Gusarova ,
a
a
a
Nataliya A. Belogorlova , Boris G. Sukhov , Anastasiya O. Sutyrina ,
Elena A. Matveeva , Sergey F. Vasilevsky , Anastasiya I. Govdi , Yuriy V. Gatilov ,d,
a
b,
c
b
c
a
a,
*
Alexander I. Albanov , 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
Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 Institutskaya Str., Novosibirsk,
a
b
Russian Federation
c
Novosibirsk State University, 2 Pirogova Str., Novosibirsk, 630090, Russian Federation
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Ave., 630090,
d
Novosibirsk, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 10 August 2015
Received in revised form 16 October 2015
Accepted 6 November 2015
Available online 10 November 2015
a-Methylstyrene and 4-chloro-a-methylstyrene react readily with elemental (red) phosphorus under
microwave-irradiation in the superbase KOH/DMSO suspension to afford, depending on the reactant
ratio and reaction time, either corresponding bis(2-arylpropyl)phosphines or tris(2-arylpropyl)phos-
ꢀ
phines in 46e54% and 69e77% yields, respectively. Upon the heating only (110e130 C, 3 h), this reaction
provides mainly tris(2-arylpropyl)phosphine oxides (up to 78% yield) along with (2-arylpropyl)phos-
phinic acids (up to 43%). The synthesized phosphines are prospective bulky ligands for metal catalysts
that has been demonstrated by the preparation of a new Pd(II) complex, trans-[Pd(PR ) Cl ], which
3 2 2
Keywords:
Elemental phosphorus
proves to be active in the Sonogashira couplings.
a
-Methylstyrene
Ó 2015 Elsevier Ltd. All rights reserved.
Phosphines
Sonogashira coupling
Superbases
1
. Introduction
However, the classical approaches for the synthesis of bulky
phosphines are mostly limited to the reactions of phosphorus ha-
lides or chlorophosphines with Grignard or organolithium re-
Currently, secondary and tertiary phosphines attract increasing
attention due to their great importance in organic chemistry,
6
agents as well as to transition-metal catalyzed phosphination of
7
catalysis and materials science. They are extensively employed as
organic halides. The obvious drawbacks of these methods are
ligands,1 reagents2 and catalysts
2a,3
for preparing various phar-
multistage procedures, the use of expensive metal catalysts, an-
hydrous conditions and inert atmosphere. Therefore, the de-
velopment of halogen- and organometallics-free step-economic
routes toward bulky phosphines from available non-hazardous
precursors such as red phosphorus remains a challenging task in
organophosphorus and green chemistry.
maceuticals, functional materials and fine chemicals. Moreover,
tertiary phosphines are among the most important capping agents
4
and coordinating solvents for fabrication of advanced nano-
materials, which are widely used in modern electronic and optical
devices. Bulky secondary and tertiary phosphines are of special
interest as ligands for diverse transition-metal catalyzed reactions.5
Noteworthy, metal complex catalysts containing bulky phosphine
ligands often perform better than those with triphenylphosphine
To date, several convenient elemental phosphorus-based ap-
proaches to CeP bond formation are known. They are exemplified
by direct reactions of white or red phosphorus with C-electro-
5
8
9
or other common ligands.
philes in superbasic media as well as by electrochemical, metal-
10
11
4
promoted and photochemical reactions of the P molecule. One
of the most economically and environmentally attractive method-
ologies for activation of elemental phosphorus, especially its red
*
Corresponding author. Tel.: þ7 395 251 1431; fax: þ7 3952419346;
e-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
http://dx.doi.org/10.1016/j.tet.2015.11.009
0
040-4020/Ó 2015 Elsevier Ltd. All rights reserved.

4
44
A.V. Artem’ev et al. / Tetrahedron 72 (2016) 443e450
form, now rapidly being developed, is based on application of the
superbase suspensions, such as KOH/polar non-hydroxylic solvent
(
DMSO or HMPA) or aqueous solution of KOH/organic solvent/
8,12
phase-transfer catalyst.
yphosphide (A) and polyphosphinite (B) anions, viz. [P
In this multi-component reaction, pol-
ꢁ
n
]
and
ꢁ
[P
m
(O)] , are generated in situ during cleavage of PeP bonds by
weakly solvated (naked) hydroxide anions. These highly active P-
centered nucleophiles then easily attack organic electrophiles (al-
kynes, alkenes or organic halides) to give phosphines, phosphine
oxides and/or phosphinic acids in good to high yields
Scheme 2. Selective synthesis of secondary phosphine 2a from red phosphorus and
a-methylstyrene.
(
Scheme 1).8,12
Prompted by these initial results, we turned our efforts to find
more effective reaction conditions for selective formation of sec-
ondary and tertiary phosphines. After optimization tests, we have
found that at the 1a/Pred/KOH molar ratio of 4:10:11 and irradiation
ꢀ
power of 200 W (corresponds to 180 C in MW-reactor), the re-
action proceeds for 15 min to selectively give secondary phosphine
2a in 54% isolated yield (Scheme 2).
Specific conditions for selective formation of tertiary phosphine
were also developed. This phosphine was obtained in 77% isolated
yield using more prolonged irradiation (30 min) and larger
amounts of alkene relative to phosphorus (1a/Pred/KOH molar ratio
was 6:10:11), Scheme 3.
Scheme 1. Plausible pathway for the reaction of elemental phosphorus with electro-
philes in superbase media.
To our knowledge, the syntheses of secondary and tertiary
phosphines directly from elemental phosphorus are limited to
1
3
preparation of tris(Z-styryl)phosphine,
tris(1-naphthyl)phos-
14
15
phine,
bis(1-methyl-2-phenylethyl)phosphine
and tris(2-
Scheme 3. Selective synthesis of tertiary phosphine 3a from red phosphorus and
pyridyl)phosphine1 from phenylacetylene, 1-bromonaphthalene,
allylbenzene and 2-bromopyridine, correspondingly, in the KOH/
DMSO(HMPA) system. Also, the electrochemical synthesis of tri-
6
a-methylstyrene.
With the optimal conditions in hand, we tried to extend this
reaction to 4-chloro-a-methylstyrene (1b). As expected, this alkene
17
phenylphosphine from P
4
and phenyl halides was described.
also readily participates in the reaction with red phosphorus in
KOH/DMSO system to furnish either secondary phosphine 2b or
tertiary phosphine 3b in 46 and 69% isolated yields, respectively
(Scheme 4). The presence of 4-chlorophenyl groups in the prepared
phosphines opens up wide opportunities for their further func-
tionalization, for example, via cross-coupling reactions.
