Synthesis of vinylphosphines by hydrophosphination of alkynes in the presence of transition metal complexes

Article abstract of DOI:10.1023/A:1022548303903

Intermolecular hydrophosphination of terminal and internal alkynes with diphenylphosphine, catalyzed by palladium and nickel complexes, was accomplished for the first time. The reaction follows the syn-addition pattern. Conditions were found which ensure

Full text of DOI:10.1023/A:1022548303903

Russian Journal of Organic Chemistry, Vol. 38, No. 10, 2002, pp. 1465 1474. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 10, 2002,
pp. 1518 1527.
Original Russian Text Copyright
2002 by Kazankova, Efimova, Kochetkov, Afanas’ev, Beletskaya.
Synthesis of Vinylphosphines by Hydrophosphination
of Alkynes in the Presence of Transition Metal Complexes*
M. A. Kazankova, I. V. Efimova, A. N. Kochetkov,
V. V. Afanas’ev, and I. P. Beletskaya
Faculty of Chemistry, Moscow State University, Vorob’evy gory, Moscow, 119899 Russia
e-mail: beletska@org.chem.msu.ru
Received August 7, 2002
Abstract Intermolecular hydrophosphination of terminal and internal alkynes with diphenylphosphine,
catalyzed by palladium and nickel complexes, was accomplished for the first time. The reaction follows the
syn-addition pattern. Conditions were found which ensure regioselective addition with predominant or
exclusive formation of the corresponding - or -adduct.
The addition of compounds with a heteroelement
hydrogen bond (E H) to alkynes is an important
reaction leading to functionally substituted olefins. Of
particular interest are processes catalyzed by transition
metal complexes, which make it possible to effect
regio- and stereoselective addition. Up to now, hydro-
silylation [1 3], hydrostannylation [4 7], and hydro-
boration [8, 9] of alkynes, catalyzed by transition
metal complexes, have been studied in sufficient
detail. Tanaka and co-workers recently initiated
studies on the addition of dialkyl hydrogen phosphites
[10, 11] and phosphine oxides [12 14] to alkynes in
the presence of palladium and rhodium complexes.
The addition of phosphines to alkynes in the presence
of metal complexes was reported by Marks and
co-workers [15 17] who performed intramolecular
cyclization of phosphinoalkynes under catalysis by
organic lanthanide derivatives. In the present com-
munication we describe a new synthetic route to
vinylphosphines, which is based on palladium- or
nickel-catalyzed direct addition of secondary phos-
phines to both terminal and internal alkynes.
is limited because of the lack of a simple and con-
venient procedure for their synthesis. Alkenylphos-
phines can be obtained by reactions of vinyl deriva-
tives of nontransition metals (such as Li, Mg, and Sn)
with halophosphines or of phosphide anion with
alkenyl halides [21]. These compounds can also be
obtained by addition of primary and secondary phos-
phines to alkynes. The first and the second methods
include a laborious procedure for isolation of final
products (removal of the metal salt); therefore, they
are low efficient from the viewpoint of green
chemistry requirements imposed on modern synthetic
procedures [22 25]. Radical or thermal, as well as
base-catalyzed, addition of primary and secondary
phosphines to alkynes provides an optimal procedure
sometimes ensuring 100% atom efficiency. How-
ever, in the general case, it was studied insufficiently.
Simple thermal addition of phosphines to alkynes
requires severe conditions (prolonged heating at
elevated temperature) and leads to mixtures of prod-
ucts which are usually formed in poor yields [26].
Several examples of radical addition of phosphines to
alkynes were reported, but catalysis by bases (e.g.,
by potassium tert-butoxide) is used more frequently
[27, 28]. In some cases, the addition was accelerated
through the use of stoichiometric amounts of alkyne
and phosphine complexes with metals (like Mo),
which were prepared preliminarily [29, 30]; however,
base catalysis was also necessary.
Alkenylphosphines constitute an important class of
phosphine ligands [18 20]. However, their application
____________
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 00-03-32747), by the
Program for Support of Leading Scientific Schools (project
no. 00-15-97406), by the Federal Program for State Support
of Integration of the Higher Education and Basic Research
2001 2002 (project no. AO115), by the INTAS Foundation
(grant no. YSF-169), and by the Program Universities of
Russia.
We were the first to effect palladium- or nickel-
catalyzed addition of diphenylphosphine to alkynes
As catalytic precursors we tried various palladium and
1070-4280/02/3810-1465$27.00 2002 MAIK Nauka/Interperiodica

1466
KAZANKOVA et al.
nickel compounds: Pd(PPh3)4, Pd2(dba)3, Pd(OAc)2,
NiBr2, Ni(acac)2, Ni[P(OEt)3]4, etc. All these com-
plexes catalyze the addition of diphenylphosphine to
phenylacetylene (Ia) in benzene or acetonitrile with
formation of three products: diphenyl-(1-phenyl-
ethenyl)phosphine (IIa, -adduct), (E)-diphenyl(2-
phenylethenyl)phosphine (E-IIIa), and (Z)-diphenyl-
(2-phenylethenyl)phosphine (Z-IIIa) ( -adducts)
(Scheme 1).
Nickel(II) bromide was the best catalyst for the pre-
paration of -adduct IIa. Its fraction was 90%, and
minor isomer E-IIIa was obtained with high stereo-
selectivity (run no. 9). When the hydrophosphination
was performed in the presence of nickel complexes at
130 C, the reaction time was considerably shorter
(1.5 2 h); the amount of the -adduct did not change
(run no. 10), whereas the fraction of the -isomer
slightly decreased (run no. 11).
