Facile synthesis of hyper-branched tetraphosphanes and tetraphosphane chalcogenides

Article abstract of DOI:10.1002/ejoc.200900382

Novel familles of hyper-branched tertiary tetraphosphanes, tetraphosphane sulfides, and tetraphosphane selenides were synthesized in 72-97% yield by treating secondary phosphanes, phosphane sulfides, and phosphane selenides with the tetravinyl ether of pe

Full text of DOI:10.1002/ejoc.200900382

FULL PAPER
DOI: 10.1002/ejoc.200900382
Facile Synthesis of Hyper-Branched Tetraphosphanes and Tetraphosphane
Chalcogenides
[
a]
[a]
[a]
Boris A. Trofimov,* Svetlana F. Malysheva, Nataliya A. Belogorlova,
[a]
[a]
[a]
Vladimir A. Kuimov, Alexander I. Albanov, and Nina K. Gusarova
Keywords: Ligand design / Phosphorylation / Radical reactions / Phosphanes
Novel families of hyper-branched tertiary tetraphosphanes,
tetraphosphane sulfides, and tetraphosphane selenides were
synthesized in 72–97% yield by treating secondary phos-
phanes, phosphane sulfides, and phosphane selenides with
the tetravinyl ether of pentaerythritol (UV irradiation, room
temp. or AIBN, 65 °C).
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
Introduction
the phosphane moieties and bulky hydrophobic substituents
that make them more adjustable and hemilabile ligands in
the metallocomplex formation as well as convenient scaf-
folds for supramolecular nanostructured materials. Gen-
erally, phosphanes and phosphane chalcogenides with
bulky organic surrounding are now the subjects of special
interest, as they often dramatically change the activity and
The chemistry of organophosphorus compounds con-
taining two or more phosphane moieties is now rapidly de-
veloped. Diphosphanes such as dipamp, duphos, prophos,
xyliphos, xantphos, josiphos, biphep, binap, bpe, dppe, and
[
1]
dppf are widely used ligands for organometallic catalysts,
[
2]
anticancer drugs,
and fluorescent sensors for heavy
[
21]
other properties of organometallic catalysts.
[
3]
metals. Triphosphanes are ligands of catalysts for homo-
The known syntheses of tetraphosphanes are based on
hazardous phosphorus halides and alkali metals, and the
procedures are often multistep, laborious, and chemical-
[
4]
geneous olefin polymerization and hydrogenolysis of
[
5]
benzothiophene. They are also employed in Wittig reac-
[
6]
tions. Among the triphosphanes, polydentate phosphane
[
9b,22]
and solvent-consuming.
Therefore, the search for a
[
7]
arms are applied for the preparation of radiopharmaceu-
more straightforward and atom-economic (“green”) route
to tertiary tetraphosphanes is justifiable.
tical imaging agents.[
8]
Less accessible and hence less understood are the tetra-
phosphanes and particularly the corresponding tetraphos-
phane chalcogenides, though some of them are used as
pincer ligands, capable of forming dimetallocycled mole-
Results and Discussion
[
7c,9]
cules.
Also, such dinuclear organometallic complexes
Here we report a facile, one-pot synthesis of novel fami-
lies of hyper-branched tetraphosphanes and tetraphosphane
chalcogenides by free-radical addition of secondary phos-
phanes 1 and 2, phosphane sulfides 3 and 4, and phosphane
selenides 5 and 6 to the tetravinyl ether of pentaerythritol
attract special attention due to their possible applications
as building blocks for new types of catalysts and materials
with magnetic, nonlinear optical (NLO), or liquid crystal-
[
10]
line properties.
Tetrapodal phosphanes, including chiral
[
9a,9b]
ones,
genation of arylenamides,
act as ligands in Rh-catalyzed asymmetric hydro-
7. The secondary phosphanes and phosphane chalcogenides
[11]
highly regioselective isomer-
belong to the still-rare classes of phosphorus hydrides that
ization of olefins, alkylation[13] and amination, Mo- or
[
12]
[14]
contain both aliphatic chain (CH ) and aromatic moieties
[
15]
2 2
W-catalyzed N–N bond cleavage of organohydrazines,
in the bulky substituents. Recently, they became available
[
16]
[17]
[18]
[19]
and Heck,
Negishi,
Sonogashira,
and Suzuki
by a one-pot synthesis from red phosphorus or PH and
[20]
3
couplings and for other important syntheses. Particularly
promising are the branched tetraphosphanes with longer
and flexible spacers containing other heteroatoms between
[
23]
styrenes (Scheme 1).
[
a] A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch
of the Russian Academy of Sciences,
1
Favorsky St., Irkutsk 664033, Russian Federation
Fax: +7-3952-419346
E-mail: boris_trofimov@irioch.irk.ru
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200900382.
Scheme 1. Synthesis of bis(2-arylethyl)phosphanes and phosphanes
chalcogenides.