Herein, we report an efficient one-pot synthesis of bulky sec-
ondary and tertiary phosphines, namely bis(2-arylpropyl)- and
tris(2-arylpropyl)phosphines, which comprises the microwave-
assisted reaction of elemental (red) phosphorus with industrially
available a-methylstyrene as well as 4-chloro-a-methylstyrene in
the superbase suspension KOH/DMSO. Also, the first example of
successful application of the synthesized tris(2-phenylpropyl)
phosphine as a ligand for a novel Pd-catalyst, active in a cross-
coupling reaction, is presented.
2
2
. Results and discussion
.1. Synthesis of ligands
Considering the recent advances in microwave (MW)-mediated
18
organophosphorus synthesis, we have applied MW assistance for
direct phosphorylation of -methylstyrene (1a) and 4-chloro-
a
a-
methylstyrene (1b) with red phosphorus in superbase suspension
KOH/DMSO.
The experiments have shown that in the case of
ene, the reaction easily occurs at 180 C for 20 min in MW-reactor
or at 600 W for 6 min in a domestic microwave oven to afford
a
-methylstyr-
ꢀ
Scheme 4. Selective synthesis of phosphines 2b and 3b from red phosphorus and
a
mixture of bis(2-phenpropyl)phosphine (2a) and tris(2-
4-chloro-a-methylstyrene.
31
phenpropyl)phosphine (3a) in nearly equal amounts ( P NMR)
with 68% total yield (Scheme 2), the conversion of alkene 1a being
about 80%. The decrease of irradiation power and the increase of
the reaction time to 15 min gave an almost quantitative conversion
of alkene 1a so that total yield of the above phosphines reaches 85%
For the comparison, the phosphorylation of alkenes 1a,b with
red phosphorus under thermal conditions has been investigated. It
was found that at 130 S this reaction proceeded for 3 h providing
an equimolar mixture of tertiary phosphines 3a,b and tertiary
phosphine oxides 4a,b along with potassium salt of phosphinic
ꢀ
(
basing on the starting alkene).
2 2
acids 5a,b and potassium hypophosphite, KH PO (Scheme 5), the

A.V. Artem’ev et al. / Tetrahedron 72 (2016) 443e450
445
conversion of alkenes 1a,b being complete. The free acids 5a,b were
isolated in 15% and 10% yields by acidification of the reaction
phosphinite-like anions B meet a stronger steric hindrance from
the -methyl group than anion A.
As an example of application of the synthesized compounds as
useful building blocks, we have implemented chalcogenation and
quaternization of tertiary phosphines 3a,b. The latter, despite their
sterically hindered structure, easily react with elemental sulfur and
selenium (rt, toluene, 1 h) to give phosphine chalcogenides 6aec in
high yields (Scheme 7).
a
mixture, whereas the crude mixture of 3a,b and 4a,b was treated
ꢀ
with hydrogen peroxide (H
2
O/acetone, 25 C) and the corre-
sponding phosphine oxides 4a,b were isolated in 78% and 72%
yields (basing on starting alkenes).
Scheme 7. Reaction of phosphine 3a with sulfur and selenium.
When phosphine 3a was contacted with methyl iodide (rt,
MeCN, 5 h), the corresponding phosphonium salt 7 was formed in
quantitative yield (Scheme 8).
Scheme 5. Reaction of alkenes 1a,b with red phosphorus in KOH/DMSO system.
The screening of the reaction conditions showed that a 1a,b/
ꢀ
P
red/KOH ratio of 6:10:11 and a temperature of 130 C seems to be
optimal for preparative synthesis of phosphine oxides 4a,b
(
Scheme 5). For instance, at a lower temperature (other conditions
ꢀ
are the same), 120 S, selectivity of the reaction sharply decreases:
apart from the expected products 3a,b, 4a,b and 5a,b, secondary
phosphines 2a,b and their oxides are formed. Meanwhile, the
Scheme 8. Reaction of phosphine 3a,b with methyl iodide.
ꢀ
subsequent decrease of the temperature to 110 C and, simulta-
neously, basicity of the media (50 mol % of water is added to the
KOH/DMSO system) leads to a remarkable alteration of the reaction
course so that the potassium salts of phosphinic acids 5a,b become
the main organophosphorus products. Under the best conditions,
i.e., at the 1a,b/Pred/KOH/H O ratio of 6:10:11:5, isolated yields of
2
the free acids 5a,b (after acidification of reaction mixture) reach 43
2.2. Structural determination
The structure of synthesized compounds have been proven by
1H, 13C, P, Se, 2D (COSY, HMBC) NMR and FTIR spectroscopy. The
31
77
stereochemistry of the prepared phosphines was established based
31
and 36%, correspondingly (Scheme 6).
on analysis of their P NMR spectra.
31
In the P NMR spectrum of secondary phosphine 2a, there are
three characteristic peaks at ꢁ81.0, ꢁ81.7 and ꢁ82.4 ppm with the
integral ratio of about 1:1.5:1 (See Supplementary data). As ex-
pected, in the spectrum, the signals of three diastereomeric pairs
are discernible. One of these pair, in which configurations of chiral
C C C C
carbons are different (i.e., R S /S R ), has an internal plane of
symmetry, so that this diastereomeric pair is a meso-isomer. The
two other diastereomeric pairs contain chiral carbons with the
identical configuration. As a result, the phosphorus atom becomes
asymmetric one in these stereoisomers, i.e., R
/R
. Apparently, the major signal (ꢁ81.7 ppm) in the
NMR spectrum of 2a can be assigned to meso-isomer (R /S
whereas the two minor peaks correspond to C,P-chiral isomers
/S and S /R ). The phosphine 2b, expectedly,
reveals similar spectral features.
C
R
C
R
P
/S
C
S
C
S
P
and
P
R ),
C C
Scheme 6. The selective synthesis of phosphinic acids 5a,b from red phosphorus and
alkenes 1a,b.
31
S
C
S
C
R
P
C
R
C
S
P
C
S
C
It should be emphasized that, unlike the
a-methylstyrenes
studied herein, unsubstituted styrene itself and its ring-substituted
derivatives in the similar reactions with red phosphorus never gave
the expected secondary phosphines, while the tertiary phosphines
were formed as w1:1 mixtures with phosphine oxide. Apparently,
(R
C
R
C
R
P
C
S
C
S
P
C C
S R
P
C C P
R S
3
1
The P NMR spectrum of 3a shows two signals (ꢁ34.4 and
ꢁ
35.9 ppm) with an integral ratio of about 1:3 (See ESI). In this case,
in the case of
a
-methylstyrene, the steric screening of
b-position of
formal stereochemical analysis indicates that this compound has
the vinyl moiety by hydrogen atoms of the
a
-methyl group plays
3
only two diastereomers (instead of four possible ones, N¼2 /2¼4),
a decisive role. As mentioned above (Scheme 1), in the reaction
course, the two types of phosphorus-centred anions A and B,
compete for the double bond. It seems reasonable that the bulkier
C C C C C C C C C C C C
namely R R R /S S S and R R S /S S R , with the quantitative ratio
of 1:3. Indeed, as seen from Fig. 1, the molecules of three possible
diastereomers with different configuration of carbons, i.e.,

4
46
A.V. Artem’ev et al. / Tetrahedron 72 (2016) 443e450
2 3
all three PeCH eCHeCH moieties adopt a s-trans conformation,
although the S(11) atom has R configuration, whereas the S(2) and
S(20) atoms have S configuration.