The rate of hydrophosphination at 80 C strongly
depends on the solvent. The reaction of diphenyl-
phosphine with phenylacetylene in acetonitrile in
the presence of 2 mol % of Ni(acac)2 was very slow:
the conversion was 80% in 200 h, i.e., its rate is com-
parable with that of the thermal reaction (no catalytic
effect was observed). The same reaction in benzene
takes 60 h (100% conversion), and the isomeric com-
position of the products almost does not change. It
should be noted that nickel and palladium salts as
catalytic precursors give rise to the -adduct as the
major product at both 80 C and 130 C (run nos. 5, 6,
9, 11) and that the minor -adduct is formed exclu-
sively as E isomer. The use of Ni(0) or Pd(0) com-
plexes, as well as of Ni(acac)2, leads to substantial
change in the regioselectivity, so that -adduct IIIa
prevails among the products (run nos. 1 4, 8, 10),
and it is formed as a mixture of E and Z isomers. In
the catalysis by Pd complexes, the fraction of Z-IIIa
is greater, whereas in the presence of Ni complex the
major isomer has E configuration.
The above data led us to presume that predominant
formation of the -adduct is observed in the presence
of those catalytic systems which could give rise to
acid species. In fact, in the reaction with unpurified
Ni[P(OEt)3]4, which may be contaminated with
(EtO)2P(O)Br and probably with (EtO)2P(O)OH, the
reaction mixture contained about 70% of the -adduct
(cf. run no. 7). In order to verify this assumption,
hydrophosphination of phenylacethylene was carried
Scheme 1.
The optimal catalytic system and reaction condi-
tions were selected on the basis of the data obtained
by 31P NMR monitoring of the reaction of diphenyl-
phosphine with phenylacetylene, following the intens-
ity of the Ph2PH signal,
41.6 ppm. The results
P
are given in Table 1. The selectivity of the process,
primarily the site of addition of the Ph2P group, was
found to strongly depend on the catalytic system.
Reactions catalyzed by Pd(0) complexes, Pd(PPh3)4
and Pd2(dba)3, on heating at 130 C for 18 h resulted
in formation of phosphine IIIa as the only product
in acetonitrile (Table 1, run nos. 1, 2) or the major
product in benzene (run nos. 3, 4). Both in acetonitrile
and in benzene, the major isomer was Z-IIIa. By con-
trast, in the presence of palladium acetate as catalyst
precursor, the corresponding -adduct (phosphine IIa)
was formed as the major product in both solvents
(run nos. 5, 6). In this case, the reaction in acetonitrile
was much faster than in benzene, and its regioselec-
tivity was also higher (run no. 6).
Scheme 2.
Catalytic systems on the basis of nickel complexes
or salts turned out to be more effective than palladium
complexes. In the presence of tetrakis(triethyl phos-
phite)nickel(0), bis(acetylacetonato)nickel(II), or
NiBr2, the addition occurred at a sufficient rate in
benzene at 80 C (run nos. 7 9). Here, the general
relations were the same as in the catalysis by pal-
ladium complexes. Phosphine IIIa was the major
product in the reaction catalyzed by the Ni(0) complex
(run no. 7). The same product also predominates in
the presence of Ni(acac)2 (run no. 8), though its frac-
tion is lower than in the presence of Ni[P(OEt)3]4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

SYNTHESIS OF VINYLPHOSPHINES BY HYDROPHOSPHINATION OF ALKYNES
1467
Table 1. Reaction of phenylacetylene (Ia) with diphenylphosphine in the presence of palladium and nickel complexes
Run
no.
Temperature,
(time, h)
C
Isomer ratioa
IIa: IIIa (E / Z)
Catalyst
Pd(PPh3)4
Pd2(dba)3
Pd(PPh3)4
Pd2(dba)3
Pd(OAc)2
Pd(OAc)2
Ni[P(OEt)3]4
Ni(acac)2
NiBr2
Ni(acac)2
NiBr2
Ni(acac)2 +(EtO)2P(O)H
Pd(PPh3)4 +MeCOOH
Solvent
Yield,a
%
1
2
3
4
5
6
7
8
9
10
11
12
13
Acetonitrile
Acetonitrile
Benzene
Benzene
Benzene
Acetonitrile
Benzene
Benzene
Benzene
Benzene
130 (18)
130 (18)
130 (18)
130 (18)
130 (20)
130 (7)
80 (10)
80 (60)
80 (10)
130 (2)
130 (2)
80 (10)
80 (12)
95
98
95
87b
90
0:100 (14/86)
0:100 (20/80)
7: 93 (30/70)
25: 75 (20/80)
64: 36 (28/72)
87: 13 (53/47)
10: 90 (50/50)
27: 73 (67/33)
86: 14 (100/0)
27: 73 (77/23)
78: 22 (100/0)
89
93b
82b
90b
92b
85b
90
Benzene
Benzene
Acetonitrile
95: 5
92: 8
(100/0)
(50/50)
92b
a
According to the 31P NMR data.
