Synthesis of alkyl(diphenyl)phosphines by hydrophosphination of vinylarenes catalyzed by transition metal complexes

Article abstract of DOI:10.1023/A:1022552404812

Hydrophosphination of styrenes and their heteroanalogs with diphenylphosphine in the presence of nickel or palladium complexes was accomplished for the first time. The reaction ensures high yields and regioselectivity: the corresponding anti-Markownikoff adducts are exclusively formed.

Full text of DOI:10.1023/A:1022552404812

Russian Journal of Organic Chemistry, Vol. 38, No. 10, 2002, pp. 1479 1484. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 10, 2002,
pp. 1532 1537.
Original Russian Text Copyright
2002 by Kazankova, Shulyupin, Borisenko, Beletskaya.
Synthesis of Alkyl(diphenyl)phosphines by Hydrophosphination
of Vinylarenes Catalyzed by Transition Metal Complexes*
M. A. Kazankova, M. O. Shulyupin, A. A. Borisenko, and I. P. Beletskaya
Faculty of Chemistry, Moscow State University, Vorob’evy gory, Moscow, 119899 Russia
e-mail: beletska@org.chem.msu.ru
Received July 7, 2002
Abstract Hydrophosphination of styrenes and their heteroanalogs with diphenylphosphine in the presence
of nickel or palladium complexes was accomplished for the first time. The reaction ensures high yields and
regioselectivity: the corresponding anti-Markownikoff adducts are exclusively formed.
Until recently, addition of compounds containing
a hydrogen heteroelement bond to unsaturated com-
pounds, primarily to alkynes and alkenes, catalyzed by
transition metal complexes, included mainly hydro-
silylation reactions [1], which are widely used in
industry. Later on, catalysis by metal complexes was
applied to hydroboration with weakly reactive boranes
like catecholborane [2]. Transition metal complex-
catalyzed addition of dialkyl hydrogen phosphites [3]
and phosphine oxides [4] to nonactivated alkynes and
alkenes was discovered relatively recently. Interest in
these reactions originates not only from their great
synthetic potential but also from the fact that synthesis
of many products by addition rather than substitution
reactions is the most efficient from the viewpoint of
green chemistry : ideally, such syntheses may be
effected without formation of by-products, i.e., with
a 100% atom efficiency.
The above stated explains our interest in the syn-
thesis of tertiary phosphines by addition reactions.
Tertiary phosphines constitute an important class of
organophosphorus compounds which are widely used
as ligands in metal-complex catalysis. It is not
an overstatement to say that success in one or another
transition metal-catalyzed reaction, which should give
a new C C or C E bond, is determined mainly
by the nature of the ligand, primarily of the phosphine
ligand. Usually, triarylphosphines are used as ligands
____________
in these processes, but in some cases the presence of
an alkyl group at the phosphorus atom is necessary to
enhance electron-donor power of the phosphine and
its ability to affect oxidative addition to a metal atom.
Just the use of (t-Bu)3P made it possible to replace
expensive aryl bromides by cheap aryl chlorides in
the oxidative addition to Pd(0) [5]. Phosphines like
Ph2PAlk are commonly prepared by reactions of
organolithium or organomagnesium compounds with
Ph2PHlg or by reactions of alkyl halides with phos-
phide anion [6]. Alkyldiarylphosphines can also be
obtained by radical addition to olefins or by acid- or
base-catalyzed addition to activated alkenes [7]. Phos-
phine addition to Michael acceptors like acrylonitrile
or alkyl acrylates was effected under catalysis by
transition metal complexes [8]. While performing
the present work, addition of diphenylphosphine to
alkenes and alkynes in the presence of lanthanide
complexes was reported [9].
We were the first to accomplish addition of di-
phenylphosphine to vinylarenes(heteroarenes) (which
can be regarded as weakly activated olefins) in the
presence of palladium or nickel complexes. Such
addition is more difficult to occur than analogous
reaction with alkynes [10]; it is successful only with
substrates having an aryl or hetaryl group. As catalytic
precursors we used NiCl2, NiBr2, Ni(PPh3)2Cl2,
Ni(PPh3)2Br2, Ni(acac)2, Ni(cod)2, Ni[P(OEt)3]4,
Ni[P(OPh)3]4, Pd(CH3CN)2Cl2, Pd(PPh3)2Cl2, and
Pd(PPh3)4. These complexes are capable of promoting
the reaction of diphenylphosphine with styrene in
benzene at 25 130 C in a sealed ampule (Table 1).
The reaction gives two products: -adduct I and tetra-
phenyldiphosphine (II) (Scheme 1). The latter is
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 00-03-32747) and by the
Leading Scientific School (project no. 00-15-97 406),
Integration of the Higher School and Russian Academy of
Sciences (project no. AO115), and Universities of Russia
Programs (project no. 05.03.006).
1070-4280/02/3810-1479$27.00 2002 MAIK Nauka/Interperiodica