2 2
2.3. Application of complex [Pd(3a) Cl ] in catalysis
For preliminary evaluation of the catalytic activity of Pd(II)
complexes with the above bulky phosphine ligands, we have syn-
thesized a complex of the structure [Pd(PR
catalytic efficiency in the Sonogashira coupling.
The complexation of 3a with PdCl
3
)
2
Cl
2
] and evaluated its
ꢀ
2
proceeds at 50 C (CHCl
3
, 8 h)
to give trans-complex 8 in 57% isolated yield (Scheme 9).
Scheme 9. Synthesis of complex 8.
1
The complex 8 is also crystallized in the chiral Pca2 space
group. Its X-ray structure (Fig. 3) proves the S, R, R, S and R,
configurations for the C(2), C(11), C(29), C(38) and C(47) atoms,
correspondingly, while the R/S ratio for the C(20) atom is
0.61(1):0.39(1) due to the disordering of the 2-phenylpropyl group
Fig. 1. Degeneration of the six possible stereoisomers of 3a.
(S19eS27 atoms). The Pd atom is coordinated by two chloride
R
C1
C2
R S
C3/SC1
S
C2
RC3, SC1
S
C2
R
C3/RC1
R
C2
S
C3 and RC1
S
C2
R
C3/SC1
R
C2
S
C3
,
anions and two phosphorus atoms of ligand 3a in a trans-
configuration.
due to the presence of a C
atom (C
3
axis passing through the phosphorus
3
symmetry), degenerate into the single RRS/SSR di-
31
astereomer. Therefore, the most intense signal in the P NMR
spectrum of 3a is assumed belong to ‘major’ RRS/SSR diastereomer,
while the low intense peak corresponds to ‘minor’ RRR/SSS di-
astereomer. The 31P NMR spectra of compounds 2b, 3b, 4a,b, 6aec
and 7 reveal a similar feature, that can be explained by the same
way.
Remarkably, phosphine oxide 4a undergoes spontaneous reso-
lution upon crystallization to afford pure SSR-enantiomer. The lat-
ter, according to an X-ray diffraction study, crystallizes in the chiral
P2
1
2
1
2
1
space group. Its molecular structure is shown in Fig. 2. Note,
Fig. 3. X-ray structure of 8 (the hydrogen atoms are omitted for clarity). The S19eS27
atoms of the CH CH(Me)Ph fragment are disordered over two position in
2
a 0.61(1):0.39(1) occupancy (a disordered component B is omitted for clarity).
Complex 8 was tested in the cross-coupling of diverse alkynes
9
aec (amphoteric, EWG- and ERG-substituted) with 1-iodo-4-
nitrobenzene and the results have been compared to those
obtained with the common catalyst, Pd(PPh Cl (Table 1). The
3
)
2
2
reaction was carried out with 3 mol % of Pd(II) source, 6 mol % of CuI
ꢀ
in triethylamine/benzene media at 70e80 C.
The results (Table 1) indicate that the isolated yields of the al-
Fig. 2. X-ray structure of SSR-isomer of 4a.
kynes 10aec are close for both catalysts (75e83%), although the

A.V. Artem’ev et al. / Tetrahedron 72 (2016) 443e450
447
Table 1
respect to the CDCl
(77.0 ppm). 85% H
PO
/D
O was used as ex-
3
3
4
2
Cross-coupling of alkynes 9aec with 1-iodo-4-nitrobenzene: the effect of catalyst on
the reaction time and product yields
31
ternal standards for P NMR. The FTIR spectra were recorded on
a Bruker Vertex 70 spectrometer. The C, H microanalyses were
performed on a Flash EA 1112 SHNS-O/MAS analyzer, while the P
contents were determined by combustion method. Melting points
were established using a Kofler micro hot stage.
a
Microwave-assisted syntheses were carried out using Anton Paar
Monowave 300 reactor (magnetron frequency 2455 MHz, power up
to 850 W) in heavy-walled glass vials sealed with Teflon septa. The
reaction temperatures were measured by infrared detector during
microwave heating. Also, modified Samsung M181DNR microwave
oven (equipped with reflux condenser) was used.
Alkyne
[Pd]
Reaction
time, h
Yield of
10aec, %b
Complex 8
Pd(PPh
10e12
1
78
80
3
)
2
Cl
2
(
9a)
Red phosphorus, alkenes 1a,b, LPO∙0.5H
2
O, DMSO (0.5% water
content), sulfur (S ) and grey selenium were used as purchased.
8
Complex 8
Pd(PPh Cl
4
0.5
75
75
3
)
2
2
2
4.2. Synthetic procedures
.2.1. General procedure for preparation of secondary phosphines
2a,b (Schemes 2 and 4). A mixture of alkene 1a or 1b (40 mmol),
red phosphorus (3.10 g, 100 mmol), hydroquinone (0.11 g),
(9b)
4
Complex 8
Pd(PPh Cl
8
2
75
83
3 2
)
2
LPO∙0.5H O (7.00 g, 107 mmol) and DMSO (30 mL) was irradiated
for 15 min. The reaction mixture was cooled to room temperature,
(
9c)
a
Conditions: alkyne 9aec (1.26 mmol), 1-iodo-4-nitrobenzene (1.0 mmol), [Pd]
0.003 mmol), CuI (0.006 mmol), Et
0e80 S).
Isolated yield.
diluted with water (30 mL), filtered from unreacted phosphorus
(
7
3
N (7 mmol), benzene (4 mL), stirring (argon,
31
and analyzed. According to R NMR spectrum, the mixture con-
ꢀ
b
tains mainly phosphine 2a (2b) along with trace amounts of po-
tassium salt of 5a (5b) and potassium hypophosphite, KH
2
PO
¼ꢁ3.1 ppm, JPH¼467 Hz). The mixture was extracted with CHCl
(3ꢂ30 mL), extract was washed with water (2ꢂ30 mL) and dried
over K CO . The solvent was removed under reduced pressure and
2
(t,
1
d
P
3
reactions with classical catalyst occur faster than with complex 8.