After distillation.
b
out over Ni(acac)2 at 80 C in benzene containing
2 mol % of diethyl hydrogen phosphite. As a result,
we obtained almost pure -isomer with an admixture
of less than 5% of the -adduct (run no. 12). Like-
wise, addition of a catalytic amount of acetic acid in
the hydrophosphination catalyzed by Pd(PPh3)4 in
acetonitrile (run no. 13) dramatically changed its
regioselectivity. In this case, -isomer IIa was also
the major product, and the ratio IIa:IIIa (E:Z) was
92:8 (50:50) (cf. run no. 1; Scheme 2). Thus, by
appropriate choice of the catalytic system we are able
to control the selectivity of the addition and obtain
phosphine II or III in high yield.
bond, and subsequent reductive elimination with
regeneration of the reactive species of the catalytic
complex (cycle A in Scheme 3). Change of the regio-
selectivity in the reactions catalyzed by Pd(II) or
Ni(II) complexes or in the presence of an acid occurs
due to appearance of the second catalytic cycle B via
oxidative addition of the acid species HX to the metal
and insertion of phenylacetylene into the M H bond
according to the Markownikoff rule. The subsequent
ligand exchange (X and PPh2) regenerates HX and
gives an intermediate species; reductive elimination
from the latter yields the cross-coupling product.
Scheme 3.
The structure of the products was confirmed by
1
elemental analysis, and IR and H, 13C, and 31P NMR
1
spectroscopy. In the H NMR spectra of -adduct IIa,
the vinyl protons give rise to an ABX spin system,
5.58 and 4.88 ppm, JPH = 12.8, 5.6 Hz. Isomers
E-IIIa and Z-IIIa of diphenyl(2-phenylethenyl)phos-
phine are much more difficult to identify, for signal
from one of the vinyl protons falls into the region
of aromatic protons. However, the proposed structures
are confirmed by combination of our spectral data
and those reported in [31 35] (1H NMR for Z-IIIa
and 13C NMR for Z-IIIa and E-IIIa).
The simplest explanation for the formation of the
-adduct may be the assumption that the reaction
involves initial oxidative addition of diphenylphos-
phine to the Pd(0) or Ni(0) complex to give a hydride
complex [36, 37], alkyne insertion into the M H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

1468
KAZANKOVA et al.
Regio- and stereoselective hydrophosphination was
The E isomer of phosphine IIIb turhed out to be
the most stable, and no E Z isomerization occurred
in the reactions over metal complexes, in contrast to
the reactions with phenylacetylene.
The addition of diphenylphosphine to 1-pentyne in
acetonitrile at 130 C in the presence of bis(acetyl-
acetonato)nickel(II) leads to formation of mixtures of
observed in the reaction of diphenylphosphine with
tert-butylacetylene (Ib). The bulky substituent at the
triple bond gives rise to anti-Markownikoff addition
with formation of the -adduct. Bis(acetylacetonato)-
nickel(II) and nickel(II) bromide turned out to be
the most efficient catalysts for hydrophosphination of
tert-butylacetylene: the reaction was complete in
2 5 h at 130 C (Table 2; run nos. 1, 2) and in 12 h at
80 C, respectively (run no. 3; Scheme 4).
the - and -adducts, the former prevailing ( :
=
70:30). Under analogous conditions in benzene, 70%
of the -adduct (a mixture of E-IIIc and Z-IIIc) and
30% of -adduct IIc were obtained. After distillation,
the overall yield was 70% (Scheme 5).
Scheme 4.
Scheme 5.
On the other hand, both triethyl phosphite Ni(0)
complex and dichlorobis(triphenylphosphine)palla-
dium(II) exhibit considerably lower catalytic activity
(Table 2, run nos. 4 6). However, in comparison to
the thermal addition which does not occur at all in
200 h at 130 C, the catalytic effect of these complexes
can be regarded as satisfactory. The only addition
product (both that detected in the reaction mixture and
isolated therefrom) was (E)-diphenyl(2-tert-butyl-
ethenyl)phosphine (E-IIIb). The yield of the isolated
phosphine was 95%, and its structure was proved by
The reaction of diphenylphosphine with 1-heptyne
(Id) at 130 C in acetonitrile or benzene in the pres-
ence of Ni(acac)2 was complete in 1.5 5 h to afford
85% of a mixture of three phosphines: -adduct IId
1
elemental analysis and H, 13C, and 31P spectroscopy.
and -adducts E-IIId and Z-IIId at an
:
ratio of
The configuration of the double bond in E-IIIb was
55:45 (Scheme 6).
3
assigned on the basis of the JHH coupling constant
equal to 17.0 Hz, which corresponds to trans arrange-
ment of the vicinal protons, i.e., the reaction of di-
phenylphosphine to tert-butylacetylene over transition
metal complexes follows the syn-addition pattern.
This is consistent with the known data on addition of
M H compounds to alkynes under catalysis by metal
complexes [38].
Scheme 6.
Table 2. Reaction of tert-butylacetylene with diphenyl-
phosphine in benzene
Run
no.
Tempera- Time, Conversion
Methyl 2-propynyl ether (Ie) reacted with diphenyl-
phosphine over nickel complex [Ni(acac)2] at 130 C
in acetonitrile, yielding mainly -adduct IIe (yield
87%, reaction time 3 h; Scheme 7).
Catalyst
ture,
C
h
of Ib, %
1
2
3
4
5
6
7
Ni(acac)2
NiBr2
NiBr2
PdCl2(PPh3)2
PdCl2(PPh3)2
Ni[P(OEt)3]4
Thermal reaction
130
130
80
2
5
12
50
100
100
100
0
Scheme 7.
80
130
80
65
60
65
20
130
200
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

SYNTHESIS OF VINYLPHOSPHINES BY HYDROPHOSPHINATION OF ALKYNES
1469
3-Dimethylaminopropyne (If) is less reactive than
methyl 2-propynyl ether (Ie), and its reaction with
diphenylphosphine in acetonitrile over Ni(acac)2
requires heating for 60 h at 130 C. Distillation of the
reaction mixture gave 84% of a mixture of addition
products containing approximately equal amounts of
-adduct IIf and E- and Z-isomeric -adducts IIIf
(Scheme 8).
dium(0) [39], tetrakis(triethyl phosphite)nickel(0)
[40], diphenylphosphine [41], and tert-butylacetylene
[42] were synthesized by known methods. Phenyl-
acetylene, 1-pentyne, 1-heptyne, and methoxymethyl-
acetylene were commercial products.
