One-pot synthesis of ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides

Article abstract of DOI:10.1016/j.tet.2012.08.091

Ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides have been synthesized by the exhaustive regioselective addition of secondary phosphines, phosphine sulfides and phosphine selenides to available tris(4-vinylbenzyl)phosphine oxide under free-radical conditions (UV irradiation or AIBN) in good to excellent yields.

Full text of DOI:10.1016/j.tet.2012.08.091

Tetrahedron 68 (2012) 9218e9225
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
One-pot synthesis of ultra-branched mixed tetradentate tripodal phosphines and
phosphine chalcogenides
Nina K. Gusarova, Vladimir A. Kuimov, Svetlana F. Malysheva, Nataliya A. Belogorlova,
*
Alexander I. Albanov, Boris A. Trofimov
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Science, 1 Favorsky St., Irkutsk 664033, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 28 May 2012
Received in revised form 9 August 2012
Accepted 28 August 2012
Available online 1 September 2012
Ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides have been syn-
thesized by the exhaustive regioselective addition of secondary phosphines, phosphine sulfides and
phosphine selenides to available tris(4-vinylbenzyl)phosphine oxide under free-radical conditions (UV
irradiation or AIBN) in good to excellent yields.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Phosphorylation
Radical reactions
Phosphines
Phosphine chalcogenides
Tris(4-vinylbenzyl)phosphine oxide
1. Introduction
multistep. The known protocols utilize moisture- and air-sensitive
phosphorus halides and organometallic compounds often accom-
Tetradentate tripodal ligands containing phosphine moieties are
widely used for design of multi-purpose metal complexes.1,2 For
instance, complexes of Cr(III),1 Fe(II, III),1,3 Co(II),1,4 Ni(II),5 Mo(III),1,6
Ru(II),1,2,7 Rh(II),1,4,8 Pd(II),9,10 W(III),2a,6 Os(II),1,7b,c Ir(II),1 Pt(II),1,9
panied by side-reactions.2b,19 Besides, the reported PP3 is limited by
the representatives with just a few substituents (Me, Et, Cy, Ph) at
the phosphorus atom. Therefore, the development of new more
straightforward phosphorus halide-free approaches to various
tetraphosphines and tetraphosphine chalcogenides is of standing
synthetic importance.
A promising approach to the synthesis of novel tetradentate
tripodal ligands could be the reaction of radical addition of sec-
ondary phosphines and phosphine chalcogenides to tri-
alkenylphosphines or their chalcogenides. This stimulated us to pay
attention to the readily available tris(4-vinylbenzyl)phosphine
oxide (1) as a possible parent starting compound capable of adding
the diverse phosphines and phosphine chalcogenides across its
three double bonds. Phosphine oxide 1 is now easily prepared in
a one-pot procedure by direct phosphorylation of commercially
available 4-vinylbenzylchloride with red phosphorus (Scheme 1).19
Hg(II),11
and
polynuclear
complexes12
with
tris[(2-
diphenylphosphano)ethyl]phosphine, (Ph2PCH2CH2)3P (PP3), which
is now one of the most thoroughly studied tetradentate tripodal li-
gands, act as catalysts for a variety of organic transformations.1,3d,g,13,14
Complexes of PP3 with Ru are applied for preparation of diagnostic
radiopharmaceutical imaging agents15 and complexes of this ligand
with Ag and Au display intenseluminescentemission atroom andlow
temperatures.16 In recent years, mixed chalcogene derivatives of PP3
(PP3Xn, X¼O, S, Se; n¼1e4) are also employed for the design of or-
ganometallic catalysts17 and useful materials.18 For example, rhodium
complexes of PP3X4 catalyze the carbonylation of methanol to acetic
acid and its ester.17e The readily regenerative and air-stable Pd com-
plex, [Pd(PP3S4)(dba)], has been used as a CeC coupling catalyst.17bee
One of the limitations in the controlled design of such com-
plexes is inaccessibility of tetradentate tripodal phosphines ligands
and their derivatives, especially their polyphosphine chalcogen-
ides. The conventional syntheses of these ligands are laborious and
O
Cl
KOH/H2O
PTC
Pred
+
P
+
PTC = PhCH2NEt3Cl-
1
55%
* Corresponding author. Fax: þ7 9392 419346; e-mail address: boris_trofimov@
irioch.irk.ru (B.A. Trofimov).
Scheme 1. Synthesis of tris(4-vinylbenzyl)phosphine oxide.
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.08.091

N.K. Gusarova et al. / Tetrahedron 68 (2012) 9218e9225
9219
In this work, for the addition to phosphine oxide 1, we have used
accessible secondary phosphines 2e4 and phosphine chalcogen-
ides 8e16, which are readily synthesized from aryl- and hetar-
ylalkenes and red phosphorus in superbasic system KOH/DMSO
(Scheme 2).20a,21
(1H, 13C, 31P NMR): mono- and diadducts were discernible in the
reaction mixtures only in trace amounts. As anticipated, tri-
phosphines 5e7 are easily oxidized by air during the isolation
and characterization to give the corresponding tetraphosphine
oxides 5oxe7ox (Scheme 3).
R2
P
R1
R2
R2
R1
X
R1
KOH/H2O
toluene
R1
X
R1
R2
PH3
Pred
H
P H
KOH/DMSO
R2
X = S, Se
Scheme 2. Synthesis of secondary phosphines and phosphine chalcogenides.
Scheme 3. Oxidation of triphosphines 5e7.
2. Results and discussion
The presence of three vinyl groups in phosphine oxide 1
assumes the formation of mono- and diadducts as well as products
of polymerization of both initial compound 1 and intermediate
adducts. Therefore, this study is aimed at the search for appropriate
conditions for chemoselective synthesis of tetradentate tripodal
phosphines and phosphine chalcogenides.
As our experiments have shown, under free-radical initiations,
phosphine oxide 1 adds phosphines 2e4 regioselectively to give
anti-Markovnikov adducts 5e7 in 60e80% yield (Table 1). The
target exhaustive addition reactions have been realized using the
1:3 reactant molar ratio, respectively, UV irradiation in benzene
(method A) or AIBN at 65e70 ꢀC in 1,4-dioxane (method B), all
experiments being carried out under argon.
Using phosphine 3 as an example, we have shown that under UV
irradiation (benzene, 25e30 ꢀC), phosphination of phosphine oxide
1 proceeds more effectively and selectively than in the presence of
AIBN (1,4-dioxane, 65e70 ꢀC): yield of triadduct 6 reaches 80%
(method A) versus 60% (method B), Table 1, cf. entries 2 and 3. In the
latter case noticeable amounts of insoluble polymer are formed,
likely due to the polymerization of the initial phosphine oxide 1
and/or intermediate mono- and diadducts.