Eur. J. Org. Chem. 2009, 3427–3431
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3427

B. A. Trofimov et al.
FULL PAPER
The choice of tetravinyl ether 7 is not occasional. This Generally, as we observed here (Table 1), for phosphane sel-
ether is produced by industrially feasible direct vinylation enides the adduct yields are about 20% lower than with the
of pentaerythritol with acetylene.[
24]
corresponding phosphanes and phosphane sulfides, obvi-
It is known that divinyl ethers of glycols, when treated ously owing to selenium extrusion.
with PH-addends under free-radical conditions, do not give Amazingly, incomplete addition products (mono-, di-,
the expected diadducts, but undergo cyclization and/or te- and triadducts) were not discernible ( H, C, P NMR) in
1
13
31
[
25]
lomerization. Therefore, it might be expected that the ad- the crude product. This implies that incomplete adducts,
dition of secondary phosphanes 1 and 2, phosphane sul- despite the growing steric hindrance in the vicinity of the
fides 3 and 4, and phosphane selenides 5 and 6 to tetravinyl remaining vinyl groups, are almost as active towards the
ether 7, which contains two 1,3-glycol divinyl ether moie- addends as starting ether 7.
ties, will be complicated by similar cycloadditions, telome-
Interestingly, the corresponding reactions with secondary
rization, oligomerization, and cross-linking reactions.
phosphane oxides and tetravinyl ether 7 gave practically no
Meanwhile, we found the conditions under which the adducts under the conditions of both methods (A and B).
above side reactions practically do not occur. To our sur- This is in agreement with literature data that lower activity
prise, when addends 1–6 and tetravinyl ether 7 (molar ratio of secondary phosphane oxides in radical additions is often
[
26]
4:1) were allowed to react under UV irradiation (method A) observed.
or in the presence of AIBN at 65 °C (method B), tetraad-
To check the reactivity of the phosphane centers in the
ducts 8–13 were readily formed in 72–97% yields (Table 1). hyper-branched surroundings of the adducts we used tetra-
They were easily purified by passing the reaction mixture phosphanes 8 and 9 in typical phosphane reactions. It was
through a thin layer of alumina.
found that tetraphosphanes 8 and 9 were smoothly oxidized
by air (room temp., 40 h, acetone) or elemental sulfur and
selenium (50 °C, 1 h, toluene) to quantitatively give the cor-
responding tetraphoshane chalcogenides 10–14 (Scheme 2).
Table 1. Exhaustive addition of phosphorus hydrides 1–6 to tetra-
vinyl ether 7.
Method / Product[b]
[
a]
Yield[c]
[%]
PH-
addend
R
X
Time [h]
Scheme 2. Oxidation of tetraphosphanes 8 and 9.
1
2
3
Ph
none
A/5
B/8
8
9
90 (94)
90 (98)
It is astounding that all four phosphane centers in tetra-
phosphane 8 are easily accessible, even for bulky electro-
philes such as 1-(bromomethyl)naphthalene. The corre-
sponding tetraphosponium salt 15 is formed in quantitative
4-tBuC
6 4
H
none
S
A/5
B/7
88 (90)
80 (85)
Ph
A/3
B/10
10
97 (99)
97 (99)
yield under mild conditions (room temp., 0.5 h, Et
2
O)
(Scheme 3).
4
5
4-tBuC
H
6 4
S
A/3
11
12
75 (96)
Ph
Se
A/4
B/14
75 (95)
35 (45)
6
4-tBuC H
6 4
Se
A/4
13
72 (82)
[
a] Standard reaction conditions: molar ratio 1–6/7 = 4:1. Experi-
ments were carried out under an inert atmosphere (argon).
Method A: UV, room temp., dioxane. Method B: AIBN (1.5–2 wt.-
%
of the reactants’ mass), 65 °C, dioxane. [b] The crude product
was purified by column chromatography on alumina (Et
ane). [c] Isolated yield (NMR yield parentheses).
2
O/hex-
Scheme 3. Exhaustive reaction of tetraphosphane 8 with 1-(bro-
As seen from Table 1, the UV-initiated addition momethyl)naphthalene.
method A) was preferred over AIBN-initiated addition
(
(
method B): the yields of tetraadducts were always higher
Moreover, this salt is capable of being efficiently involved
and the reaction times were shorter. Besides, in the case in Wittig–Horner-type reactions. For example, when salt 15
of method B, the reaction with phosphane selenide 5 was was treated with benzenecarbaldehyde (aq. 50% NaOH,
accompanied by the precipitation of elemental selenium, benzene, EtBnNCl, room temp., 1 h), expected stilbenoid
which sharply decreased the yield of adduct 12 (35%) ap- 16 (85%) and tetraphosphane oxide 14 (82%) were formed
parently as a result of the elevated temperature (65 °C). (Scheme 4).