The progress of reactions was monitored, and the
1
products were identified, by IR and H and 13C NMR
1
spectroscopy. The H NMR spectra were recorded on
Tesla BS-467 and Varian VXR-400 spectrometers at
60 and 400 MHz, respectively, using TMS, HMDS,
or residual solvent signals as reference. The 13C NMR
spectra were obtained on a Varian VXR-400 instru-
ment operating at 100.6 MHz; the chemical shifts
were measured relative to the solvent signals: CD2Cl2,
CD3CN, C6D6, and CDCl3. The 31P NMR spectra
were recorded on a Varian FT-80A spectrometer at
32.2 MHz using 85% H3PO4 as external reference.
Scheme 8.
The reactions were carried out in 8-mm (i.d.)
ampules filled with argon, which were charged with
0.57 g (0.56 ml, 3 mmol) of diphenylphosphine, 0.3 g
(0.36 ml, 3 mmol) of phenylacetylene, 2 ml of ap-
propriate solvent, and catalyst. The ampule was sealed
and heated to a required temperature.
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of Pd(PPh3)4. A 40-mg
(1.2 mol %) amount of tetrakis(triphenylphosphine)-
palladium(0) was used. a. In acetonitrile at 130 C.
The reaction mixture was heated at 130 C. After 2 h
(10% conversion), the 31P NMR spectrum of the mix-
ture contained a signal from initial diphenylphosphine
Internal alkynes are also capable of reacting with
diphenylphosphine under catalysis by transition metal
complexes. Using tolan as an example, we showed
that the reaction catalyzed by bis(acetylacetonato)-
nickel(II) occurs under fairly mild conditions (12 h at
80 C) and yields (E)-1,2-diphenylethenylphosphine
(IIIg) in quantitative yield (Scheme 9).
Scheme 9.
and a signal at
24.72 ppm from phosphine Z-IIIa.
P
After 8 h, the only product was diphenyl(2-phenyl-
ethenyl)phosphine (IIIa) as a mixture of E and Z
isomers at a ratio of 14:86.
b. In benzene at 130 C. After 2 h (85% conver-
sion), the 31P NMR spectrum of the mixture contained
signals belonging to phosphines IIa, E-IIIa, and
Z-IIIa at a ratio of 1:3:7. After 8 h (95% conver-
sion), the product ratio was the same. The mixture
was heated for 18 h to obtain 0.86 g (100%) of
a mixture of phosphines IIa, E-IIIa, and Z-IIIa at
a ratio of 7:93 (IIa:IIIa) (E:Z = 30:70) [43, 44].
Thus, we were the first to accomplish transition
metal-catalyzed addition of diphenylphosphine at the
triple bond and find optimal conditions for selective
preparation of a number of tertiary alkenylphosphines.
EXPERIMENTAL
All operation with readily hydrolyzable and oxidiz-
able compounds and transition metal complexes were
carried out under dry argon; the glassware was kept
in a drying box or heated by a burner prior to use.
To remove traces of moisture, argon was passed
through a column filled with phosphoric anhydride.
The solvents were dried and purified by standard
methods: petroleum ether, hexane, pentane, benzene,
and diethyl ether were refluxed and distilled over
metallic sodium, and acetonitrile was distilled over
calcium hydride. Tetrakis(triphenylphosphine)palla-
Phosphine (IIa). 31P NMR spectrum:
5.3 ppm.
P
1H NMR spectrum, , ppm: 4.88 d.d (1H, cis-H, JHH
=
3
1.0, JPH = 5.6 Hz), 5.58 d.d (1H, trans-H, JHH = 1.0,
3JPH = 12.8 Hz), 7.3 m (15H, Harom). 13C NMR spec-
2
trum, C, ppm: 125.07 d (CH2, JPC = 3.9 Hz),
1
1
142.44 d (CP, JPC = 21.4 Hz), 136.13 d (Ci, JPC
=
13.0 Hz).
Phosphine E-IIIa. 31P NMR spectrum:
P
1
11.54 ppm. H NMR spectrum, , ppm: 6.88 d.d
3
(1H, cis-H, JHH = 10.8, JPH < 1 Hz), 7.32 d.d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

1470
KAZANKOVA et al.
2
PCH, JHH = 10.8, JPH < 1 Hz), 7.3 m (15H, Harom).
nickel(0) was used. The reaction mixture (a suspen-
sion in benzene) was heated at 80 C in a sealed
ampule. After 8 h (80% conversion), the 31P NMR
13C NMR spectrum, C, ppm: 126.65 d (CPh, JPC
=
2
1
11.4 Hz), 143.71 d (CP, JPC = 30.5 Hz), 136.85 d
spectrum of the mixture contained signals at
5.3
(Ci, JPC = 13.1 Hz).
1
(IIa), 11.54 (E-IIIa), and 24.72 ppm (Z-IIPIa) at
a ratio of 0.1:1:1. The mixture was heated for 10 h
at 80 C, and by the end of the reaction the isomer
ratio IIa:IIIa (E/Z) was 10:90 (50:50). The mixture
was filtered through a thin layer of silica gel on
a glass filter to remove the catalyst. The filtrate was
evaporated under reduced pressure, and the residue
was distilled in a vacuum to obtain 0.8 g (93%) of
a mixture of phosphines IIa, E-IIIa, and Z-IIIa at the
Phosphine Z-IIIa. 31P NMR spectrum:
P
1
24.72 ppm. H NMR spectrum, , ppm: 6.40 d.d
3
(1H, trans-H, JHH = 12.5, JPH < 1 Hz), 7.3 d.d (1H,
2
PCH, JHH = 12.5, JPH < 1 Hz), 7.3 m (15H, Harom).