The real yields of the products (according to GC/MS analysis) reach
2
3
8
5e98%. Moreover, in all the cases, up to3% of 1,4-diynes are formed.
residue was distillated in vacuum to give 2a (2.92 g, 54%) or 2b
As for reactivity within alkyne series, the reaction with electron-
deficient alkyne 9b, as expected, proceeds more rapidly compared
to electron-rich (9c) and amphoteric (9a) alkynes (Table 1).
Thus, the new Pd(II) complex does exhibit the expected catalytic
activity in the Sonogashira reaction, although it is slightly less time-
efficient than the classic catalyst. Since Pd(II) complexes with bulky
phosphines often secure better performance, sometimes even
changing chemo-, regio- and stereodirections of the reactions, the
synthesized ligand may provide additional possibilities for con-
trolling various catalytic processes.
(3.12 g, 46%).
4.2.2. General procedure for preparation of tertiary phosphines 3a,b
(Schemes 3 and 4). A mixture of alkene 1a or 1b (60 mmol), red
phosphorus (3.10 g, 100 mmol), hydroquinone (0.11 g),
LPO∙0.5H O (7.00 g, 107 mmol) and DMSO (30 mL) was irradiated
2
in for 30 min. The reaction mixture was cooled to room tempera-
ture, diluted with water (30 mL), filtered from unreacted phos-
phorus and analyzed. According to R NMR spectrum, the mixture
contains mainly phosphine 3a (3b) along with potassium salt of 5a
31
(
5b) and potassium hypophosphite. The mixture was extracted
with CHCl
(3ꢂ30 mL). The extract was washed with water
2ꢂ30 mL) and dried over K CO . The solvent was removed under
reduced pressure and the residue was distillated in vacuum to give
3
3
. Conclusion
(
2
3
In summary, a straightforward synthesis of secondary and ter-
3
a (5.98 g, 77%) or 3b (6.79 g, 69%).
tiary phosphines bearing bulky substituents has been developed
using one-pot phosphorylation of readily available -methylstyr-
ene and 4-chloro- -methylstyrene with elemental (red) phospho-
a
4.2.3. General procedure for preparation of phosphine oxides 4a,b
a
(Scheme 5). A mixture of alkene 1a or 1b (60 mmol), red phos-
rus in the superbase suspension KOH/DMSO. The reaction readily
proceeds under microwave irradiation to give hitherto inaccessible
bis(2-arylpropyl)phosphines or tris(2-arylpropyl)phosphines in
phorus (3.10 g, 100 mmol), hydroquinone (0.10 g), LPO∙0.5H
2
O
ꢀ
(7.00 g, 107 mmol) and DMSO (30 mL) was stirred at 130 S for 3 h.
The reaction mixture was cooled to room temperature, diluted with
water (50 mL) and analyzed. The R NMR spectrum reveals the
4
6e77% isolated yields. Tris(2-phenpropyl)phosphine has been
used as a ligand for trans-[Pd(PR Cl ] type complex, which proves
to be active in the Sonogashira couplings.
31
3
)
2
2
presence of phosphine 3a (3b) and phosphine oxide 4a (4b) in a 1:1
molar ratio along with minor amounts of potassium salt of 5a (5b)
and potassium hypophosphite. Unreacted phosphorus was filtered
off and filtrate was extracted with chloroform (3ꢂ30 mL). The ex-
tract was washed with water (2ꢂ30 mL) and the solvent was re-
moved. The residue was redissolved in acetone (15 mL) and
aqueous hydrogen peroxide (3 mL, 30%) was added to a resulting
solution. The mixture was stirred at ambient temperature for 5 min,
then diluted with water (30 mL) and extracted with chloroform
(2ꢂ20 mL). The extract was evaporated and the residue was dried
in vacuum to give 4a (6.31 g, 78%) or 4b (7.31 g, 72%).
4
4
. Experimental section
.1. General
All reactions were conducted under inert atmosphere (argon).
31
1
The monitoring was carried out by P{ H} NMR spectroscopy of the
1
13
31
reaction mixtures. The H, C and P NMR spectra were recorded
using a Bruker AV-400 spectrometer at 400.13, 100.62 and
1
1
61.98 MHz, respectively. The H NMR chemical shifts are expressed
The aqueous layer of reaction mixture was acidified with
aqueous HCl and extracted with chloroform (3ꢂ30 mL). The extract
with respect to residual protonated CDCl
as an internal standard. The C NMR shifts are expressed with
3
(7.27 ppm), which served
13
was washed with water (2ꢂ20 mL) and dried over Na
2 4
SO . The

4
48
A.V. Artem’ev et al. / Tetrahedron 72 (2016) 443e450
1
solvent was removed and residue was dried in vacuum to give 5a
1603, 1584, 1494, 1453, 1402, 1378, 1357, 1285, 1180, 764, 700. H
3
(
1.66 g, 15%) or 5b (1.31 g, 10%).
NMR (400.13 MHz, CDCl
1.51e1.95 (m, 4H, CH
1H, PH), 7.13e7.25 (m, 10H, Ph). C NMR (100.62 MHz, CDCl
3
):
d¼1.27 (d, 6 H,
J
H,H ¼ 6.6 Hz, Me),
Single crystals of SSR-4a were obtained by slow evaporation of i-
PrOH solution of 4a in an open vessel (ambient temperature, sev-
eral days).
2
P), 2.76e2.83 (m, 2 H, CHPh), 6.21 and 7.56 (s,
13
3
):
¼23.20 (d, JP,C ¼ 7.3 Hz, Me), 29.30, 30.11 and 30.26 (d, JP,C ¼ 10.3,
3
1
d
1
1
2
J
P,C ¼ 12.0 and
JP,C ¼ 11.4 Hz, CH
2
P), 39.00 (d,
J
P,C ¼ 10.3 Hz,
4
(
.2.4. General procedure for preparation of phosphinic acids 5a,b
Scheme 6). A mixture of alkene 1a or 1b (40 mmol), red phos-
phorus (3.10 g, 100 mmol), hydroquinone (0.07 g), LPO∙0.5H
7.00 g, 107 mmol), DMSO (30 mL) and water (1 mL, 55 mmol) was
CHPh), 126.20 (p-C in Ph), 126.78, 128.42 (o,m-C in Ph), 147.28 (d,
3
31
J
PC ¼ 4.5 Hz, i-C in Ph). P NMR (161.98 MHz, CDCl
3
):
d
¼ꢁ81.0,
1
1
1
2
O
ꢁ81.7 and ꢁ82.4 (d, JP,H ¼ 203.4, JP,H ¼ 204.4 and JP,H ¼ 201.5 Hz,
(
respectively). Anal. Calcd for C18
Found: S, 79.80; O, 8.44; R, 11.32.