Under similar free-radical initiation, secondary phosphine
sulfides 8e12 and phosphine selenides 13e16 undergo ready
addition to phosphine oxide 1 (the reactant molar ratio 3:1,
respectively) to afford, in the case of UV irradiation (benzene,
25e30 ꢀC), corresponding anti-Markovnikov triadducts 17e25,
tetradentate tripodal phosphine chalcogenides, in high yields
(Table 2).
As with the secondary phosphines (Table 1), the UV-initiated
reaction of phosphine oxide 1 with phosphine chalcogenides
8e16 (method A) is preferred over AIBN-promoted one (method B):
the yield of triadduct 17 is by 1.5 times higher and the reaction time
is significantly shorter (Table 2, entry 1). Noteworthy, the nature of
the solvent substantially influences the efficacy of the reaction
studied. In the example of phosphine sulfide 8, it has been dem-
onstrated that UV irradiation of the reactants in 1,4-dioxane (in-
stead of benzene) leads to a cross-linked polymer in almost
quantitative yield. The structure and composition of this polymer
was similar to that of the phosphine oxide 1 homopolymer, pre-
pared and characterized previously.22
As seen from Tables 1 and 2, diverse secondary phosphines and
phosphine chalcogenides containing Bu, Ph(CH2)2, PhCH(Me)CH2,
4-tBuC6H4(CH2)2, 4-MeOC6H4(CH2)2, 2-Fur(CH2)2, and 6-Me-3-
Py(CH2)2 substituents at phosphorus atom react easily with phos-
phine oxide 1 that supports the generality of this process.
As exemplified by triadduct 17, triphosphine sulfides can be
readily reduced with metal sodium (reflux toluene) to the corre-
sponding triphosphines (Scheme 4).
Note that secondary phosphine oxides do not react with phos-
phine oxide 1 under the above free-radical conditions. So, the UV
irradiation (20e35 ꢀC, 6 h, benzene) of the mixture of bis(2-
phenethyl)phosphine oxide and phosphine oxide 1 gives only
polymer of phosphine oxide 1 and the unreacted initial secondary
phosphine oxide. This is consistent with the known data about low
reactivity of secondary phosphine oxides in the radically induced
addition reactions.23 However, tetraphosphine oxides 5oxe7ox can
be easily prepared by the oxidation of the corresponding phos-
phines (Scheme 2).
Table 1
Exhaustive addition of secondary phosphines 2e4 to phosphine oxide 1
R1
R1
P
O
P
UV
R1
R1
P
3H
+
P
or AIBN
O
R1
2-4
R1
1
P
P
R1
R1
5-7
Entry
Secondary
phosphine
R1
Methoda/
time (h)
Productb
Yieldc (%)
1
2
3
2
3
Et
Ph
B/7.5
A/7.5
B/10
5
6
48 (70)
80 (96)d
60 (70)e
4
4
A/15
7
63 (85)
Me
N
a
Standard reaction conditions: molar ratio 1/2e4¼1:3, argon. Method A: UV,
25e30 ꢀC (heating resulted from irradiation), benzene. Method B: AIBN (1.5e2 wt %
of the reactants’ mass), 65e70 ꢀC, 1,4-dioxane.
b
Triphosphines 5, 7 were isolated as tetraoxides 5ox, 7ox, the corresponding
phosphines 5, 7 were identified in the reaction mixture by 31P NMR.
c
Isolated yield (31P NMR yield was given in parentheses).
d
Triphosphine 6 was isolated.
e
Triphosphine oxide 6ox was prepared.
The reaction has been monitored by 31P NMR spectroscopy to
follow the disappearance of the signals of the initial secondary
phosphines 2e4 at ꢁ71Oꢁ68 ppm and appearance of the signals
of the forming triadducts 5e7 at ꢁ30Oꢁ23 ppm. Under the
above conditions, the reaction is highly regio- and chemo-
selective to give almost exclusively anti-Markovnikov triadducts
The results obtained show (Tables 1 and 2) that the reactivity of the
PH-addends used in the reaction with phosphine oxide 1 falls in the
order: secondary phosphine selenides>secondary phosphine

9220
N.K. Gusarova et al. / Tetrahedron 68 (2012) 9218e9225
Table 2
Exhaustive addition of secondary phosphines chalcogenides 8e16 to phosphine oxide 1
X
R
R
P
O
P
X
R
UV
X
P
R
P
P
3
+
H
R
or AIBN
R
O
1
8-16
X
P
R
R
17-25
Entry
PH-addend
Methoda/time (h)
Product
Yieldb (%)
S
P
S
P
O
P
17
S
1
2
A/3.5
B/12
92 (99)
60 (70)
P
8
8
S
H
P
S
A/1
A/3
c
c
P
H
S
P
S
P
O
P
S
18
3
90(98)
P
9
H
S
P
S
P
S
P
t
Bu
O
P
t
Bu
But
But
19
S
P
4
A/4
87 (97)
10
S
t
t
Bu
Bu
H
P
t
Bu
t
Bu
Me
S
P
O
Me
Me
P
Me
S
P
S
20
5
A/4
77 (95)
Me
P
11
H
S
Me
Me
P
Me
S
P
S
P
MeO
O
P
OMe
MeO
MeO
21
S
6
A/8
78 (98)
P
S
MeO
12
H
MeO
OMe
P
MeO

N.K. Gusarova et al. / Tetrahedron 68 (2012) 9218e9225
9221
Table 2 (continued )
Entry
PH-addend
Methoda/time (h)
Product
Yieldb (%)
Se
P
Se
P
O
P
22
Se
P
H
7
A/2
85 (99)
13
Se
P
Se
P
Se
P
t
Bu
O
P
t
Bu
But
23
Se
8
A/3
78 (95)
P
Se
t
t
Bu
14
Bu
H
P
But
t
Bu
t
Bu
Me
Se
P
O
Me
Me
Se
P
Me
Me
P
Se
H
24
9
A/3.5
89 (97)
P
15
Me
Se
Me
P
Me
Se
P
Se
P
O
O
O
P
25
O
Se
H
O
10
A/4
85 (95)
16
O
P
Se
O
P
O
O
a
Standard reaction conditions: molar ratio 1/8e16¼1:3. Experiments were carried out under argon. Method A: UV, 25e30 ꢀC, benzene. Method B: AIBN (1.5e2 wt % of the
reactants’ mass), 65e70 ꢀC, 1,4-dioxane.
b
Isolated yield (31P NMR yield was given in parentheses).