13C NMR spectrum, C, ppm: 129.34 d (CPh, JPC
=
2
1
12.2 Hz), 144.89 d (CP, JPC = 20.9 Hz), 138,12 d
(Ci, JPC = 9.4 Hz).
1
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of Pd2(dba)3 CHCl3.
A 20-mg (0.5 mol %) amount of dibenzylideneacetone
palladium complex was used. a. In acetonitrile at
130 C. The reaction mixture was heated for 18 h at
130 C. Appropriate treatment of the mixture (without
distillation) gave 0.86 g (100%) of phosphine IIIa as
the only product (E:Z = 20:80).
b. In benzene at 130 C. After 2 h (70% conver-
sion), the 31P NMR spectrum of the mixture contained
signals from initial diphenylphosphine and products
II, E-IIIa, and Z-IIIa (ratio 1.5:1:3). After 8 h (95%
conversion), the product ratio was 2.2:1:4. The mix-
ture was heated for 18 h. By appropriate treatment
(without distillation) we isolated 0.86 g (100%) of
a mixture of phosphines IIa and IIIa at a ratio of
25:75 (the E/Z isomer ratio of IIIa was 20:80).
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of Pd(OAc)2. A 13-mg
(2 mol %) of palladium(II) acetate was used. a. In
benzene at 130 C. After 20 h, the 31P NMR spectrum
of the reaction mixture contained signals from phos-
phines IIa, E-IIIa, and Z-IIIa. The ratio IIa:IIIa
was 64:36 (E/Z ratio 28:72). The solvent was dis-
tilled off, and the residue was kept for 3 h under
reduced pressure (1 2 mm, oil pump) to obtain 0.78 g
(90%) of a mixture of phosphines IIa, E-IIIa, and
Z-IIIa at the same ratio.
b. In acetonitrile at 130 C. The reaction mixture
was heated for 7 h at 130 C and was then filtered
through a thin layer of silica gel on a glass filter to
remove the catalyst. The filtrate was evaporated under
reduced pressure to obtain 0.77 g (89%) of a mixture
of diphenyl(1-phenylethenyl)phosphine (IIa), (E)-di-
phenyl(2-phenylethenyl)phosphine (E-IIIa), and (Z)-
diphenyl(2-phenylethenyl)phosphine (Z-IIIa); IIa/IIIa
ratio 87:13 (E/Z 53:47).
2
same ratio. bp 140 145 C (7 10 mm).
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of Ni(acac)2. A 20-mg
(1.3 mol %) of bis(acetylacetonato)nickel(II) was
used. a. In benzene at 80 C. After 10 h (40% conver-
sion), the 31P NMR spectrum of the reaction mixture
contained signals from phosphines IIa, E-IIIa, and
Z-IIIa at a ratio of 1:17.3:3. The mixture was heated
for 50 h and filtered through a thin layer of silica gel
on a glass filter to remove the catalyst. The filtrate
was evaporated to obtain 0.86 g (100%) of a mixture
of phosphines IIa and IIIa at a ratio of 27:73 ((E/Z
ratio in IIIa 67:33). Distillation gave 0.7 g (82%) of
a product mixture with the same isomer ratio. bp 140
2
145 C (7 10 mm).
b. In benzene at 130 C. The mixture was heated
for 2 h at 130 C and was then treated as described
above to obtain 0.86 g (100%) of a mixture of phos-
phines IIa and IIIa at a ratio of 27:73 (E/Z ratio in
IIIa 77:23). Vacuum distillation gave 92% of the
same mixture.
c. In acetonitrile at 130 C. An ampule was purged
with argon, charged with 0.56 g (0.56 ml, 0.003 mol)
of diphenylphosphine and 20 mg (1.3 mol %) of bis-
(acetylacetonato)nickel(II) in 2 ml of anhydrous aceto-
nitrile, and sealed. The mixture was heated for 3 h
at 140 C, the ampule was opened, 0.3 g (0.36 ml,
0.003 mol) of phenylacetylene was added to the
yellow solution, and the ampule was sealed and
heated for 1.5 h at 130 C. When the reaction was
complete, the mixture was treated as described above
to obtain 0.86 g (100%) of a mixture of phosphines
IIa, E-IIIa, and Z-IIIa at a ratio of 2.14:5.43:1.
Further heating of the isomer mixture for 25 h at
140 C resulted in change of the IIa:IIIa ratio to
25:75 (E/Z 84:26).
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of NiBr2. A 10-mg
(1 mol %) amount of nickel(II) bromide was used.
a. In benzene at 80 C. The mixture was heated for
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of Ni[P(OEt)3]4. A 25-mg
(1 mol %) amount of tetrakis(triethyl phosphite)-
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SYNTHESIS OF VINYLPHOSPHINES BY HYDROPHOSPHINATION OF ALKYNES
1471
3
2
10 h at 80 C in a sealed ampule. After appropriate
treatment (without distillation), 0.86 g (100%) of
a mixture of phosphines IIa and E-IIIa at a ratio of
86:14 was obtained. Vacuum distillation gave 90%
of the same product mixture.
b. In benzene at 130 C. The mixture was heated
for 2 h at 130 C in a sealed ampule. After appropriate
treatment (without distillation), 0.85 g (100%) of
a mixture of spectrally pure phosphines IIa and E-IIIa
at a ratio of 78:22 was obtained. Vacuum distillation
gave 0.73 g (85%) of the same product mixture.