H23P: S, 79.97; O, 8.58; R, 11.46.
ꢀ
stirred at 110 S for 2 h. The reaction mixture was cooled to room
3
1
temperature, diluted with water (40 mL) and analyzed. The
NMR spectrum reveals the presence of potassium salt of acid 5a
5b) [major product] and secondary phosphine 2a (2b), tertiary
R
4.3.2. Bis[2-(4-chlorophenyl)propyl]phosphine (2b). Colorless oil, bp
ꢀ
1
(
235e238 C (3 Torr). H NMR (400.13 MHz, CDCl
6 H, Me), 1.48ꢁ1.90 (m, 4 H, CH P), 2.73ꢁ2.79 (m, 2 H, CHAr),
7.05ꢁ7.23 (m, 8 H, Ar). C NMR (100.62 MHz, CDCl ): ¼23.26 (Me),
3
):
d
¼1.23ꢁ1.25 (m,
phosphine 3a (3b), phosphine oxide 4a (4b) and potassium hypo-
phosphite. Unreacted red phosphorus was filtered off and filtrate
was extracted with chloroform (3ꢂ30 mL) to removed compounds
2
13
3
d
1
1
1
29.71, 29.91 and 30.07 (d, JP,C ¼ 12.8, JP,C ¼ 11.8 and JP,C ¼ 10.2 Hz,
2
2,3,5,6
2
a (2b), 3a (3b) and 4a (4b). The aqueous layer of reaction mixture
CH
2
P), 38.5 (d, JP,C¼10.8 Hz, CHAr), 128.1 j128.5 (C
in Ar),131.8
4
3
1
31
was acidified with aqueous HCl and extracted with CHCl
3ꢂ20 mL). The extract was washed with water (2ꢂ20 mL) and
dried over Na SO . The solvent was removed and residue was dried
in vacuum to give 5a (3.16 g, 43%) or 5b (3.15 g, 36%).
3
(C in Ar), 145.5 (d,
J
P,C¼4.9 Hz, C in Ar). P NMR (161.98 MHz,
1 1
(
CDCl
and
3
):
d
¼ꢁ81.97, ꢁ82.45 and ꢁ82.78 (d, JP,H ¼ 203.7, JP,H ¼ 203.7
1
2
4
J
P,H ¼ 203.0 Hz, respectively). Anal. Calcd for C18
H21Cl
2
P: S,
63.73; O, 6.24; P, 9.13. Found: S, 63.65; O, 6.28; P, 9.30.
ꢀ
4
(
.2.5. General procedure for preparation of phosphine chalcogenides
Scheme 7). To a solution of phosphine 3a or 3b (1.0 mmol) in
toluene (15 mL), powdered sulfur (32 mg, 1.0 mmol) or selenium
72 mg, 1.0 mmol) was added. The mixture was stirred at ambient
4.3.3. Tris(2-phenylpropyl)phosphine (3a). Colorless oil, bp 240
C
1
(1 Torr). H NMR (400.13 MHz, CDCl
3
):
d
¼1.18, 1.22 and 1.28 (d, 9 H,
P), 2.71ꢁ2.79 (m, 3 H,
CHPh), 7.04e7.27 (m, 15H, Ph). C NMR (100.62 MHz, CDCl ):
¼23.20, 23.23 and 23.29 (d, JP,C ¼ 8.5, JP,C ¼ 9.3 Hz and JP,C ¼ 8.5
3
J
H,H ¼ 7.0 Hz, Me), 1.34e1.63 (m, 6H, CH
2
13
(
3
3
3
3
temperature for 1 h. The solvent was removed under reduced
pressure, residue washed with hexane (10 mL) and dried in vacuum
to afford phosphine chalcogenides 6a (380 mg, 90%), 6b (430 mg,
d
1
1
Hz, Me), 37.87, 37.98, 38.0 and 38.01 (d, JP,C ¼ 14.4, JP,C ¼ 15.6 and
1
2
2
J
J
P,C ¼ 15.1 Hz, CH
2
P), 38.96, 39.03, 39.12 and 39.22 (d, JP,C ¼ 7.2,
2
2
9
2%) or 6c (525 mg, 92%).
P,C ¼ 8.1, JP,C ¼ 9.8 and JP,C ¼ 8.5 Hz, CHPh),126.0 (p-C in Ph),126.7
3
31
(
o-C in Ph), 128.3 (m-C in Ph), 147.8 (d, JP,C¼5.6 Hz, i-C in Ph).
NMR (161.98 MHz, CDCl ):
¼ꢁ35.95 and ꢁ34.42. Anal. Calcd for
33P: S, 83.47; O, 8.56; R, 7.97. Found: S, 83.28; O, 8.44; R, 7.69.
P
4
8
.2.6. Procedure for preparation of phosphonium salt 7 (Scheme
). To a solution of phosphine 3a (314 mg, 0.81 mmol) in acetoni-
3
d
27
C H
trile (10 mL), methyl iodide (172 g, 1.2 mmol) was added. The
mixture was stirred at ambient temperature for 5 h. The pre-
cipitated crystalline powder was filtered, washed with diethyl
ether and dried in vacuum to give salt 7 (407 mg, 95%).
4.3.4. Tris[2-(4-chlorophenyl)propyl]phosphine (3b). Light-yellow
1
oil. H NMR (400.13 MHz, CDCl
J
(
3
):
H,H¼7.0 Hz, Me), 1.35e1.95 (m, 6H, CH
m, 3H, CHAr), 6.94e7.27 (m, 12H, Ar). C NMR (100.62 MHz,
d
¼1.15, 1.21, 1.22 and 1.27 (d, 9H,
3
2
P), 2.57, 2.59, 2.67 and 2.76
13
3
4
.2.7. Procedure for preparation of complex 8 (Scheme 9). To a so-
lution of phosphine 3a (485 mg, 1.25 mmol) in CHCl (15 mL), PdCl
111 mg, 0.62 mmol) was added. The suspension was stirred at
CDCl
3
):
d
¼23.3, 23.4, 23.4 and 23.5 (d, JP,C¼6.9, 7.1, 7.1 and 7.5 Hz,
1
3
2
Me), 37.62, 37.64, 37.66 and 37.69 (d,
J
P,C¼16.0, 16.6 Hz, SO
2
P),
2
(
5
38.6, 39.06, 39.08 and 39.1 (d,
J
P,C¼4.1, 6.0, 6.0 and 9.0 Hz, CH),
ꢀ
2,6
0 C for 8 h and then filtered. The filtrate was concentrated under
128.22, 128.25, 128.28 and 128.33 (C in Ar), 128.58, 128.59, 128.59
3
,5
4
vacuum to ca. 4 mL and hexane (8 mL) was added to a resulting
solution. After a day, X-ray quality crystals were precipitated. They
were filtered off, washed with hexane and dried in air. Yield 340 mg
and 128.61 (C in Ar), 132.31, 132.45, 132.50 and 132.50 (C in Ar),
3
1
146.02, 146.06, 146.07 and 146.13 (d, JPC¼5.8, 5.1, 5.1 and 5.7 Hz, C
31
in Ar). P NMR (161.98 MHz, CDCl
3
):
d
¼ꢁ37.55 and ꢁ38.34. Anal.