Experiment was carried out in 1,4-dioxane. The homopolymer of 1 was isolated as a main product in this case.
c
been developed by exhaustive free-radical addition of secondary
X
P
P
phosphines and phosphine chalcogenides to available tris(4-
vinylbenzyl)phosphine oxide thus providing a facile short-cut to
a new family of prospective tetradentate tripodal ligands for design
of multi-purpose metal complexes. Importantly, all substrates
required for the presented syntheses are readily derived directly
from elemental phosphorus.
O
P
O
P
Na, toluene
reflux, 4 h
X
P
X
P
P
P
6
17
Scheme 4. Reduction of tris{4-[2-(diphenethylphosphorothioyl)ethyl]benzyl}phos-
phine oxide.
4. Experimental section
4.1. General
sulfides>secondary phosphines>secondary phosphine oxides that is
in agreement with the published data.23,24
IR spectra were run on
a ‘Bruker IFS 25’ spectrometer
(400e4000 cmꢁ1, KBr pellets).1H (400.13 MHz),13C (100.62 MHz), 31
P
3. Conclusions
NMR (161.98 MHz), and 77Se NMR (76.27 MHz) spectra were recorded
on a ‘Bruker DPX-400’ instrument in CDCl3 solutions and referenced to
internal HDMS (1H NMR), external 85% H3PO4 (31P NMR), and Me2Se
In summary, the one-pot chemoselective synthesis of ultra-
branched mixed phosphines and phosphine chalcogenides has
(
77Se NMR). Melting points were recorded on a ‘Micro Hot Stage

9222
N.K. Gusarova et al. / Tetrahedron 68 (2012) 9218e9225
POLYTHERM A’ apparatus. The photochemical reactions were per-
formed by using argon-purged solutions in quartz tubes. The photol-
yses were performed on OKN apparatus using a high-pressure
4.3.1. Tris{4-[2-(butylphosphoryl)ethyl]benzyl}phosphine oxide (5ox).
Colorless oil (375 mg, yield 50%, method B). IR (KBr):
2965, 2958, 2929, 2870, 1605, 1525,1490,1465,1437, 1420, 1407, 1379,
1290, 1273, 1214, 1209, 1198, 1159, 1129, 1070, 1034, 1011, 916, 896,
830, 814, 1055, 963, 948, 860, 751, 699, 558, 476, 449 cmꢁ1. 1H NMR
n¼3050, 3033,
mercury lamp (200 W, hn >200 nm). Benzene and 1,4-dioxane were
purified by distillation under argon over sodium benzophenone ketyl
immediately before use. Phosphine 2 was synthesized from butyl-
bromide and red phosphorus in the superbasic system
LietBuOHeNH3(l).25 Secondary phosphines 3, 4 were prepared from
styrene,21 or 2-methyl-5-vinylpyridine26 and phosphine as described
in the literature. Phosphine chalcogenides 8e16 were prepared by
reaction of corresponding phosphines with elemental sulfur and
selenium.27 The reaction studied was monitored using 31P NMR by
(400.13 MHz, CDCl3):
d
¼1.42e1.44 (m, 18H, CH3), 1.56 (m, 12H,
CH3CH2), 1.70 (m, 12H, EtCH2), 1.82 (m, 12H, PrCH2), 1.97 (m, 6H,
PCH2C6H4CH2), 2.98e2.89 (m, 12H, PCH2C6H4CH2CH2P), 6.98e7.14
(m, 12H, C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
d¼13.5 (Me), 23.3
(EtCH2), 24.1 (MeCH2), 27.2 (PrCH2), 27.5 (CH2C6H4), 29.9
(PCH2CH2C6H4), 34.6 (d, 1JPC¼61.0 Hz, CH2P), 127.7 (C-m), 128.5 (C-o),
130.1 (d, 3JPC¼5.1 Hz, C-i), 140.5 (d, 3JPC¼15.0 Hz, C-p) ppm. 31P NMR
disappearance of signal (d, ppm) of the starting PH-addends (the
(161.98 MHz, CDCl3):
d¼49.15 (Bu2P]O), 53.40 (CH2P]O) ppm.
ꢁ71Oꢁ68 ppm region for phosphines 2e4; the ꢁ4O22 ppm interval
for phosphine chalcogenides 8e16) and appearance of a new reso-
nance in the region of ꢁ30Oꢁ23 and 37O50 ppm for tertiary phos-
phines 5e7, phosphine sulfides 17e21, and selenides 22e25,
correspondingly. All experiments were carried out upon argon
atmosphere. The compounds synthesized were purified by
recrystallization (for 6ox, 7ox, 17e25) or reprecipitation (for 5ox, 6).
C51H84O4P4 (885.105): calcd C 69.21, H 9.57, P 14.00; found C 69.00, H
9.27, P 14.15.
4.3.2. Tris{4-[2-(2-diphenethylphosphoryl)ethyl]benzyl}phosphine
oxide (6ox). White powder (375 mg, yield 80%, method A and
281 mg, yield 60%, method B). Mp 135e138 ꢀC (iso-propanol). IR
(KBr):
1209, 1164, 1129, 1070, 963, 948, 860, 751, 699, 558, 493 cmꢁ1. 1H
NMR (400.13 MHz, CDCl3):
¼2.03e2.05 (m, 18H, CH2P), 2.92e2.94
(m, 24H, CH2Ph, CH2C6H4), 7.15e7.27 (m, 42H, Ph, C6H4) ppm. 13
NMR (100.62 MHz, CDCl3):
n
¼3058, 3025, 2925, 2860, 1602, 1512, 1496, 1454,1421, 1403,
d
4.2. Synthesis of tris{4-[2-(2-diphenethylphosphino)ethyl]
benzyl}phosphine oxide (6) (Table 1, entry 2)
C
d
¼27.5 and 27.5 (CH2C6H4, CH2Ph), 29.8
(d, 1JPC¼64.2 Hz, PhCH2CH2P), 29.8 (d, 1JPC¼62.9 Hz, PCH2CH2C6H4),
34.6 (d, 1JPC¼61.4 Hz, C6H4CH2P), 126.4 (C-p in Ph), 127.9 (C-o in Ph),
127.8 (C-m in C6H4), 128.5 (C-o in C6H4), 128.5 (C-m in Ph), 129.9 (d,
2JPC¼5.3 Hz, C-i in C6H4), 139.8 (d, 3JPC¼12.5 Hz, C-i in Ph), 140.5 (d,
3JPC¼12.9 Hz, C-p in C6H4) ppm. 31P NMR (161.98 MHz, CDCl3):
Method A: A solution of phosphine oxide 1 (0.16 g, 0.4 mmol)
and secondary phosphine 2 (0.29 g, 1.2 mmol) in benzene (0.5 mL)
was irradiated in quartz ampoule for 7.5 h. Benzene was removed
and the residue was dissolved in ether (1.5 mL) and reprecipitated
in hexane (10 mL). The solvents were decanted from the residue,
the latter was dried in vacuum to give triphosphine 6. Colorless oil
d
¼46.86 (PhCH2CH2)2P]O, 41.60 (CH2P]O). C75H84 O4P4
(1173.36): calcd C 76.77, H 7.22, P 10.56; found C 76.71, H 7.20, P
10.44.