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of Ni(acac)2 and diethyl
hydrogen phosphite. A solution of 0.57 g (0.56 ml,
0.003 mol) of diphenylphosphine, 0.3 g (0.36 ml,
0.003 mol) of phenylacetylene, 20 mg (1.3 mol %) of
bis(acetylacetonato)nickel(II), and 20 mg (2.5 mol %)
of diethyl hydrogen phosphite in 2 ml of dry benzene
was heated for 10 h at 80 C in a sealed ampule. After
appropriate treatment (without distillation), 0.86 g
(100%) of a mixture of phosphines IIa and E-IIIa at
a ratio of 95:5 was obtained. Vacuum distillation
gave 90% of the same product mixture.
Reaction of diphenylphosphine with phenyl-
acetylene in the presence of Pd(PPh3)4 and acetic
acid. A solution of 0.57 g (0.56 ml, 0.003 mol) of
diphenylphosphine, 0.3 g (0.36 ml, 0.003 mol) of
phenylacetylene, 40 mg (1.2 mol %) of tetrakis(tri-
phenylphosphine)palladium(0), and 10 mg (2.5 mol %)
of acetic acid in 2 ml of dry benzene was heated for
12 h at 80 C in a sealed ampule. After appropriate
treatment (without distillation), 0.86 g (100%) of
(CCH3, JPC = 12.0 Hz), 120.08 d (CR, JPC
=
9.1 Hz), 157.96 d (CP, JPC = 32.5 Hz), 138.06 d (Ci,
1JPC = 9.7 Hz). Found, %: C 80.99; H 7.64; P 11.40.
C18H21P. Calculated, %: C 80.30; H 7.81; P 11.52.
Reaction of diphenylphosphine with tert-butyl-
acetylene in the presence of NiBr2. A suspension of
0.57 g (0.56 ml, 3 mmol) of diphenylphosphine,
0.42 g (0.63 ml, 5 mmol) of tert-butylacetylene (Ib),
and 10 mg (1.5 mol %) of nickel(II) bromide in 2 ml
of dry benzene was heated for 5 h at 130 C. Vacuum
distillation gave 0.77 g (95%) of (E)-(2-tert-butyl-
ethenyl)diphenylphosphine (E-IIIb).
1
Reaction of diphenylphosphine with 1-pentyne
in the presence of Ni(acac)2. A suspension of 0.57 g
(0.56 ml, 3 mmol) of diphenylphosphine, 0.34 g
(0.49 ml, 5 mmol) of 1-pentyne (Ic), and 20 mg
(1.3 mol %) of bis(acetylacetonato)nickel(II) in 2 ml
of dry benzene was heated for 1.5 h at 130 C. Distilla-
tion gave 0.67 g (88%) of a mixture of diphenyl-
(1-propylethenyl)phosphine (IIc), (E)-diphenyl(2-pro-
pylethenyl)phosphine (E-IIIc), and (Z)-diphenyl-
(2-propylethenyl)phosphine (Z-IIIc) at a ratio of
32:68 (IIc:IIIc), E/Z 85:15. bp 110 115 C (2 mm).
Found, %: C 79.83; H 7.52; P 12.22. C17H19P. Cal-
culated, %: C 80.31; H 7.48; P 12.20.
Phosphine IIc. 31P NMR spectrum:
4.41 ppm.
P
1H NMR spectrum, , ppm: 0.83 t (3H, RCH3),
1.39 m (2H, RCH2CH3), 2.11 t (2H, CCH2R),
4.93 d.d. (1H, cis-H, JHH = 1.1, JPH = 9.1 Hz),
5.55 d.d (1H, trans-H, JHH = 1.1, JPH = 19.3 Hz),
7.32 m (10H, Harom). 13C NMR spectrum, C, ppm:
13.46 s (RCH3), 21.58 s (RCH2CH3), 36.92 d
( CCH2R, JPC = 12.2 Hz), 122.41 d ( CH2, JPC
2
3
2
3
a
mixture of phosphines IIa and E-IIIa at
3
2
=
a ratio of 92:8 was obtained. Vacuum distillation
gave 92% of the same product mixture.
1
10.7 Hz), 148.45 d (CP, JPC = 13.8 Hz).
Phosphine E-IIIc. 31P NMR spectrum:
P
Reaction of diphenylphosphine with tert-butyl-
acetylene in the presence of Ni(acac)2. An ampule
was purged with argon and charged with 0.57 g
(0.56 ml, 3 mmol) of diphenylphosphine, 0.42 g
(0.63 ml, 5 mmol) of tert-butylacetylene (Ib), and
20 mg (1.3 mol %) of bis(acetylacetonato)nickel(II) in
2 ml of dry benzene. The ampule was sealed and
heated for 2 h at 130 C. After appropriate treatment
(without distillation), we obtained 0.81 g (100%) of
(E)-(2-tert-butylethenyl)diphenylphosphine (E-IIIb).
Vacuum distillation gave 0.73 g (90%) of phosphine
1
14.80 ppm. H NMR spectrum, , ppm: 0.81 t (3H,
RCH3), 1.34 m (2H, RCH2CH3), 2.07 d.t (2H,
CCH2R), 6.18 q.t (1H, CH, JHH = 13.5, JPH
3
3
=
=
,
3
2
15.1 Hz), 6.23 d.d (1H, PCH, JHH = 13.5, JPH
5.5 Hz, 7.13 m (10H, Harom). 13C NMR spectrum,
ppm: 13.57 s (RCH3), 21.58 s (RCH2CH3), 36.71 Cd
3
2
( CCH2R, JPC = 11.4 Hz), 134.44 d ( CR, JPC
=
1
10.7 Hz), 148.21 d (CP, JPC = 33.6 Hz), 139.21 d
(Ci, JPC = 9.2 Hz).