3428
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 3427–3431

Hyper-Branched Tetraphosphanes and Tetraphosphane Chalcogenides
2
1603, 1583, 1495 [νC=C(Ph)], 1452 (δCH ), 1365, 1201, 1179, 1166
[
δCH(Ph)], 1099 (νC–O), 1030, 1004 [δCH(Ph)], 754 [νP–C,
–
1
1
δCH(Ph)], 698 [δCH(Ph)], 495 (δCPC) cm .
400.13 MHz, CDCl ): δ = 7.22–7.13 (m, 40 H, Ph), 3.53–3.47 (m,
H, OCH CH P), 3.37 (s, 8 H, CH C), 2.72–2.66 (m, 16 H,
CH Ph), 1.74–1.70 (m, 24 H, CH P) ppm. C NMR (100.62 MHz,
CDCl ): δ = 142.94 (d, JP,C = 11.1 Hz, C-i), 128.53 (C-m), 128.20
H
NMR
(
8
3
2
2
2
1
3
2
2
3
3
2
(
C-o), 126.05 (C-p), 69.95 (CH
2
2
C), 69.46 (d,
J
P,C = 19.4 Hz,
), 32.34 (d, JP,C = 15.9 Hz, CH Ph), 29.37 (d,
), 27.57 (d, 1JP,C = 14.3 Hz, PCH
CH O)
NMR (161.98 MHz, CDCl3): –31.77 ppm.
CH
2
O), 45.36 (CCH
2
2
1
J
P,C = 14.0 Hz, PCH
2
2
2
3
1
Scheme 4. Wittig–Horner reaction between salt 15 and benzene-
ppm.
P
δ =
carbaldehyde.
77 96 4 4
C H O P (1209.48): calcd. C 76.46, H 8.00, P 10.24; found C
76.65, H 8.02, P 9.98.
Conclusions
Tetra(2-{bis[2-(4-tert-butyl)phenethyl]phosphanyl}ethoxy)neopen-
tane (9): Colorless oil. Yield: 146 mg, 88% (Method A); 199 mg,
To conclude, a facile synthesis of novel families of hyper-
branched tetraphosphanes and tetraphosphane chalcogen-
ides was accomplished by using free-radical addition of sec-
ondary phosphanes and phosphane chalcogenides to the
8
2
0 % (Method B). IR: ν˜ = 3091, 3054, 3022 [ν=CH(Ph)], 2960,
926, 2906, 2868 (νCH), 1613, 1516 [νC=C(Ph)], 1463, 1411, 1393
(
δCH
2
1
), 1364 (δCH
3
), 1107 (νC–O), 817 [δCH(Ph)], 562 (δCPC)
–1
cm . H NMR (400.13 MHz, CDCl ): δ = 7.29–7.08 (m, 32 H,
3
tetravinyl ether of pentaerythritol. These specific tetraphos- C H ), 3.68 (m, 8 H, OCH CH P), 3.53 and 3.42 (m, 8 H, CH C),
6
4
2
2
2
phanes and tetraphosphane chalcogenides of dendrimer- 2.68 (m, 16 H, CH
2
C
6
H
4
), 1.74–1.72 (m, 24 H, CH
2
P), 1.28 (s, 64
1
3
H, Me) ppm. C NMR (101.6 MHz, CDCl
3
): δ = 148.83 (C-p),
39.78 (d, JP,C = 10.1 Hz, C-i), 127.76 (C-m), 125.32 (C-o), 69.43
like structure thus synthesized are promising pincer ligands
for novel organometallic catalysts as well as reagents for
organic synthesis and building blocks to design new types
of supramolecular architectures with special magnetic,
NLO, or liquid crystalline properties.
3
1
1
(
=
2
–
7
CH
2
C), 67.09 (CH
17.0 Hz, CH Ph), 31.39 (Me), 29.22 (d, JP,C = 11.6 Hz, CH
CH ): δ =
O) ppm. 31P NMR (161.98 MHz, CDCl
31.84 ppm. C109 (1658.33): calcd. C 78.94, H 9.72, P
.47; found C 78.65, H 9.52, P 7.68.