1480
KAZANKOVA et al.
formed via oxidative dimerization of Ph2PH [11], and
the product ratio depends on the catalyst.
absence of styrene, oxidative dimerization of di-
phenylphosphine to diphosphine II is promoted by
Ni(PPh3)2Br2, but under considerably more severe
conditions (Table 1, run no. 2); no reaction occurs at
room temperature.
Scheme 1.
Taking into account that oxidation of diphenyl-
phosphine to tetraphenyldiphosphine by the action of
Ni(II) could lead to formation of HBr which in turn
is capable of converting Ni(0) into Ni(II) via oxidative
addition (Scheme 1), we performed the reaction in
the presence of triethylamine to neutralize liberated
hydrogen bormide (Table 1, run nos. 3, 4). In the
absence of styrene about 5% of tetraphenyldiphos-
phine was formed (run no. 3), whereas in the presence
of styrene a mixture of the addition product and tetra-
phenyldiphosphine was obtained (run no. 4). Probably,
in this case tetraphenyldiphosphine is formed by
a different mechanism.
In the presence of Ni(II), Pd(II), and Pd(0) com-
plexes, oxidative dimerization of diphenylphosphine
to tetraphenyldiphosphine occurs very readily and is
the main reaction pathway (Table 1, run no. 1). The
process is strongly accelerated in the presence of
styrene which (as was shown by special experiments)
is converted into ethylbenzene (Scheme 2). In the
Scheme 2.
Table 1. Transformation of diphenylphosphine in the
presence of Ni(PPh3)2Br2
a
Run Temperature, C Conversion
Ratio I: II,
no.
(time, h)
of Ph2PH, %
%
1b 20 (48) or 50 (5)
100
100
5
0: 100
0: 100
0: 5
2
130 (30)
130 (30)
130 (28)
3c
4d
100
50: 50
a
Amounts of the reactants: diphenylphosphine, 1.5 mmol;
benzene, 2 ml; Ni(PPh3)2Br2, 5 mol %.
Styrene, 3 mmol, was added.
Triethylamine, 0.15 ml, was added.
Styrene, 3 mmol, and triethylamine, 0.15 ml, were added.
b
c
d
The pattern dramatically changed when Ni(0) com-
plexes were used as catalysts (Table 2, run nos. 1, 2).
Here, adduct I was the major product, and it was
formed as the only one in the presence of triethyl-
amine (Table 2, run nos. 3, 4). The reaction can be
accelerated to a considerable extent through the use
of excess styrene (Table 2, run no. 4).
Table 2. Addition of diphenylphosphine to styrene in
the presence of Ni(0) complexesa
Run
no.
Catalyst,
5 mol%
Temp., C Conver- Ratio I: II,
(time, h) sion, %
%
The reaction under study is regioselective, and it
yields exclusively the corresponding -adduct. We
also performed reactions with substituted styrenes
under the optimal conditions (Table 3). According to
the NMR data, in all cases the products were formed
in almost quantitative yield, and the yield of the
isolated products was 85 95%.
The absence of -substituted products in the addi-
tion of Ph2PH to styrene and vinylpyridines allows
us to exclude formation of a -allyl intermediate like
1
2
3b
Ni[P(OEt)3]4
Ni[P(OEt)3]4
Ni[P(OEt)3]4
90 (40)
130 (40)
130 (40)
130 (20)
85
95
95
100
100
95: 5
90: 10
100: 0
100: 0
100: 0
4b, c Ni[P(OEt)3]4
5b, c Ni[P(OPh)3]4 130 (30)
a
Amounts of the reactants: styrene, 1.5 mmol; diphenylphos-
phine, 1.5 mmol; benzene, 2 ml.
Triethylamine, 0.15 ml, was added.
b
c
The amount of styrene was 3 mmol.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