(360 mg, yield 80%, method A). IR (KBr):
n
¼3070, 3055, 2975, 2930,
2900, 2863, 1606, 1582, 1522, 1499, 1457, 1425, 1406, 1211, 1165,
1130, 1056, 1034, 1012, 965, 947, 926, 876, 863, 820, 817, 753, 699,
Polymer: IR (KBr):
1511, 1496, 1453, 1421, 1210, 1180, 1127, 1069, 1019, 971, 859, 752,
699, 559, 467 cmꢁ1. Found: C 69.77, H 6.93, P 10.22.
n
¼3274, 3024, 2919, 2854, 1668, 1628, 1603,
560, 474, 450 cmꢁ1. 1H NMR (400.13 MHz, CDCl3):
d
¼1.73e2.13 (m,
18H, CH2P), 2.71e2.99 (m, 24H, CH2Ph, CH2C6H4CH2), 7.14e7.29 (m,
42H, Ph, C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼22.3 (d,
4.3.3. Tris{4-(2-bis[2-(6-methylpyrid-3-yl)ethyl]phosphoryl)ethyl]
1
1JPC¼12.1 Hz, PCH2CH2C6H4), 29.0 (d, JPC¼16.0 Hz, PCH2CH2Ph),
30.1 (d, 1JPC¼63.8 Hz, CH2P]O), 32.2 (d, 2JPC¼15.0 Hz, PhCH2), 34.5
(d, 2JPC¼10.6 Hz, CH2C6H4), 126.7 (C-p in Ph), 128.4 (C-o in Ph),128.7
(C-m in C6H4), 128.8 (C-m in Ph), 129.8 (d, 2JPC¼7.0 Hz, C-i in C6H4),
benzyl}-phosphine oxide (7ox). White powder (80 mg, yield 63%,
method B). Mp 138e140 ꢀC (iso-propanol). IR (KBr):
n
¼3008, 2924,
2856, 1667, 1651, 1604, 1569, 1512, 1493, 1448, 1396, 1336, 1299,
1245, 1217, 1163, 1141, 1127, 1034, 944, 915, 860, 832, 751, 732, 645,
3
3
130.3 (d, JPC¼5.2 Hz, C-o in C6H4), 139.4 (d, JPC¼13.6 Hz, C-p in
548, 491 cmꢁ1. 1H NMR (400.13 MHz, CDCl3):
d
¼1.68e1.76 (m, 6H,
C6H4), 140.3 (d, 3JPC¼13.6 Hz, C-i in Ph) ppm. 31P NMR (161.98 MHz,
PCH2CH2C6H4), 2.0e2.06 (m, 12H, PyCH2CH2P), 2.50 (18H, Me),
2.67e2.71 (m, 6H, CH2P), 2.87e2.98 (m, 18H, CH2Py), 7.09e8.33 (m,
C6D6):
d
¼ꢁ28.23 (CH2P), 38.19 (CH2P]O) ppm. C75H84OP4
(1125.36): calcd C 80.05, H 7.52, P 11.01; found C 79.41, H 7.55, P
10.92. Trisphosphine 6 was easily and practically quantitatively
oxidized in the presence of O2 (air, 25 min) to give tetraphosphine
30H, in C6H4 and Py) ppm. 13C NMR (100.62 MHz, CDCl3):
d¼24.5
1
(Me), 25.4 (PyCH2), 27.9 (PCH2CH2C6H4), 30.7 (d, JPC¼60.5 Hz,
CH2PCH2CH2Py), 34.9 (d, 1JPC¼72.2 Hz, CH2P), 123.9 (C]CMe in Py),
129.1 (C-m in C6H4), 130.2 (d, 2JPC¼7.2 Hz, C-i in C6H4), 130.9 (C-o in
C6H4),133.0 (d, 3JPC¼13.5 Hz, C-i in Py),133.7 (d, 3JPC¼16.8 Hz, C-p in
C6H4), 136.9 (HC]C in Py), 149.1 (C]N in Py), 157.4 (CMe in
oxide 6ox
.
4.3. General procedure for the preparation of phosphine ox-
Py) ppm. 31P NMR (161.98 MHz, CDCl3):
(PyP]O) ppm. C75H90 N6O4P4 (1263.45): calcd C 71.30, H 7.18, N
d
¼40.18 (P]O), 45.09
ides 5oxe7ox (Table 1, entries 1, 3, 4)
6.65, P 9.81; found C 71.21, H 7.20, N 6.57, P 9.74.
Method B: A solution of phosphine oxide 1 (0.15 mmol) and
secondary phosphines 2e4 (0.45 mmol) in dioxane (5 mL) in the
presence of AIBN (1e2 wt % of the total mass of reactants) was
stirred for 65e70 ꢀC in a closed reactor with magnetic stirrer (re-
action times were given in Table 1). A white polymer precipitate
was formed in each case. Benzene (3 mL) was added to the reaction
mixture, undissolved polymer was filtered off through paper filter.
Benzene was removed, the residue was reprecipitated from chlo-
roform to ether (in the case of compound 5ox) or recrystallized (for
compounds 6ox, 7ox), dried in vacuum to give tetraphosphine oxides
5oxe7ox. In the case of tetraphosphine oxide 5ox, the residue was
additionally washed with hot hexane before the reprecipitation
procedure.
4.4. General procedure for the preparation of tetraphosphine
chalcogenides 17e25 (Table 2)
Method A: A solution of phosphine oxide 1 (0.1 mmol) and
secondary phosphine chacogenides 8e16 (0.3 mmol) in benzene
(0.5 mL) was irradiated in quartz ampoule (reaction times were
given in Table 2). Benzene (3 mL) was added to the reaction mix-
ture, undissolved polymer was filtered off through paper filter.