2 2
O), 45.01 (CCH ), 34.35 (CMe), 32.18 (d, JP,C
2
2
2
P),
7.51 (PCH
2
2
3
H
160 4 4
O P
Tetra{2-[bis(2-phenethyl)phosphorothioyl]ethoxy}neopentane (10):
Light-yellow oil. Yield: 130 mg, 97% (Method A); 191 mg, 95%
(Method B). IR: ν˜ = 3106, 3084, 3060, 3025, 3001 [=CH(Ph)], 2918,
Experimental Section
General: IR spectra were obtained with a Bruker IFS-25 spectrome-
–1
1
13
ter (400–4000 cm , KBr pellets). H (400.13 MHz), C NMR 2904, 2863 (=CH), 1602, 1583, 1496 [C=C(Ph)], 1453, 1401 (δCH ),
2
–1
1
(
101.6 MHz), and 31P NMR (161.98 MHz) spectra were recorded 1099 (C-O), 752, 697 [δCH(Ph)], 598 (P=S) cm
. H NMR
with a Bruker DPX 400 instrument in CDCl
enced to internal hexamethyldisiloxane ( H NMR) and external
3
solutions and refer-
(400.13 MHz, CDCl ): δ = 7.26–7.16 (m, 40 H, Ph), 3.54–3.50 (m,
3
1
8 H, CH O), 3.14 (s, 8 H, CH C), 2.90–2.89 (m, 16 H, CH Ph),
2
2
2
3
1
13
8
5% H
red phosphorus and styrenes.
were prepared by reaction of phosphanes 1 and 2 with elemental
3
PO
4
( P NMR). Phosphanes 1 and 2 were prepared from
2.14–2.13 and 1.99–1.98 (m, 24 H, CH P) ppm. C NMR
(101.6 MHz, CDCl ): δ = 140.43 (d, J = 19.6 Hz, C-i), 128.43
2
[23a,23c]
3
Phosphane chalcogenides 3–6
3
P,C
(C-m), 127.97 (C-o), 126.30 (C-p), 69.61 (CH C), 65.21 (CH O),
2
2
[
23c,27]
1
1
sulfur or selenium.
Ether 7 was synthesized from pentaeryth-
44.70 (CCH ), 33.18 (d, J = 54.8 Hz, CH P), 30.95 (d, J
55.2 Hz, PCH CH O), 28.33 (CH Ph) ppm. P NMR
P,C
=
2
P,C
2
ritol and acetylene in the system KOH/DMSO.[
24]
3 1
2
2
2
(
3 96 4 4 4
161.98 MHz, CDCl ): δ = 48.35 ppm. C77H O P S (1337.74):
General Procedures for the Preparation of Tetraphosphanes 8 and 9
and Tetraphosphane Chalcogenides 10–13
calcd. C 69.13, H 7.23, P 9.26, S 9.59; found C 69.35, H 7.32, P
.98, S 9.35.
8
Method A: A solution of PH-addend 1–6 (0.4 mmol) and ether 7
Tetra(2-{bis[2-(4-tert-butyl)phenethyl]phosphorothioyl}ethoxy)neo-
pentane (11): Colorless powder. Yield: 134 mg, 75% (Method A).
M.p. 159–160 °C (hexane). IR (KBr): ν˜ = 3091, 3055, 3024
(0.1 mmol) in dioxane (0.5 mL) was irradiated (200-W Hg arc
lamp) in a quartz ampoule (reaction times are given in Table 1).
Method B: A solution of PH-addend 1–6 (0.6 mmol) and ether 7
[
=CH(C
463, 1393 (δCH
δCH(C )], 565, 552 (sh., P=S) cm . H NMR (400.13 MHz,
): δ = 7.28–7.22 and 7.10–7.09 (m, 32 H, C ), 3.70–3.66
O), 3.31 (m, 8 H, CH C), 2.86 (m, 16 H, CH ),
2.12–2.05 (m, 24 H, CH P), 1.26 (s, 72 H, Me) ppm. C NMR
(101.6 MHz, CDCl ): δ = 149.46 (C-p), 137.42 (d, JP,C = 20.2 Hz,
C-i), 127.91 (C-m), 125.55 (C-o), 70.63 (CH C), 65.58 (CH O),
), 34.41 (CMe), 33.66 (d, JP,C = 50.7 Hz, CH P),
O), 27.99
): δ = 47.80 ppm.
(1786.59): calcd. C 73.28, H 9.03, P 6.93, S 7.18;
6
H
4
)], 2961, 2905, 2855 (=CH), 1626, 1515 [C=C(C
6 4
H )],
(0.15 mmol) in dioxane (5 mL) in the presence of AIBN (1–2 wt.-
1
[
2
), 1364, 1269 (δCH ), 1107 (C–O), 818
3
%
of the total mass of reactants) was stirred at 65 °C in a sealed
–1 1
6 4
H
ampoule (reaction times are given in Table 1).
CDCl
(m, 8 H, CH
3
6 4
H
The reaction was monitored by 31P NMR spectroscopy by disap-
pearance of the signal of the starting PH-addends (the –70 to –68
region for phosphanes 1 and 2; the 2 to 23 interval for phosphane
chalcogenides 3–6) and appearance of a new resonance in the –32
to –30 and 36 to 49 regions, corresponding to tertiary tetraphos-
phanes 8 and 9 and tetraphosphane chalcogenides 10–13. Crude
2
2
2 6 4
C H
1
3
2
3
3
2
2
1
45.22 (CCH
31.38 (Me), 30.75 (d,
2
2
1
J
P, C = 53.9 Hz, PCH
2 2
CH
3
1
products 8–13 were purified by column chromatography (Al
2
O
3
;
(CH
C
2
C
6
H
4
) ppm. P NMR (161.98 MHz, CDCl
3
hexane/diethyl ether, 1:1). All steps of the experiments were carried
out under an atmosphere of argon.