1
Phosphine Z-IIIc. 31P NMR spectrum:
P
1
E-IIIb. bp 92 95 C (2 mm). 31P NMR spectrum:
32.49 ppm. H NMR spectrum, , ppm: 0.81 t (3H,
RCH3), 1.34 m (2H, RCH2CH3), 2.37 d.t (2H,
1
14.56 ppm. H NMR spectrum, , ppm: 0.99 s
P
3
3
3
2
CCH2R), 6.32 q.t (1H, CH, JHH = 11.3, JHH
=
(9H, CH3), 6.18 d.d (1H, PCH, JHH = 17.00, JPH
3.3 Hz), 6.31 d.d (1H, HC , JHH = 17, JPH
17.1 Hz), 7.30 m (10H, Harom). 13C NMR spectrum,
=
=
7.1, JPH = 23.6 Hz), 6.13 d.q (1H, PCH, 3JHH = 11.3,
3
3
3
3JHH = 1.1, JPH = 2.2 Hz), 7.13 m (10H, Harom). 13C
2
NMR spectrum, C, ppm: 13.52 s (RCH3), 22.18 s
(RCH2CH3), 32.73 d ( CCH2R, JPC = 19.8 Hz),
4
3
C, ppm: 29.51 d (CH3, JPC = 7.7 Hz), 33.53 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

1472
KAZANKOVA et al.
2
133.58 d ( CR, JPC = 10.9 Hz), 147.31 d ( CP,
E-IIIe, and Z-IIIe was obtained; IIe:IIIe ratio 88:12
(E/Z 83:17). Distillation gave 0.57 g (87%) of a mix-
ture of phosphines IIe and IIIe at the same ratio.
bp 135 140 C (2 mm).
1JPC = 24.5 Hz, 139.25 d (Ci, 1JPC = 9.2 Hz).
Reaction of diphenylphosphine with 1-heptyne
in the presence of Ni(acac)2. A mixture of 0.57 g
(0.56 ml, 3 mmol) of diphenylphosphine, 0.48 g
(0.65 ml, 5 mmol) of 1-heptyne (Id), and 20 mg
(1.3 mol %) of bis(acetylacetonato)nickel(II) in 2 ml
of anhydrous acetonitrile was heated for 1.5 h at
130 C in a sealed ampule. After appropriate treatment
(without distillation), 0.84 g (100%) of a mixture of
(1-pentylethenyl)diphenylphosphine (IId), (E)-(1-hep-
tenyl)diphenylphosphine (E-IIId), and (Z)-(1-hep-
tenyl)diphenylphosphine (Z-IIId) was obtained;
(1-Methoxymethylethenyl)diphenylphosphine
1
(IIe). 31P NMR spectrum:
8.76 ppm. H NMR
spectrum, , ppm: 3.25 s (3PH, OCH3), 3.88 d (2H,
3
2
OCH2, JPH = 1 Hz), 5.21 d.d (1H, cis-H, JHH = 1.5,
3JPH = 10.2 Hz), 5.91 d.d (1H, trans-H, JHH = 1.5,
2
3JPH = 22.2 Hz), 7.35 m (10H, Harom). 13C NMR
spectrum, C, ppm: 55.46 s (OCH3), 74.71 d (OCH2,
2
2JPC = 22.9 Hz), 124.83 d ( CH2, JPC < 1 Hz),
1
1
145.24 d ( CP, JPC = 16.8 Hz), 135.64 d (Ci, JPC
=
IId:IIId
ratio
55:45.
Vacuum
distillation
10.7 Hz).
gave 0.71 g (85%) of the same product mixture.
bp 135 140 C (2 mm). Found, %: C 80.00; H 8.14;
P 11.09. C19H23P. Calculated, %: C 80.85; H 8.15;
P 10.99.
(E)-(3-Methoxy-1-propenyl)diphenylphosphine
1
(E-IIIe). 31P NMR spectrum:
15.5 ppm. H NMR
P
spectrum, , ppm: 3.3 s (3H, OCH3), 3.95 d.d (2H,
3
4
Phosphine IId. 31P NMR spectrum:
3.57 ppm.
OCH2, JHH = 5.0, JHH = 1.5 Hz), 6.11 q.t (1H,
3
3
3
1H NMR spectrum, , ppm: 5.04 d.dP(1H, cis-H,
CH, JHH = 16.8, JHH = 5.0, JPH = 13.5 Hz),
3
4
2
2JHH = 1.4, JPH = 9.7 Hz), 5.53 d.d (1H, trans-H,
3
6.48 q.t (1H, PCH, JHH = 16.8, JHH = 1.6, JPH
=
,
9.3 Hz), 7.41 m (10H, Harom). 13C NMR spectrum,
2JHH = 1.4, 3JPH = 20.6 Hz), 7.40 m (10H, Harom).