(
57%).
Calcd for C27
3
H30Cl P: S, 65.93; O, 6.15; R, 6.30. Found: S, 65.79; O,
6.24; R, 6.15.
4
.2.8. General procedure for cross-coupling of alkynes 9aec with 1-
iodo-4-nitrobenzene (Table 1). A mixture of alkyne 9aec
1.26 mmol), 1-iodo-4-nitrobenzene (249 mg, 1.0 mmol), CuI (1 mg,
.006 mmol), Et N (708 mg, 7 mmol) and Pd(II) source [0.003 mmol
of complex 8 or Pd(PPh
4.3.5. Tris(2-phenylpropyl)phosphine oxide (4a). Colorless crystals,
mp 81e82 C (i-PrOH). FTIR (KBr), cm : 3104, 3083, 3060, 3028,
3002, 2957, 2927, 2870,1603,1583,1494,1453,1408,1398,1154,1138,
ꢀ
ꢁ1
(
0
3
1
3
)
2
Cl
2
] in benzene (4 mL) was stirred under
766, 699, 600. H NMR (400.13 MHz, CDCl
3
):
d
¼1.15,1.16,1.21 and 1.23
ꢀ
3
an argon atmosphere at 70e80 S. The reaction mixture was cooled
and filtered through alumina (1.5ꢂ1 cm), eluted with toluene
(d, 9H, JHH ¼ 6.7, 6.4, 7.3 and 7.8 Hz, Me),1.37, 1.54 and 1.49, 1.62 and
2 3 3
1.78 (dd, 6H, JH,H¼14.9, JH,H¼8.3, JP,H¼11.0 Hz, CH
2
P), 2.84e3.11 (m,
13
(
40 mL). The solvents were evaporated under reduced pressure,
3H, CHPh), 7.06e7.27 (m, 15H, Ph). C NMR (100.62 MHz, CDCl ):
3
3
and residue was recrystallized to give pure alkynes 10aec. Melting
d
¼24.4 and 24.6 (d, JP,C ¼ 9.7 and 10.9 Hz, Me), 33.9, 34.0 and 34.4 (d,
19
2
1
points of 2-methyl-4-(4-nitrophenyl)but-3-yn-2-ol (10a), 1,2-
J
P,C¼3.7, 2.2 and 2.9 Hz, CH), 36.5, 38.3 and 38.8 (d, JP,C¼62.5, 60.2
2
0
bis(4-nitrophenyl)ethyne
(10b)
and
1-methoxy-4-((4-
2
and 62.5 Hz, CH P), 126.3, 126. 5 and 126.5 (p-C in Ph), 126.7, 126.81
2
1
nitrophenyl)ethynyl)benzene (10c) were consistent with the lit-
and 126.84 (o-C in Ph),128.4,128.5 and 128.6 (m-C in Ph),146.7,146.5,
3
31
erature data.
146.6 and 146.8 (d, JP,C ¼ 8.1, 7.6, 7.8 and 7.0 Hz, i-C in Ph). P NMR
161.98 MHz, CDCl ): 33OP: S,
¼44.72 and 45.82. Anal. Calcd for C27
80.17; O, 8.22; R, 7.66. Found: S, 80.31; O, 8.14; R, 7.47.
(
3
d
H
4
.3. Characterization data for synthesized compounds
ꢀ
4
.3.1. Bis(2-phenylpropyl)phosphine (2a). Colorless oil, bp 180 C (1
4.3.6. Tris[2-(4-chlorophenyl)propyl]phosphine oxide (4b). Colorless
ꢁ1
ꢀ
ꢁ1
crystals, mp 97e99 C (hexane). FTIR (film), cm : 3083, 3058,
Torr). FTIR (film), cm : 3084, 3061, 3028, 3002, 2963, 2928, 2873,

A.V. Artem’ev et al. / Tetrahedron 72 (2016) 443e450
449
3
025, 2964, 2927, 2876, 1651, 1596, 1575, 1494, 1454, 1412, 1376,
2
CH P), 126.54, 126.58, 126.68 and 126.77 (p-C in Ph), 127.00, 127.17,
1
8
340, 1296, 1276, 1182, 1167, 1094, 1032, 1013, 957, 944, 916, 907,
127.24 and 127.32 (o-C in Ph), 128.46, 128.51, 128.52 and 128.59 (m-
1
3
61, 850, 828, 752, 720, 655, 634, 620, 546, 535, 500, 472. H NMR
C in Ph), 145.65, 145.70, 146.03 and 146.07 (d, JP,C¼5.2, 4.3, 3.9 and
3
31
(
400.13 MHz, CDCl
3
):
d
¼1.14, 1.19, 1.22 and 1.29 (d, 9H, JHH¼6.9 and
5.0 Hz, i-C in Ph). P NMR (161.98 MHz, CDCl
3
):
d
¼39.02 and 40.32
1
7.0 Hz, Me), 1.32e1.40, 1.43e1.55, 1.57e1.63 and 1.63e1.71 (m, 6H,
( JP,Se¼683 Hz). Anal. Calcd for C27
H33PSe: S, 69.37; O, 7.12; R, 6.63.
2
CH P), 2.91e2.95 and 3.04e3.13 (m, 3H, CHAr), 7.98e7.26 (m, 12H,
Found: S, 69.22; O, 7.10; R, 6.48.