109
H
160
O P S
4 4 4
found C 73.30, H 9.02, P 6.80, S 7.16.
Tetra{2-[bis(2-phenethyl)phosphanyl]ethoxy}neopentane (8): Color-
less oil. Yield: 109 mg, 90% (Methods A and B). IR: ν˜ = 3105,
Tetra{2-[bis(2-phenethyl)phosphoroselenoyl]ethoxy}neopentane (12):
Light-yellow oil. Yield: 114 mg, 75% (Method A); 80 mg, 35%
(Method B). IR: ν˜ = 3103, 3083, 3059, 3024, 3000 [=CH(Ph)], 2897,
3083, 3061, 3025, 3000 [ν=CH(Ph)], 2929, 2892, 2862, 2880 (νCH),
Eur. J. Org. Chem. 2009, 3427–3431
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3429

B. A. Trofimov et al.
FULL PAPER
2
1
904, 2863 (=CH), 1602, 1583, 1495 [C=C(Ph)], 1453, 1400 (δCH
2
), phenylethenylnaphthalene 16 (Z/E = 1:4, 82 mg, 85%) as a color-
–
1 1
099 (C–O) 750, 697 [δCH(Ph)], 573 (P=Se) cm
): δ = 7.24–7.18 (m, 40 H, Ph), 3.62–3.48 (m, data.[
O), 3.23 and 3.13 (m, 8 H, CH C), 2.91–2.89 (m, 16 H,
Ph), 2.27–2.26 (m, 16 H, CH P), 2.09–2.08 (m, 8 H,
CH ): δ = 140.50 (d,
O) ppm. 13C NMR (101.6 MHz, CDCl
P,C = 14.5 Hz, C-i), 128.85 (C-m), 128.35 (C-o), 126.67 (C-p),
.
H NMR
less oil. Spectral characteristics of 16 correspond to the reference
28]
(400.13 MHz, CDCl
3
8
H, CH
2
2
Tetra{2-[bis(2-phenethyl)phosphoryl]ethoxy}neopentane (14): Color-
less oil. Yield: 110 mg, 82%. IR: ν˜ = 3065, 3026 [=CH(Ph)], 2950,
CH
PCH
2
2
2
2
3
2
2871 (CH), 1604, 1563, 1493 [C=C(Ph)], 1452 (δCH ), 1403, 1369,
3
J
1
220 [δCH(Ph)], 1100 (CO), 1158 (P=O), 995 [δCH(Ph)], 754 [P–
1
6
4
9.79 (CH
3.2 Hz, CH
2
C), 66.27 (CH
2
O), 45.28 (CCH
2
), 33.23 (d, JP, C
P), 30.71 (d, JP, C = 49.2 Hz, PCH CH O), 29.44
Ph) ppm. 31P NMR (161.98 MHz, CDCl
): δ = 36.85 ppm.
Se (1525.32): calcd. C 60.63, H 6.34, P 8.12, Se 20.71;
=
–1
1
C, δCH(Ph)], 702 [δCH(Ph)], 493 (δCPC) cm .
400.13 MHz, CDCl ): δ = 7.26–7.14 (m, 40 H, Ph), 3.51–3.44 (m,
O), 3.21 (m, 8 H, CH C), 2.89–2.83 (m, 16 H, CH Ph),
P) ppm. C NMR (101.6 MHz, CDCl ):
H NMR
1
2
2
2
(
3
(CH
2
3
8
2
H, CH
.02–1.83 (m, 24 H, CH
2
2
2
C
77
H
96
O
4
P
4
4
13
2
3
found C 60.45, H 6.23, P 8.18, Se 20.35.
3
δ = 140.40 (d, JP,C = 23.1 Hz, C-i), 128.30 (C-m), 127.59 (C-o),
Tetra(2-{bis[2-(4-tert-butyl)phenethyl]phosphoroselenoyl}ethoxy)neo- 126.12 (C-p), 69.52 (CH
2
C), 64.47 (CH
2
O), 44.48 (CCH
2
), 30.35
CH O),
): δ =
(1273.48): calcd. C 72.62, H 7.60, P 9.73;
found C 72.65, H 7.56, P 9.68.
1
1
pentane (13): Colorless powder. Yield: 142 mg, 72% (Method A).