Benzene was removed, the residue was reprecipitated from chlo-
roform to ether, dried in vacuum to give tetraphosphine chalco-
genides 17e25 (purified additionally by recrystallization from
iso-propanol).

N.K. Gusarova et al. / Tetrahedron 68 (2012) 9218e9225
9223
4.4.1. Tris(4-{2-[diphenethylphosphorothioyl]ethyl}benzyl)phosphine
oxide (17). White powder (168 mg, yield 92% method A and 110 mg,
yield 60%, method B). Mp 100e102 ꢀC (iso-propanol). IR (KBr):
C6H4), 129.2 and 129.3 (C-m in Ph), 129.9 (C-i in C6H4), 130.6 (C-o in
C6H4), 137.02 (C-p in C6H4), 146.1, 146.7 and 146.7(C-i in Ph) ppm.
31P NMR (161.98 MHz, CDCl3):
d
¼42.20 (P]O), 48.81, 49.31 and
n
¼3084, 3058, 3003, 2922, 2901, 2858, 1602, 1583, 1511, 1495, 1453,
1421, 1401, 1239, 1207, 1130, 1108, 1072, 1020, 1006, 950, 910, 906,
858, 752, 697, 598, 546, 493 cmꢁ1 1H NMR (400.13 MHz, CDCl3):
49.60 (P]S). The presence of three signals in the 31P NMR is likely
attributable to several asymmetric carbons in molecule 20.
C81H96OP4S3 (1305.72): calcd C 74.51, H 7.41, P 9.49, S 7.37; found C
74.47, H 7.39, P 9.43, S 7.33.
.
d
¼2.11e2.13 (m, 18H, CH2P), 2.90e2.92 (m, 24H, CH2Ph, CH2C6H4),
7.10e7.26 (m, 42H, Ph, C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
1
d
¼28.1 (CH2C6H4), 28.5 (CH2Ph), 32.7 (d, JPC¼48.0 Hz,
4.4.5. Tris(4-{2-[bis(4-methoxyphenethyl)phosphorothioyl]ethyl}
1
PCH2CH2C6H4), 32.8 (d, JPC¼48.3 Hz, PhCH2CH2P), 34.7 (d,
benzyl)phosphine oxide (21). Pale yellow powder (110 mg, yield 78%
1JPC¼61.2 Hz, CH2PO), 126.5 (C-p in Ph), 127.9 (C-m in C6H4), 128.2
method A). Mp 70e74 ꢀC (iso-propanol). IR (KBr):
n
¼3104, 3090,
2
(C-o in Ph), 128.7 (C-m in Ph), 129.7 (d, JPC¼7.4 Hz, C-i in C6H4),
3054, 3027, 2995, 2919, 2850, 2833, 1611, 1512, 1463, 1441, 1301,
3
3
130.1 (d, JPC¼4.4 Hz, C-o in C6H4), 139.4 (d, JPC¼15.1 Hz, C-p in
1246, 1177, 1129, 1033, 952, 849, 819, 734, 595, 540, 518 cmꢁ1. 1H
C6H4), 140.4 (d, 3JPC¼13.6 Hz, C-i in Ph) ppm. 31P NMR (161.98 MHz,
NMR (400.13 MHz, CDCl3):
d
¼2.02e2.10 (m,18H, CH2PS), 2.85e2.93
CDCl3):
d¼41.38 (P]O) and 48.38 (P]S) ppm. C75H84OP4S3
(m, 24H, CH2C6H4CH2), 3.74 (18H, MeO), 6.77e7.34 (m, 36H, Ph,
(1221.56): calcd C 73.74, H 6.93, P 10.14, S 7.87; found C 73.70, H
6.91, P 10.09, S 7.73.
C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
d¼27.69 (MeOC6H4CH2),
1
28.13 (CH2C6H4), 33.01 (d, JPC¼47.8 Hz, CH2PCH2), 37.42 (d,
1JPC¼67.1 Hz, CH2PO), 55.21 (MeO), 114.09 (C-o in MeOC6H4), 128.66
(C-m in C6H4), 129.17 (C-m in MeOC6H4), 130.20 (C-o in C6H4),
4.4.2. Tris(4-[2-(diphenylphosphorothioyl)ethyl]benzyl)phosphine
oxide (18). Pasty mass (95 mg, yield 90%, method A). IR (KBr):
2
3
132.53 (d, JPC¼7.8 Hz, C-i in C6H4), 133.07 (d, JPC¼16.1 Hz, C-i in
MeOC6H4), 135.27 (C-p in C6H4), 158.26 (C-p in MeOC6H4) ppm. 31
NMR (161.98 MHz, CDCl3):
n
¼3074, 3056, 3035, 2922, 2904, 2852, 1608, 1588, 1574, 1513, 1480,
P
1437, 1422, 1403, 1331, 1309, 1241, 1199, 1183, 1160, 1128, 1105, 1070,
1027, 998, 910, 863, 797, 733, 692, 645, 623,612, 580, 532, 501,
d¼44.81 (P]O), 48.56 (P]S) ppm.
C81H96 O7P4S3 (1401.718): calcd C 69.41, H 6.90, P, 8.84, S 6.86;
found C 69.35, H 6.87, P 8.74, S 6.59.
441 cmꢁ1
.
1H NMR (400.13 MHz, CDCl3):
d
¼2.76 (m, 6H, CH2PS),
2
2.93 (m, 6H, CH2C6H4), 2.99 (d, 6H, JPH¼13.7 Hz, CH2PO), 7.11 (m,
12H, C6H4), 7.49 (m,18H, HeC-p, HeC-m in Ph), 7.88 (m,12H, HeC-o
4.4.6. Tris(4-{2-[diphenethylphosphoroselenoyl]ethyl}benzyl)phos-
phine oxide (22). Beige powder (173 mg, yield 85%, method A). Mp
in Ph) ppm. 13C NMR (100.62 MHz, CDCl3):
d¼28.0 (CH2C6H4), 34.3
1
1
(d, JPC¼61.2 Hz, CH2PO), 34.4 (d, JPC¼55.1 Hz, SPCH2), 129.0 (d,
3JPC¼13.4 Hz, C-o in C6H4), 130.2 (d, 3JPC¼5.0 Hz, C-m in C6H4), 128.8
(d, 3JPC¼11.9 Hz, C-o in Ph), 131.1 (d, 3JPC¼10.3 Hz, C-m in Ph), 131.7
(d, 3JPC¼2.7 Hz, C-p in Ph), 139.8 (d, 2JPC¼17.2 Hz, C-i in C6H4), 141.9
(d, 3JPC¼16.8 Hz, C-p in C6H4),132.6 (d, 1JPC¼80.0 Hz, C-p in Ph) ppm.