SYNTHESIS OF ALKYL(DIPHENYL)PHOSPHINES BY HYDROPHOSPHINATION
1481
%
Table 3. Addition of diphenylphosphine to substituted phenyl- and pyridylethenesa
Run no.
1
Initial compound
C6H5CH CH2
Adduct
Time, h
20
Yield,b
(I)
>99 (95)
>99 (85)
>99 (95)
>99 (90)
>99 (85)
>99 (85)
>95 (90)
>99 (87)
2
3
4
5c
6
7
8
4-MeOC6H4CH CH2
2-MeOC6H4CH CH2
4-MeC6H4CH CH2
4-ClC6H4CH CH2
(Ia)
(Ib)
(Ic)
(Id)
(Ie)
(If)
(Ig)
25
25
20
20
20
10
20
(C5H4N-2)CH CH2
(2-MeC5H3N-5)CH CH2
(C5H4N-4)CH CH2
a
A typical experiment was carried out with 3 mmol of alkene, 1.5 mmol of diphenylphosphine, 5 mol % of Ni[P(OEt)3]4, 2 ml of
benzene, and 0.152 ml of triethylamine; 130 C.
According to the 31P NMR data; the yield of the isolated product is given in parentheses.
The reaction was carried out with 1 equiv. of 4-chlorostyrene.
b
c
that assumed for the Pd-catalyzed hydroamination of
styrene [12]. Scheme 3 shows a probable catalytic
cycle which includes oxidative addition of phosphine
to Ni(0) with formation of a hydridophosphide com-
plex, olefin insertion into the Ni H bond, and reduc-
tive elimination.
It was interesting to perform hydrophosphination of
-methylstyrene, which should give rise to an asym-
metric center. Here, the possibility for stereoselective
synthesis exists. The reaction with -methylstyrene
occurred at a considerably lower rate (Table 4, run
nos. 1 5). Increase in the catalyst amount did not
affect the reaction rate (Table 4, run nos. 2, 3). The
Scheme 3.
Scheme 4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

1482
KAZANKOVA et al.
Table 4. Addition of diphenylphosphine to -methyl-
2-methoxystyrene [17], and 4-methoxystyrene [17]
were synthesized by known methods. Styrene, 2-vinyl-
pyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine,
4-chlorostyrene, 4-methylstyrene, and -methylstyrene
were commercial products.
styrenea
Run Temperature,
C
Conversion
Ratio III: II,
no.
(time, h)
of Ph2PH, %
%
General procedure for hydrophosphination of
aryl- and hetarylethenes with diphenylphosphine.
A 8-mm (i.d.) ampule was charged with 279 mg
(1.5 mmol) of diphenylphosphine, 2 ml of benzene or
toluene, and 54 mg (5 mol %) of tetrakis(triethyl
phosphite)nickel(0). Alkene, 3 mmol, and triethyl-
amine, 152 mg (1.5 mmol), were then added, and the
ampule was sealed and heated at 130 C until the reac-
tion was complete (according to the 31P NMR data).
When the signal of initial diphenylphosphine,
1
2
3b
4c
5c
130 (20)
130 (40)
130 (40)
130 (40)
130 (100)
35
46
46
49
82
100: 0
98: 2
98: 2
99: 1
98: 2
a
Amounts of the reactants: -methylstyrene, 3 mmol; diphenyl-
phosphine, 1.5 mmol; Ni[P(OEt)3]4, 5 mol %; toluene, 2 ml;
triethylamine, 0.152 ml.
The catalyst was added in 5% portions every 20 h.
After 20 h, an additional 1.5 mmol of -methylstyrene was
added.
b
c
40.6 ppm, disappeared from the spectrum, the
P
ampule was cooled and opened, and the solvent and
excess alkene were distilled off under reduced pres-
sure. The residue was either recrystallized from
THF hexane (on cooling to 18 C) or purified by
chromatography on silica gel using gradient elution
with hexane to 3:1 hexane benzene.
addition was accelerated by the use of 3 equiv of
-methylstyrene (Table 4, run nos. 2, 4), but in this
case the complete conversion cannot be attained
(Table 4, run no. 5). The resulting phosphine readily
undergoes oxidation during isolation, and the product
was characterized as phosphine oxide IIIa (Scheme 4).
Thus we have developed a new almost wasteless
procedure for synthesizing alkyl(diphenyl)phosphines.
The procedure is applicable to sterically hindered
styrenes. We are now studying the possibility for
asymmetric hydrophosphination of alkenes.
Diphenyl(2-phenylethyl)phosphine (I) [18] was
obtained from 312 mg (3 mmol) of styrene; reaction
time 20 h. The product was purified by chromatog-
1
raphy. Yield 560 mg (92%), colorless oil. H NMR
spectrum (C6D6), , ppm: 2.31 2.36 m (2H), 2.74
2.80 m (2H), 7.06 7.21 m (11H), 7.48 7.52 m (4H).
31P {1H} NMR spectrum (C6D6): P 16.1 ppm.
[2-(4-Methoxyphenyl)ethyl]diphenylphosphine
(Ia) was synthesized from 402 mg (3 mmol) of
4-methoxystyrene; reaction time 25 h. After chro-
matographic purification, 410 mg (95%) of compound
EXPERIMENTAL
1
All operations, including preparation, isolation, and
generation of phosphorus(III) compounds, were per-
formed under dry argon. The solvents were purified
by standard procedures: hexane, benzene, toluene,
and THF were refluxed over metallic sodium and then
distilled over it.
The progress of reactions was monitored, and the
newly synthesized compounds were identified, by H
and 31P NMR spectroscopy. The H NMR spectra
were recorded on a Varian VXR-400 spectrometer at
400 MHz using TMS or HMDS as internal reference.
The 31P NMR spectra were measured on the same
instrument at 161.9 MHz using 85% H3PO4 as
external reference. The chemical shifts are given
relative to TMS (1H) or 85% H3PO4 (31P).
Dichlorobis(triphenylphosphine)nickel(II) [13],
tetrakis(triethyl phosphite)nickel(0) [14], dibromobis-
(triphenylphosphine)nickel(II) [13], tetrakis(triphenyl
phosphite)nickel(0) [15], diphenylphosphine [16],
Ia was isolated as a colorless oil. H NMR spectrum
(C6D6), , ppm: 2.33 2.37 m (2H), 2.74 2.80 m (2H),
3.43 s (3H), 6.79 6.86 m (4H), 7.15 7.21 m (6H),
7.50 7.54 m (4H). 31P {1H} NMR spectrum (C6D6):
16.3 ppm. Found, %: C 79.01; H 6.52. C21H21PO.
P
Calculated, %: C 78.75; H 6.56.
[2-(2-Methoxyphenyl)ethyl]diphenylphosphine
(Ib) was obtained from 402 mg (3 mmol) of
2-methoxystyrene; reaction time 25 h. The product
was purified by recrystallization. Yield 455 mg (95%).
1H NMR spectrum (C6D6), , ppm: 2.45 2.49 m (2H),
2.97 3.03 m (2H), 3.36 s (3H), 6.61 d (1H), 6.91 t
(1H), 7.08 7.20 m (8H), 7.54 7.58 m (4H). 31P {1H}
1
1
NMR spectrum (C6D6):
15.6 ppm. Found, %:
P
C 78.11; H 7.03. C21H21PO. Calculated, %: C 78.75;
H 6.56.
[2-(4-Methylphenyl)ethyl]diphenylphosphine
(Ic) was obtained from 354 mg (3 mmol) of 4-methyl-
styrene; reaction time 20 h. The product was purified
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