M.p. 159–160 °C (hexane). IR (KBr): ν˜ = 3091, 3054, 3021
(d, JP,C = 68.8 Hz, CH
2
P), 28.43 (d, JP,C = 68.8 Hz, PCH
2
2
3
1
27.19 (CH
)], 46.90 ppm. C77
3
), 1107, (C–O), 818
2 3
Ph) ppm. P NMR (161.98 MHz, CDCl
[
1
[
=CH(C
463, 1394 (δCH
δCH(C )], 564, 551 (sh., P=Se) cm . H NMR (400.13 MHz,
): δ = 7.27–7.10 (m, 32 H, C ), 3.80–3.60 (m, 8 H, CH O),
), 2.24 (m, 24
6
H
4
)], 2961, 2904, 2865 (=CH), 1626, 1516 [C=C(C
6
H
4
96 8 4
H O P
2
), 1363, 1268 (δCH
–1 1
6 4
H
Supporting Information (see footnote on the first page of this arti-
cle): Characterization data of 8–13 and copies of the H, C, and
P NMR spectra of new compounds.
CDCl
3
3
6
H
4
2
1
13
.47–3.23 (m, 8 H, CH
2
C), 2.87 (m, 16 H, CH
2
C
6
H
4
31
H, CH
CDCl
2
P), 1.27 (s, 72 H, Me) ppm. 13C NMR (101.6 MHz,
3
3
): δ = 149.46 (C-p), 137.20 (d, JP,C = 14.5 Hz, C-i), 127.92
(
3
(
C-m), 125.56 (C-o), 70.59 (CH
2
C), 66.44 (CH
2
O), 45.08 (CCH
2
), Acknowledgments
1
4.38 (CMe), 33.27 (d, JP,C = 45.2 Hz, CH P), 31.34 (Me), 29.82
2
1
31
d,
J
P,C = 37.9 Hz, PCH
2
CH
2
O), 28.82 (CH
2
C
6
H
4
) ppm.
P
This work was supported by a research grant from the Russian
Foundation of Basic Research (07-03-00562a).
NMR (161.98 MHz, CDCl
3
): δ = 37.46 ppm. C109
H
160 4 4 4
O P Se
(1974.17): calcd. C 66.31, H 8.17, P 6.28, Se 16.0; found C 66.45,
H 8.23, P 6.18, Se 16.35.
[
1] a) E. I. Klabunovskii, Catalysis in Industry 2006, 52; b) H.
Doucet, Eur. J. Org. Chem. 2008, 2013; c) A. Börner (Ed.),
Phosphorus Ligands in Asymmetric Catalysis: Synthesis and Ap-
plications, Wiley-VCH, Weinheim, 2008, vol. 1.
Synthesis of Salt 15: A solution of phosphane 8 (420 mg,
0
.35 mmol) and 1-(bromomethyl)naphthalene (310 mg, 1.4 mmol)
in diethyl ether (5 mL) was stirred under an argon atmosphere at
3–25 °C for 0.5 h. The solvent was removed in vacuo, and the
residue was precipitated from CHCl (1 mL) in pentane (7 mL) to
[2] a) H. Kodama, K. Ohto, N. Oohara, K. Nakatsui, Yo. Kaneda,
Int. Appl. WO patent 139176, 2007 [Chem. Abstr. 2008, 148,
2
3
3
3888y]; b) H. Kodama, K. Owatari, N. Chara, K. Nakatsui,
Yo. Kaneda, JP Patent 308437, 2007 [Chem. Abstr. 2008, 148,
3892v].
3] M.-H. Ha-Thi, M. Penhoat, V. Michelet, I. Leray, Org. Lett.
007, 9, 1133.
4] R. J. Baker, P. G. Edwards, J. Chem. Soc., Dalton Trans. 2002,
960.
give phosphonium bromide 15 (725 mg, 99%).
3
Tetra{2-[bis(2-phenethyl)(1-naphthylmethyl)phosphonio]ethoxy}-
neopentane Tetrabromide (15): Colorless powder. Yield: 725 mg,
[
[
2
99%. M.p. 109–110 °C. IR (KBr): ν˜ = 3006, 3085, 3058, 3027, 3000
[=CH(Ph)], 2921, 2872 (=CH), 1602, 1510, 1499 [C=C(Ph)], 1455,
2
–
1 1
2
1396 (δCH ), 1106 (C–O), 810, 778, 749, 670 [δCH(Ph)] cm . H [5] C. Bianchini, M. Frediani, F. Vizza, Chem. Commun. 2001,
NMR (400.13 MHz, CDCl
3
1
): δ = 8.45–8.43 and 7.86–7.00 (m, 68
479.
[6] M. Albrecht, S. Burk, P. Weis, Ch. A. Schalley, M. Kogej, Syn-
thesis 2007, 3736.