1
3
C
H
6 4
). C NMR (100.62 MHz, CDCl
3
):
d
¼24.0, 24.2, 24.3 and 24.4 (d,
3
J
J
P,C¼8.2, 9.5, 8.2 and 8.5 Hz, Me), 33.5, 33.6, 33.7 and 34.8 (d,
4.3.11. Tris[2-(4-chlorophenyl)propyl]phosphine selenide (6c). Light-
2
ꢁ1
P,C¼3.6, 3.7, 3.2 and 3.2 Hz, CH), 37.2, 38.0, 38.5 and 39.3 (d,
yellow oil. FTIR (film), cm : 3080, 3025, 2959, 2918, 2850, 1655,
1JP,C¼62.0, 63.0, 62.1 and 62.7 Hz, CH
P), 128.1, 128.2, 128.26 and
1648,1596,1493,1462,1452,1411,1375,1342,1275,1241,1151,1095,
2
2,6
3,5
1
128.30 (C in Ar), 128.78, 126.82 and 128.83 (C in Ar), 132.30,
1013, 960, 916, 903, 853, 825, 765, 720, 702, 651, 620, 544, 508. H
4
3
1
32.31 and 132.36 (C in Ar), 144.7, 144.8, 145.0 and 145.0 (d,
NMR (400.13 MHz, CDCl
3
):
d
¼1.09, 1.12, 1.12, and 1.22 (d, 9H, JH,H
¼
3
1
31
J
P,C¼6.1, 6.5, 6.5 and 7.1 Hz, C in Ar). P NMR (161.98 MHz, CDCl
¼44.87 and 44.42. Anal. Calcd for C27 30Cl OP: S, 63.85; O, 5.95;
R, 6.10. Found: S, 63.77; O, 6.07; R, 5.64.
3
):
7.0, 6.8, 7.3 and 6.8 Hz, Me), 1.18, 1.66, 1.23, 1.72; 1.63, 1.70 and 1.74,
1.87 (m, 6H, CH P), 2.99, 3.15, 3.25 and 3.41 (m, 3H, CHAr),
6.98e7.29 (m, 12H, Ar). C NMR (100.62 MHz, CDCl
d
H
3
2
13
3
):
d
¼23.94,
3
24.16, 24.57 and 24.60 (d,
J
P,C¼9.9, 12.1, 10.8 and 12.5 Hz, Me),
2
4.3.7. 2-Phenylpropylphosphinic acid (5a). Colorless oil. FTIR (film),
34.71, 34.91, 35.10 and 35.40 (d, JP,C¼2.2, 2.5, 2.8 and 3.2 Hz, CH),
ꢁ
1
1
cm : 3084, 3061, 3028, 3002, 2963, 2928, 2873, 1603, 1584, 1494,
38.16, 38.80, 40.10 and 40.35 (d, JP,C¼39.8, 42.1, 40.5 and 42.4 Hz,
1
2,6
1453, 1402, 1378, 1357, 1285, 1180, 764, 700. H NMR (400.13 MHz,
2
CH P), 128.44, 128.66, 128.76 and 128.82 (C in Ar), 128.85, 128.86,
3
3,5
4
CDCl
3
):
d
¼1.36 (d, 3 H, JH,H = 8.3 Hz, Me), 1.97 (m, 2H, CH
2
P), 3.19
128.90 and 128.92 (C in Ar), 132,50, 132,57, 132.61 and 132.69 (C
1
3
(
1
m, 1H, CH), 6.84 (d, 1H, JP,H¼531 Hz, PH), 7.20e7.27 (m, 5H, Ph),
in Ar), 144.12, 144,34, 144.44 and 144.57 (d,
J
PC¼4.6, 6.9, 4.1 and
):
¼38.74 and 37.87.
¼ꢁ371 (d, JP,Se¼699 Hz). Anal. Calcd
3
H30Cl PSe: S, 56.81; O, 5.30; R, 5.43. Found: S, 56.72; O,
1.58 (s, 1H, OH). 13C NMR (100.62 MHz, CDCl
):
d
¼23.7 (d, JP,C
3
¼
5.9 Hz, C in Ar). P NMR (161.98 MHz, CDCl
1
31
d
3
3
1
77
1
8
.2 Hz, Me), 34.0 (SOPh), 38.4 (d, JP,C¼92.4 Hz, CH
2
P), 126.7 (p-C in
Se NMR (76.31 Hz, CDCl
for C27
5.41; R, 5.29.
3
): d
3
31
Ph), 128.68 (o,m-C in Ph), 146.0 (d, JP,C¼10.0 Hz, i-C in Ph). P NMR
1
(
161.98 MHz, CDCl
3
):
d
¼32.06 ( JP,H¼531 Hz). Anal. Calcd for
9 13 2
C H O
P: S, 58.69; O, 7.11; R, 16.82. Found: S, 58.53; O, 7.24; R,
1
6.69.
4.3.12. Iodo(methyl)tris(2-phenylpropyl)phosphorane
(7). Yellow
ꢀ
ꢁ1
crystals, mp 158e164 C (ethyl acetate). FTIR (KBr), cm : 3103,
3083, 3062, 3025, 2963, 2917, 2900, 1601, 1582, 1495, 1452, 1410,
1395, 1372, 1360, 1303, 1287, 1260, 1200, 1183, 1164, 1080, 1054,
4
.3.8. 2-(4-Chlorophenyl)propylphosphinic acid (5b). Colorless oil.
1
3
H NMR (400.13 MHz, CDCl
3
):
d
¼1.37 (d, 3H,
J
H,H¼6.4 Hz, Me),
1
2
.00e2.07 (m, 2H, CH P), 3.16e3.28 (m, 1H, CH), 6.87 (s, 1H,
2
1029, 1011, 930, 900, 872, 811, 773, 767, 736, 721, 706, 563, 547. H
1
3
2
J
P,H¼540 Hz, PH), 7.16 and 7.28 (d, 4H, JH,H¼8.5 Hz, Ar),11.81 (s,1H,
NMR (400.13 MHz, CDCl
J
3
):
P,H¼2.0 and 2.3 Hz, CHMe), 1.07 (d, 3H,
1.97e2.03, 2.08e2.14, 2.26e2.45 and 2.49e2.60 (m, 6H, CH
d
¼1.06, 1.31 and 1.36 (d, 9H, JH,H¼6.9,
1
3
3
4
2
OH). C NMR (100.62 MHz, CDCl
3
3
):
d
¼23.4 (d, JP,C¼10.1 Hz, Me),
J
P,H¼13.6 Hz, PMe),
P),
1
2,3,5,6
3.3 (SOAr), 37.5 (d, JP,C¼93.8 Hz, CH
2
P), 128.0 and 128.7 (C
in
2
4
3
P,C¼10.0 Hz, C in Ar). 31P NMR
1
Ar), 132.3 (C in Ar), 143.8 (d,
161.98 MHz, CDCl ):
¼34.24 (d,
12ClO
J
2.63e2.77, 2.75e2.98 and 3.04e3.07 (m, 3H, CHPh), 7.36e7.10 (m,
1
13
1
(
C
3
d
J
P,H¼540 Hz). Anal. Calcd for
15H, Ph). C NMR (100.62 MHz, CDCl
3
):
d
¼6.52 (d, JP,C¼49.3 Hz,
3
9
H
2
P: S, 49.45; O, 5.53; R, 14.17. Found: S, 49.29; O, 5.65; R,
MeP), 25.38, 25.56, 25.64 and 25.66 (d,
JP,C ¼ 16.6, 16.2, 15.8 and
1
14.01.