SYNTHESIS OF ALKYL(DIPHENYL)PHOSPHINES BY HYDROPHOSPHINATION
1483
by chromatography. Yield 460 mg (90%), colorless
oil. H NMR spectrum (C6D6), , ppm: 2.28 s (3H),
Detection of ethylbenzene in the reaction of di-
phenylphosphine with styrene. A 5-mm NMR
ampule was purged with argon and charged with
0.1395 g of diphenylphosphine, 0.117 g of styrene,
and 11 mg (5 mol %) of Ni(PPh3)2Br2, and 0.6 ml of
benzene-d6 was added. The mixture was kept for
2 days at room temperature. The 31P {1H} NMR
1
2.40 2.44 m (2H), 2.80 2.90 m (2H), 7.09 7.25 m
(10H), 7.55 7.63 m (4H). 31P {1H} NMR spectrum
(C6D6):
16.5 ppm. Found, %: C 82.46; H 6.85.
C21H21P. PCalculated, %: C 82.89; H 6.90.
[2-(4-Chlorophenyl)ethyl]diphenylphosphine
(Id) was obtained from 229 mg (1.5 mmol) of
4-chlorostyrene; reaction time 10 h. The product was
purified by chromatography. Yield 430 mg (85%),
colorless oil. 1H NMR spectrum (C6D6), , ppm:
2.17 2.21 m (2H), 2.56 3.62 m (2H), 7.13 7.20 m
(10H), 7.45 7.51 m (4H). 31P {1H} NMR spectrum
spectrum contained only one signal at
17.6 ppm
P
1
(Ph2PPPh2). In the H NMR spectrum we observed
signals belonging to ethylbenzene, , ppm: 1.19
1.23 t (3H), 2.55 2.61 q (2H).
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16.7 ppm. Found, %: C 74.44; H 5.53.
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P
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P
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1
144 mg (30%) of product IIIa. H NMR spectrum
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2.43 2.50 m (1H), 3.35 3.50 m (1H), 7.03 7.15 m
(12H), 7.75 7.83 m (3H). 31P {1H} NMR spectrum
(C6D6):
23.5 ppm. Found, %: C 78.21; H 6.54.
P
C21H21PO. Calculated, %: C 78.75; H 6.56.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

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