H, naph, Ph), 4.80–4.76 (d, JP,H = 18.8 Hz, 8 H, CH
.85 (m, 8 H, CH O), 3.55 (m, 8 H, CH C), 2.92 (m, 24 H,
PCH CH O, CH Ph), 2.51 (m, 16 H, CH
101.6 MHz, CDCl
2
naph), 3.89–
3
2
2
P) ppm. 1 C NMR
3
[7] a) H. Schill, A. Meijere, Org. Lett. 2007, 9, 2617; b) M. Ala-
jarín, C. López-Leonardo, J. Berná, Tetrahedron 2007, 63, 4450;
c) M. Alajarín, J. Berná, C. López-Leonardo, J. W. Steed,
Chem. Commun. 2008, 2337.
2
2
2
2
3
(
(
(
(
3
): δ = 138.62 (d, JP,C = 13.3 Hz, C-i), 134.00
C ), 131.99 (C ), 129.45 (C ), 129.14 (C ), 128.69 (C-m), 128.28
C-o), 127.67 (C ), 126.89 (C-p), 126.59 (C ), 125.62 (C ), 125.14
2
11
6
10
3
5
8
[
8] a) C. M. Archer, J. R. Dilworth, D. V. Griffiths, J. M. Hughes,
J. D. Kelly, S. Morton in Technetium in Chemistry and Nuclear
Medicine (Eds.: M. Nicolini, G. Bandoli, U. Mazzi), SGEditor-
ial, Padova, 1995, pp. 173–175; b) D. V. Griffiths, H. J. Groom-
bridge, P. M. Mahoney, S. P. Swetnam, G. Walton, D. C. York,
Tetrahedron 2005, 61, 4595.
4,7
9
C
), 124.08 (C ), 70.29 (CH
2
C), 64.14 (CH
naph), 21.66 (d, JP,C
P,C = 50.0 Hz, PCH CH O) ppm.
): δ = 31.99 ppm. C121
2093.85): calcd. C 69.41, H 6.35, Br 15.26, P 5.92; found C 69.53,
2 2
O), 44.91 (CCH ),
1
1
2
7.58 (CH
38.7 Hz, CH
2
Ph), 25.01 (d, JP,C = 45.2 Hz, CH
2
=
2
P), 21.11 (d, 1
J
2
2
3
1
P NMR (161.98 MHz, CDCl
3
4 4 4
H132Br O P
(
[
9] a) A. L. Airey, G. F. Swiegers, A. C. Willis, S. B. Wild, Inorg.
Chem. 1997, 36, 1588; b) S. Chatterjee, F. K. E. Moore, G. Sa-
lem, P. Waring, A. C. Willis, J. Chem. Soc., Dalton Trans. 2000,
4487; c) I. P. Beletskaya, A. V. Chuchuryukin, H. P. Dijkstra,
G. P. M. van Klink, G. van Koten, Tetrahedron Lett. 2000, 41,
H 6.32, Br 15.16, P 5.98.
Wittig–Horner Reaction: A mixture of tetrabromide 15 (220 mg,
0
Et
H
2
.105 mmol),
benzenecarbaldehyde
BzN Cl (≈0.001 mg), NaOH (700 mg), benzene (5.0 mL), and
O (2 mL) was stirred vigorously under an argon atmosphere at
3–25 °C for 1 h. The organic part was separated, washed with
water (3ϫ0.5 mL), and dried with K CO . Benzene was removed
in vacuo, and the residue was dissolved in CHCl (1 mL) and pre-
(446 mg,
0.42 mmol),
+
–
3
1075; d) C. M. Habeck, Ch. Hoberg, G. Peters, Ch. Näther,
2
F. Tuczek, Organometallics 2004, 23, 3252; e) D. Watanabe, S.
Gondo, H. Seino, Ya. Mizobe, Organometallics 2007, 26, 4909.
10] M. E. van der Boom, S.-Y. Liou, Y. Ben-David, L. J. W. Shi-
mon, D. Milstein, J. Am. Chem. Soc. 1998, 120, 6531.
2
3
[
[
3
cipitated with ether (10 mL). The sediment (colorless oil) was sepa-
rated and dried in vacuo to furnish phosphane oxide 14 (110 mg,
11] D. Zhao, Z. Wang, K. Ding, Tetrahedron Lett. 2007, 48, 5095.
[12] Y. Yan, Xi. Zhang, Xu. Zhang, J. Am. Chem. Soc. 2006, 128,
82%). Removal of chloroform and ether from the extract gave 2-
16058.
3430
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 3427–3431

Hyper-Branched Tetraphosphanes and Tetraphosphane Chalcogenides
[
13] M. Feuerstein, D. Laurenti, H. Doucet, M. Santelli, Chem.
[23] a) B. A. Trofimov, L. Brandsma, S. N. Arbuzova, S. F. Malysh-
eva, N. K. Gusarova, Tetrahedron Lett. 1994, 35, 7647; b) B. A.
Trofimov, S. F. Malysheva, N. K. Gusarova, V. A. Kuimov,
N. A. Belogorlova, B. G. Sukhov, Tetrahedron Lett. 2008, 49,
3480; c) N. K. Gusarova, S. F. Malysheva, V. A. Kuimov, N. A.