15.0 Hz, Me), 29.38, 29.67 and 29.87 (d, JP,C ¼ 46.1, 46.9 and 45.2
2
Hz, CH
2
P), 33.88, 34.04 and 34.44 (d,
J
P,C ¼ 4.3, 4.2 and 4.3 Hz,
4.3.9. Tris(2-phenylpropyl)phosphine sulfide (6a). Yellowish oil.
CHPh), 127.04, 127.17, 127.18 and 127.21 (o-C in Ph), 127.86, 127.96,
127.98 and 128.01 (p-C in Ph),129.39, 129.48,129.49 and 128.01 (m-
ꢁ1
FTIR (film), cm : 3151, 3103, 3083, 3061, 3027, 3002, 2961, 2928,
871, 1602, 1583, 1493, 1453, 1404, 1374, 1357, 1285, 1245, 1196,
3
2
C in Ph), 143.27, 143.34, 145.37 and 143.50 (d, JP,C¼2.2, 2.3, 2.9 and
1
31
1
155, 1079, 1051, 1029, 1008, 916, 853, 765, 700, 602, 563, 542. H
NMR (400.13 MHz, CDCl ):
¼1.02, 1.06, 1.08 and 1.18 (d, 9H,
H,H¼6.9, 7.0, 6.9 and 7.1 Hz, Me), 1.53e1.84 (m, 6H, CH P),
.80e3.35 (m, 3H, CHPh), 7.03e7.28 (m, 15H, Ph). C NMR
2.4 Hz, i-C in Ph). P NMR (161.98 MHz, CDCl
3
):
d
¼28.97, 30.15.
3
d
Anal. Calcd for C28H36IP: S, 63.40; O, 6.84; R, 5.84. Found: S, 63.31;
O, 6.92; R, 5.72.
3
J
2
13
2
3
(
100.62 MHz, CDCl
3
):
d
¼24.68, 24.70, 24.82 and 24.86 (d,
J
P,C
2
¼
4.3.13. Bis[tris(2-phenylpropyl)phosphine]palladium(II)
dichloride
ꢀ
ꢁ1
11.9,11.5,11.3 and 12.6 Hz, Me), 34.35, 34.51, 34.67 and 35.46 (d, JP,C
(8). Yellow crystals, mp 198e204 C. FTIR (KBr), cm : 3082, 3059,
3024, 2962, 2925, 2870, 1601, 1493, 1452, 1400, 1376, 1353, 1324,
1286, 1239, 1230, 1198, 1176, 1157, 1144, 1079, 1050, 1039, 1027, 1010,
¼
3.2, 3.1, 3.2 and 3.6 Hz, CHPh), 37.8, 39.4, 40.6 and 41.3 (d,
P,C¼46.9, 48.6, 48.3 and 46.8 Hz, CH
1
J
2
P), 126.6, 126.7, 126.76 and
1
126.79 (p-C in Ph), 126.9, 127.0, 127.1 and 127.2 (o-C in Ph), 128.4,
997, 919, 854, 836, 790, 771, 727, 705, 531. H NMR (400.13 MHz,
3
1
J
28.46, and 128.51 (m-C in Ph), 145.8, 145.9, 146.2 and 146.25 (d,
CDCl
3
):
d
¼1.17, 1.19, 1.33, 1.34 and 1.36 (d, 18H,
J
H,H¼7.1 Hz, Me),
P),
3.07e3.08, 3.17e3.29 and 3.33e3.35 (m, 6H, CHPh), 7.88e7.23 (m,
3
31
P,C¼5.8, 4.9, 4.4 and 6.1 Hz, i-C in Ph). P NMR (161.98 MHz,
1.53e1.54, 1.65e1.67, 1.74, 2.10e2.14 and 2.28e2.33 (m, 12H, CH
2
CDCl
3
):
d
¼49.32 and 49.44. Anal. Calcd for C27
H33PS: S, 77.10; O,
13
7.91; R, 7.36. Found: S, 77.01; O, 7.69; R, 7.20.
30H, Ph). C NMR (100.62 MHz, CDCl
3
):
d
¼23.00, 23.11, 25.02,
2
5.05, 25.44 and 25.49 (Me), 30.18, 30.39, 30.77 and 32.10 (CHP),
4
.3.10. Tris(2-phenylpropyl)phosphine selenide (6b). Yellowish oil.
36.81, 37.22, 37.27, 37.32 and 37.42 (CH
2
Ph), 126.29, 126.72, 126.82,
ꢁ
1
FTIR (film), cm : 3103, 3082, 3061, 3027, 3001, 2961, 2926, 2871,
602, 1583, 1493, 1453, 1401, 1374, 1358, 1285, 1241, 1196, 1155,
127.04, 127.47, 127.49, 128.43, 128.70, 128.91 and 128.97 (o,m,p-C in
31
1
Ph), 147.02 and 147,74 (i-C in Ph). P NMR (161.98 MHz, CDCl
3
):
1
1079, 1051, 1029, 1008, 916, 853, 765, 700, 602, 563, 542. H NMR
d
¼13.92 and 13.95. Anal. Calcd for C54
2 2
H66Cl P
Pd: S, 67.96; O, 6.97;
3
(
6
400.13 MHz, CDCl
3
):
d
¼1.98, 1.06, 1.08 and 1.17 (d, 9H,
P), 2.75e3.36 (m, 3H,
CHPh), 7.03e7.28 (m, 15H, Ph). C NMR (100.62 MHz, CDCl ):
¼24.45, 24.53, 24.57 and 24.68 (d, JP,C¼12.8, 12.1, 11.4 and 12.8 Hz,
J
H,H¼6.8,
R, 6.49. Found: S, 67.70; O, 7.08; R, 6.31.
.5, 6.5 and 6.8 Hz, Me), 1.55e1.95 (m, 6H, CH
2
1
3
3
Acknowledgements
3
d
2
Me), 34.98, 35.12, 35.37 and 36.12 (d, JP,C¼2.9 and 4.0 Hz, CHPh),
The work was supported by the President of the Russian Fed-
eration (program for the support of leading scientific schools, grant
1
3
6.88, 38.72, 39.85 and 41.00 (d, JP,C¼39.6, 42.2, 41.4 and 39.6 Hz,

450
A.V. Artem’ev et al. / Tetrahedron 72 (2016) 443e450
6. For example, see: (a) Kara c¸ ar, A.; Th
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(
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The spectral data were obtained using the instrument park of
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8
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