100e102 ꢀC (iso-propanol). IR (KBr):
n
¼3106, 3083, 3024, 3002,
2922, 2900, 2858, 1602, 1583, 1511, 1495, 1453, 1421, 1400, 1269,
1238, 1203, 1180, 1130, 1108, 1072, 1019, 1002, 949, 910, 858, 749,
697, 572, 492, 463 cmꢁ1. 1H NMR (400.13 MHz, CDCl3):
d¼2.19e2.26
(m, 18H, CH2P), 2.89e2.99 (m, 24H, CH2Ph, CH2C6H4), 7.10e7.26 (m,
31P NMR (161.98 MHz, CDCl3):
d
¼41.67 (P]O), 41.90 (P]S) ppm.
42H, Ph, C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
d¼29.03
1
Anal. Calcd for: C63H60OP4S3. C, 71.84; H, 5.74; P, 11.76; S, 9.13.
Found: C, 76.24; H, 8.51; P, 7.91; S, 6.13.
(CH2C6H4), 29.43 (CH2Ph), 32.45 (d, JPC¼42.0 Hz, PCH2CH2C6H4),
32.52 (d, 1JPC¼40.9 Hz, PhCH2CH2P), 34.80 (d, 1JPC¼61.1 Hz, CH2PO),
126.71 (C-p in Ph), 128.35 (C-o in Ph), 128.67 (C-m in C6H4), 128.82
2
4.4.3. Tris(4-{2-[bis(4-tert-butylphenethyl)phosphorothioyl]ethyl}
benzyl)phosphine oxide (19). White needles (163 mg, yield 87%
(C-m in Ph), 129.78 (d, JPC¼7.0 Hz, C-i in C6H4), 130.28 (d,
3JPC¼5.2 Hz, C-o in C6H4), 139.36 (d, JPC¼13.6 Hz, C-p in C6H4),
3
3
method A). Mp 100e101 ꢀC (iso-propanol). IR (KBr):
3024, 2961, 2904, 2866, 1661, 1609, 1513, 1475, 1463, 1444, 1403,
1394, 1363, 1269, 1203, 1134, 1109, 1018, 953, 855, 838, 816, 776,
n
¼3091, 3054,
140.33 (d, JPC¼13.6 Hz, C-i in Ph) ppm. 31P NMR (161.98 MHz,
CDCl3):
NMR (76.27 MHz, CDCl3):
C75H84OP4Se3 (1362.24): calcd C 66.13, H 6.22, P 9.09, Se 17.39;
found C 66.11, H 6.21, P 9.02, Se 17.33.
d
¼42.26 (P]O) and 37.30 (P]Se, JPSe¼701.2 Hz) ppm. 77Se
d
¼ꢁ390.9 (1JPSe¼701.3 Hz) ppm.
678, 562 cmꢁ1. 1H NMR (400.13 MHz, CDCl3):
d
¼1.29 (s, 54H, Me),
2.10e2.28 (m, 18H, CH2PS), 2.88e3.04 (m, 24H, CH2C6H4, CH2PO),
7.10e7.33 (m, 36H, C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼28.1 (tBuC6H4CH2), 28.2 (CH2C6H4), 31.4 (Me), 32.8 (d,
4.4.7. Tris(4-{2-[bis(4-tert-butylphenethyl)phosphoroselenoyl]ethyl}
1JPC¼47.9 Hz, CH2P(S)CH2), 34.4 (Me3C), 37.3 (d, JPC¼67.8 Hz,
benzyl)phosphine oxide (23). Buff powder (183 mg, yield 78%,
1
t
t
CH2PO), 125.6 (C-o in BuC6H4), 127.9 (C-m in BuC6H4), 128.7 (C-m
in C6H4), 129.3 (d, 2JPC¼7.0 Hz, C-i in C6H4), 130.3 (C-o in C6H4), 137.4
(d, 3JPC¼13.6 Hz, C-i in tBuC6H4), 138.1 (d, 3JPC¼16.2 Hz, C-p in C6H4),
method A). Mp 102e104 ꢀC (iso-propanol). IR (KBr):
n
¼3090, 3053,
3022, 2960, 2903, 2865, 1512, 1475, 1474, 1463, 1442, 1403, 1363,
1268, 1203, 1134, 1109, 1019, 951, 858, 839, 816, 752, 563 cmꢁ1. 1H
149.5 (C-p in tBuC6H4) ppm. 31P NMR (161.98 MHz, CDCl3):
d¼42.64
NMR (400.13 MHz, CDCl3):
d
¼1.26 (s, 54H, Me), 2.19e2.24 (m, 18H,
(P]O), 48.32 (P]S) ppm. C99H132OP4S3 (1558.20): calcd C 76.31, H
CH2PCH2), 2.86e2.88 (m, 24H, CH2C6H4CH2), 7.09e7.29 (m, 36H,
8.54, P 7.95, S 6.17; found C 76.24, H 8.51, P 7.91, S 6.13.
C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼28.77 (tBuC6H4CH2),
1
28.91 (PCH2CH2C6H4), 31.32 (Me3C), 32.28 (d, JPC¼41.3 Hz,
4.4.4. Tris(4-{2-[bis(2-phenylpropyl)phosphorothioyl]ethyl}benzyl)
phosphine oxide (20). White powder (130 mg, yield 77% method A).
CH2PCH2), 34.39 (CMe), 34.80 (d, 1JPC¼62.0 Hz, CH2PO), 125.60 (C-o
t
t
in BuC6H4), 127.93 (C-m in BuC6H4), 128.70 (C-m in C6H4), 129.72
2
Mp 107e110 ꢀC (iso-propanol). IR (KBr):
n
¼3082, 3058, 3026, 2959,
(d, JPC¼6.6 Hz, C-i in C6H4), 130.17 (C-o in C6H4), 137.10 (d,
2923, 2870, 2851, 1602, 1583, 1511, 1493, 1452, 1421, 1375, 1359,
1305, 1283, 1241, 1199, 1180, 1156, 1125, 1090, 1049, 1008, 996, 911,
3JPC¼13.6 Hz, C-i in tBuC6H4), 139.27 (d, 3JPC¼15.1 Hz, C-p in C6H4),
149.55 (C-p in tBuC6H4) ppm. 31P NMR (161.98 MHz, CDCl3):
853, 764, 700, 603, 558, 528, 489 cmꢁ1
.