Belogorlova, V. L. Mikhailenko, B. A. Trofimov, Mendeleev
Commun. 2008, 18, 260.
Commun. 2001, 43.
[
14] M. Lemhadri, H. Doucet, M. Santelli, Synthesis 2005, 1359.
15] D. Watanabe, S. Gondo, H. Seino, Ya. Mizobe, Organometal-
lics 2007, 26, 4909.
[
[16] a) M. Lemhadri, H. Doucet, M. Santelli, Tetrahedron 2004, 60,
11533; b) A. Battace, T. Zair, H. Doucet, M. Santelli, Tetrahe-
dron Lett. 2006, 47, 459; c) F. Berthiol, H. Doucet, M. Santelli,
Synthesis 2006, 1518; d) M. Lemhadri, H. Doucet, M. Santelli,
Synlett 2006, 2935; e) A. Battace, T. Zair, H. Doucet, M. San-
telli, Synthesis 2006, 3495.
[
24] a) B. A. Trofimov, S. F. Malysheva, R. N. Kudyakova, E. P. Vy-
alykh, V. K. Stankevich, SU Patent 1504968, 1987 [Chem.
Abstr. 1995, 123, 285214]; b) B. A. Trofimov, S. F. Malysheva,
E. P. Vyalykh, L. M. Sinegovskaya, N. K. Gusarova, Russ. J.
Org. Chem. (Engl. Transl.) 1998, 34, 474.
[
17] I. Kondolff, H. Doucet, M. Santelli, Organometallics 2006, 25,
5219.
[
25] B. A. Trofimov, in Heteroatomic Derivatives of Acetylene – New
Polyfunctional Monomers, Reagents and Intermediates, Nauka,
Moscow, 1981 (in Russian) [Chem. Abstr. 1982, 96, 68296p].
26] a) D. Semenzin, G. Etemad-Moghadam, D. Albouy, O. Diallo,
M. Koenig, J. Org. Chem. 1997, 62, 2414; b) A. F. Parsons,
D. J. Sharpe, Ph. Taylor, Synlett 2005, 2981; c) Ch. M. Jesop,
A. F. Parsons, A. Routledge, D. J. Irvine, Eur. J. Org. Chem.
[
18] a) M. Feuerstein, F. Berthiol, H. Doucet, M. Santelli, Synthesis
004, 1281; b) M. Feuerstein, H. Doucet, M. Santelli, Tetrahe-
2
dron Lett. 2005, 46, 1717; c) M. Lemhadri, H. Doucet, M. San-
telli, Tetrahedron 2005, 61, 9839.
[
[
19] a) M. Feuerstein, H. Doucet, M. Santelli, J. Organomet. Chem.
2003, 687, 327; b) I. Kondolff, H. Doucet, M. Santelli, Tetrahe-
dron 2004, 60, 3813; c) I. Kondolff, H. Doucet, M. Santelli,
Synlett 2005, 2057; d) I. Kondolff, H. Doucet, M. Santelli, J.
Heterocycl. Chem. 2008, 45, 109.
2006, 1547.
[
27] a) B. G. Sukhov, N. K. Gusarova, N. I. Ivanova, M. V. Bog-
danova, O. N. Kagheva, G. G. Alexandrov, O. A. D’yachenko,
L. M. Sinegovskaya, S. F. Malysheva, B. A. Trofimov, J. Struct.
Chem. 2005, 46, 1066; b) N. K. Gusarova, M. V. Bogdanova,
N. I. Ivanova, N. A. Chernysheva, B. G. Sukhov, L. M. Sine-
govskaya, O. N. Kazheva, G. G. Alexandrov, O. A. D’yach-
enko, B. A. Trofimov, Synthesis 2005, 3103.
[
20] a) I. Kondolff, H. Doucet, M. Santelli, Synlett 2004, 1561; b)
F. Berthiol, H. Doucet, M. Santelli, Catal. Lett. 2005, 102, 281;
c) A. Battace, T. Zair, H. Doucet, M. Santelli, J. Organomet.
Chem. 2005, 690, 3790; d) M. Feuerstein, L. Chahen, H. Dou-
cet, M. Santelli, Tetrahedron 2006, 62, 112.
21] L. Ropartz, K. J. Haxton, D. F. Foster, R. E. Morris, A. M. Z.
Slawin, D. J. Cole-Hamilton, J. Chem. Soc., Dalton Trans.
[
[
28] E. Alacid, C. Nájera, Adv. Synth. Catal. 2006, 348, 2085.
Received: April 8, 2009
Published Online: May 18, 2009
2002, 4323.
[
22] Clegg, K. Izod, W. McFarlane, P. O’Shaughnessy, Organome-
tallics 1998, 17, 5231.
Eur. J. Org. Chem. 2009, 3427–3431
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3431