1H NMR (400.13 MHz,
d
¼41.44 (P]O), 37.18 (P]Se, JPSe¼690.8 Hz) ppm. 77Se NMR
CDCl3):
d
¼1.15, 1.24 and 1.32 (m, 18H, Me), 1.54e2.43 (m, 18H,
(76.27 MHz, CDCl3):
d
¼ꢁ385.2 (1JPSe¼690.8 Hz) ppm.
CH2PS), 2.63 (m, 6H, PCH2CH2C6H4), 2.94 (m, 6H, CH2PO), 3.09, 3.25
C99H132OP4Se3 (1698.88): calcd C 69.99, H 7.83, P 7.29, Se 13.94;
found C 69.91, H 7.80, P 7.23, Se 13.73.
and 3.40 (m, 6H, CHPh), 7.17e7.24 (m, 42H, Ph, C6H4) ppm. 13C NMR
(100.62 MHz, CDCl3):
d
¼23.2, 25.2 and 25.5 (Me), 28.7 (CH2C6H4),
34.5 35.3 and 35.8 (d, 1JPC¼21.0, 10.3 and 28.4 Hz, CH2PS), 38.4, 39.2
4.4.8. Tris(4-{2-[bis(2-phenylpropyl)phosphoroselenoyl]ethyl}ben-
1
and 39.9 (CHPh), 40.9 (d, JPC¼48.6 Hz, CH2PO), 127.2, 127.3 and
zyl)-phosphine oxide (24). Pale yellow powder (129 mg, yield 89%,
127.4 (C-p in Ph), 127.7, 127.8 and 127.9 (C-o in Ph), 128.1 (C-m in
method A). Mp 102e104 ꢀC (iso-propanol). IR (KBr):
n¼3104, 3082,

9224
N.K. Gusarova et al. / Tetrahedron 68 (2012) 9218e9225
2. (a) Hierso, J. C.; Amardeil, R.; Bentabet, E.; Broussier, R.; Gautheron, B.; Meunier,
P.; Kalck, P. Coord. Chem. Rev. 2003, 236, 143e206; (b) Gilbert-Wilson, R.; Field,
L. D.; Bhadbhade, M. M. Inorg. Chem. 2012, 51, 3239e3246.
3058, 3025, 2959, 2869, 1601, 1493, 1452, 1399, 1374, 1239, 1198,
1154,1126,1092,1046,1029,1009, 915, 850, 764, 700, 530, 484 cmꢁ1
1H NMR (400.13 MHz, CDCl3):
1.40e2.26 (m, 18H, CH2P), 2.63 (m, 6H, PCH2CH2), 2.87 (m, 6H,
CH2PO), 3.09, 3.31 and 3.45 (m, 6H, CHPh), 7.19e7.29 (m, 42H, Ph,
.
d
¼1.15, 1.24 and 1.37 (18H, Me),
3. (a) Bampos, N.; Field, L. D.; Messerle, B. A.; Smernik, R. J. Inorg. Chem. 1993, 32,
4084e4088; (b) Field, L. D.; Messerle, B. A.; Smernik, R. J.; Hambley, T. W.;
Turner, P. Inorg. Chem. 1997, 36, 2884e2892; (c) Field, L. D.; Messerle, B. A.;
ꢀ
Smernik, R. J. Inorg. Chem. 1997, 36, 5984e5990; (d) Basallote, M. G.; Duran, J.;
C6H4) ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼21.82, 21.97, 22.56,
ꢀ
ꢀ~
Fernandez-Trujillo, M. J.; Manez, M. A.; De La Torre, J. R. J. Chem. Soc., Dalton
Trans. 1998, 745e750; (e) Field, L. D.; Lawrenz, E. T.; Shaw, W. J.; Turner, P. Inorg.
Chem. 2000, 39, 5632e5638; (f) Field, L. D.; Shaw, W. J.; Turner, P. Organome-
tallics 2001, 20, 3491e3499; (g) Boddien, A.; Mellmann, D.; Gartner, F.; Jackstell,
R.; Junge, H.; Dyson, P. J.; Laurenczy, G.; Ludwig, R.; Beller, M. Science 2011, 333,
1733e1736.
3
23.71, 23.76, 24.68 and 24.78 (d, JPC¼8.8, 9.1, 13.4, 14.2, 8.4 and
12.3 Hz, Me), 34.72, 34.80, 35.31, 35.61 and 35.91 (CHPh), 36.88,
37.46, 37.94 and 38.52 (d, 1JPC¼42.9, 43.7 and 46.6 Hz, PhCH2CH2P),
37.38 (PCH2CH2C6H4), 38.71 (d, 1JPC¼41.0 Hz, PCH2CH2C6H4), 39.47
1
4. Perez-Carreno, E.; Paoli, P.; Ienco, A.; Mealli, C. Eur. J. Inorg. Chem. 1999,
1315e1324.
5. Miedaner, A.; Curtis, C. J.; Wander, S. A.; Goodson, P. A.; DuBois, D. L. Organo-
metallics 1996, 15, 5185e5190.
(d, JPC¼40.6 Hz, CH2PO), 126.64e127.15 (C-o,m,p in Ph), 128.66,
128.71 (C-o,m in C6H4),142.23 and 144.38 (d, 2JPC¼4.6 and 4.9 Hz, C-i
in C6H4), 145.55 and 145.65 (d, 3JPC¼10.0 and 10.3 Hz, C-p in C6H4),
146.36 (C-i in Ph) ppm. 31P NMR (161.98 MHz, CDCl3):
d¼42.34 (P]
6. Horng, D.-N.; Ueng, C.-H. Inorg. Chim. Acta 1995, 232, 175e181.
7. (a) Bianchini, C.; Casares, J. A.; Osman, R.; Pattison, D. I.; Peruzzini, M.; Perutz,
R. N.; Zanobini, F. Organometallics 1997, 16, 4611e4619; (b) Osman, R.; Pattison,
D. I.; Perutz, R. N.; Bianchini, C.; Casares, J. A.; Peruzzini, M. J. Am. Chem. Soc.
1997, 119, 8459e8473; (c) Bianchini, C.; Peruzzini, M.; Ceccanti, A.; Laschi, F.;
Zanello, P. Inorg. Chim. Acta 1997, 259, 61e70.
O), 38.01, 37.62 and 37.11 (P]Se, JPSe¼690.8 Hz) ppm. The presence
of three signals in the 31P NMR is likely attributable to several
asymmetric carbons in molecule 24. 77Se NMR (76.27 MHz, CDCl3):
d
¼ꢁ380.1 (1JPSe¼690.6 Hz) ppm. C81H96OP4Se3 (1446.40): calcd C
ꢀ
8. Gabor, L. Chimia 2011, 65, 663e666.
67.26, H 6.69, P 8.57, Se 16.38; found C 67.21, H 6.68, P 8.50, Se 16.33.
9. (a) Aizawa, S.; Kobayashi, T. Chem. Lett. 2004, 33, 384e385; (b) Aizawa, S.;
Kobayashi, T.; Kawamoto, T. Inorg. Chim. Acta 2005, 358, 2319e2326; (c)
Fernandez, D.; Garcia-Seijo, M. I.; Kegl, T.; Petocz, G.; Kollar, L.; Garcia-Fer-
nandez, M. E. Inorg. Chem. 2002, 41, 4435e4443.
10. (a) Aizawa, S.; Iida, T.; Funahashi, S. Inorg. Chem. 1996, 35, 5163e5167; (b)
Aizawa, S.; Sano, T.; Fujita, Y. J. Organomet. Chem. 2008, 693, 3638e3642.
11. Cecconi, F.; Ghilardi, C. A.; Ienco, A.; Midollini, S.; Orlandini, A. J. Organomet.
Chem. 1999, 575, 119e125.
12. (a) Schuh, W.; Kopacka, H.; Wurst, K.; Peringer, P. Eur. J. Inorg. Chem. 2001,
2399e2404; (b) Fernandez, D.; Garcia-Seijo, M. I.; Sevillano, P.; Castineiras, A.;
Garcia-Fernandez, M. E. Inorg. Chim. Acta 2005, 358, 2575e2584; (c) Aizawa, S.;
Saito, K.; Kawamoto, T.; Matsumoto, E. Inorg. Chem. 2006, 45, 4859e4866; (d)
Fernandez-Anca, D.; Garcia-Seijo, M.; Castineiras, A.; Garcia-Fernandez, M. In-
org. Chem. 2008, 47, 5685e5695.
13. (a) Wachtler, H.; Schuh, W.; Ongania, K. H.; Kopacka, H.; Wurst, K.; Peringer,
P. J. Chem. Soc., Dalton Trans. 2002, 2532e2535; (b) Pascariu, A.; Iliescu, S.;
Popa, A.; Ilia, G. J. Organomet. Chem. 2009, 694, 3982e4000; (c) Rieckborn,
T. P.; Huber, E.; Karakoc, E.; Prosenc, M. H. Eur. J. Inorg. Chem. 2010,
4757e4761.
4.4.9. Tris[4-(2-bis[2-(2-furyl)ethyl]phosphoroselenoylethyl)benzyl]
phosphine oxide (25). Pinkish needles (70 mg, yield 85%, method A).
Mp 110e112 ꢀC (iso-propanol). IR (KBr):
n
¼2954, 2922, 2852, 1718,
1709, 1638, 1596, 1507, 1463, 1378, 1336, 1233, 1213, 1146, 1072, 1007,
961, 916, 801, 731, 598, 481 cmꢁ1 1H NMR (400.13 MHz, CDCl3):
.
d
¼2.11e2.25 (m,18H, CH2PSe), 2.85e2.88 (m, 6H, CH2PO), 2.98e2.99
(m,18H, CH2Fur, CH2C6H4), 6.06 (s, 6H, HC]C in Fur), 6.25(s, 6H, HC]
CHeCH in Fur), 7.14 (s, 6H, OCH in Fur), 7.25e7.28 (m,12H, C6H4) ppm.
13CNMR(100.62MHz,CDCl3):
d
¼22.14(FurCH2),28.7(d,1JPC¼41.0Hz,
1
FurCH2CH2), 28.80 (PCH2CH2C6H4), 32.16 (d, JPC¼40.9 Hz,
PCH2CH2C6H4), 35.01 (d, 1JPC¼64.1 Hz, CH2PO),106.19 (HC]C in Fur),
110.43 (HC]CHeCH in Fur), 128.67 (C-m in C6H4), 129.76 (d,
2JPC¼7.7 Hz, C-i in C6H4), 130.15 (C-o in C6H4), 139.14 (d, 3JPC¼15.1 Hz,
3
14. (a) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Zanobini, F. Coord. Chem. Rev.
C-p in C6H4), 141.48 (OCH in Fur), 153.23 (d, JPC¼14.4 Hz, CO in
€
1992, 120, 193e208; (b) Wienhofer, G.; Westerhaus, F. A.; Jagadeesh, R. V.;
Fur) ppm. 31P NMR (161.98 MHz, CDCl3):
d
¼43.75 (P]O) and 38.19
€
Junge, K.; Junge, H.; Beller, M. Chem. Commun. 2012, 4827e4829; (c) Wienhofer,
(P]Se, JPSe¼690.8 Hz) ppm. 77Se NMR (76.27 MHz, CDCl3):
¼ꢁ370.3
d
G.; Sorribes, I.; Boddien, A.; Westerhaus, F.; Junge, K.; Junge, H.; Llusar, R.;
Beller, M. J. Am. Chem. Soc. 2011, 133, 12875e12879.
(1JPSe¼690.8 Hz) ppm. C63H72O7P4Se3 (1302.02): calcd C 58.12, H 5.57,
15. (a) Elgavish, G. A. EP Patent 173163, 1986; Chem. Abstr. 1986, 105, 38786; (b)
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Acknowledgements
This work was supported by a research grant from the Russian
Foundation of Basic Research (11-03-00286a) and the President of
the Russian Federation (program for the support of leading scien-
tific schools, grant NSh-1550.2012.3).
20. (a) Gusarova, N. K.; Kuimov, V. A.; Malysheva, S. F.; Sukhov, B. G.; Trofimov, B. A.
Russ. J. Gen. Chem. 2006, 76, 325e326; (b) Trofimov, B. A.; Gusarova, N. K.
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Supplementary data
Dokl. Chem. 2008, 418, 5e7.
ˇ
Complete results of the ligand screening (6, 6ox, 7ox, 17e25) and
copies of 1H, 13C, and 31P NMR spectra of new compounds. Sup-
plementary data associated with this article can be found in the
online version, at http://dx.doi.org/10.1016/j.tet.2012.08.091.
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