ppm: 55.5 d (OCH3, JPC = 6.1 Hz), 73.55 d (OCHC2,
Phosphine E-IIId. 31P NMR spectrum:
2
P
JPC = 12.2 Hz), 132.40 d ( CHCH2, JPC = 19.9 Hz),
1
14.56 ppm. H NMR spectrum, , ppm: 0.79 t (3H,
RCH3), 1.35 m (6H, RCH2CH3), 2.13 d.t (2H,
CCH2R), 6.18 q.t (1H, CH, JHH = 8.5, JPH
18.4 Hz), 6.24 d.d (1H, PCH, JHH = 8.8, JPH
5.8 Hz), 7.43 m (10H, Harom). 13C NMR spectrum,
1
1
142.0 d ( CP, JPC = 27.5 Hz), 126.25 d (Ci, JPC
=
13.8 Hz).
3
3
=
=
Reaction of diphenylphosphine with 3-dimethyl-
aminopropyne. An ampule was purged with argon
and charged with 0.57 g (0.56 ml, 3 mmol) of di-
phenylphosphine, 0.33 g (0.43 ml, 4 mmol) of 3-di-
methylaminopropyne (If), and 20 mg (1.3 mol %) of
bis(acetylacetonato)nickel(II) in 2 ml of anhydrous
acetonitrile. The ampule was sealed and heated for
1.5 h at 130 C. The conversion was 10%, and the 31P
NMR spectrum of the mixture contained signals at
3
2
,
C
ppm: 13.75 s (RCH3), 22.18 s (RCH2CH3), 28.01
(RCH2CH2CH3) 34.76 d ( CCH2R, 3JPC = 13.44 Hz),
2
1
138.93 d ( CR, JPC = 9.2 Hz), 148.75 d (CP, JPC
=
33.5 Hz).
Phosphine Z-IIId. 31P NMR spectrum:
32.51 ppm. H NMR spectrum, , ppm: 0.79 t (3H,
RCH3), 1.21 m (6H, RCH2CH3), 2.45 d.t (2H,
P
1
6.34, 14.83, and 31.37 ppm, belonging to
P
3
3
(1-dimethylaminomethylethenyl)diphenylphosphine
(IIf), (E)-(3-dimethylamino-1-propenyl)diphenyl-
phosphine (E-IIIf), and (Z)-(3-dimethylamino-1-
propenyl)diphenylphosphine (Z-IIIf), respectively, at
a ratio of 1.5:2:1. The mixture was then heated for
10 h (35% conversion), and the product ratio changed
to 1.3:1.3:1; it no longer changed on subsequent
heating for 30 h. After 60 h at 130 C, the reaction was
complete, and the ratio IIf:IIIe was 43:57 (E/Z
50:50). After appropriate treatment (without distilla-
tion), 0.81 g (100%) of a mixture of phosphines IIf,
E-IIIf, and Z-IIIf was obtained. Distillation gave
0.68 g (83%) of the same mixture. bp 145 150 C
(2 mm). Found, %: P 12.4. C17H20NP. Calculated, %:
P 11.85.
CCH2R), 6.35 q.t (1H, CH, JHH = 11.2, JHH
=
7.5, JPH = 23.6 Hz), 6.13 d.q (1H, PCH, 3JHH = 11.2,
3
3JHH = 1.4, JPH = 2.2 Hz), 7.37 m (10H, Harom). 13C
2
NMR spectrum, C, ppm: 13.75 s (RCH3), 22.18 s
(RCH2CH3), 28.57 s (RCH2CH2CH3), 31.06 s
( CCH2CH2R), 30.82 d ( CCH2R, JPC = 21.4 Hz),
3
2
1
139.28 d ( CR, JPC = 9.1 Hz), 147.61 d (CP, JPC
=
24.4 Hz), 134.44 d (Ci, JPC = 9.2 Hz).
1
Reaction of diphenylphosphine with methyl
2-propynyl ether. An ampule was purged with argon
and charged with 0.57 g (0.56 ml, 3 mmol) of di-
phenylphosphine, 0.28 g (0.28 ml, 4 mmol) of methyl
2-propynyl ether (Ie), and 20 mg (1.3 mol %) of bis-
(acetylacetonato)nickel(II) in 2 ml of anhydrous aceto-
nitrile. The ampule was sealed and heated for 10 h
at 130 C. After appropriate treatment (without distilla-
tion), 0.77 g (100%) of a mixture of phosphines IIe,
Phosphine IIf. 31P NMR spectrum:
6.34 ppm.
1H NMR spectrum, , ppm: 2.18 s (6H, NCH3),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

SYNTHESIS OF VINYLPHOSPHINES BY HYDROPHOSPHINATION OF ALKYNES
1473
3
3.26 d (2H, NCH2, JPH = 6.4 Hz), 5.01 d.d (1H,
8. Burgess, K. and Ohlmeyer, M.J., Chem. Rev., 1991,
vol. 91, p. 1179.
9. Beletskaya, I.P. and Pelter, A., Tetrahedron, 1997,
vol. 53, p. 4957.
10. Han, L.-B. and Tanaka, M., J. Am. Chem. Soc.,
1996, vol. 118, p. 1571.
11. Zhao, Ch.-Q., Han, L.-B., Goto, M., and Tanaka, M.,
Angew. Chem., Int. Ed., 2001, vol. 40, p. 1929.
12. Han, L.-B., Choi, N., and Tanaka, M., Organo-
metallics, 1996, vol. 15, p. 3259.
13. Han, L.-B., Hua, R., and Tanaka, M., Angew. Chem.,
Int. Ed., 1998, vol. 37, p. 94.
14. Han, L.-B., Zhao, Ch.-Q., and Tanaka, M., J. Org.
Chem., 2001, vol. 66, p. 5929.
15. Douglass, M.R. and Marks, T.J., J. Am. Chem. Soc.,
2000, vol. 122, p. 1824.
16. Douglass, M.R., Stern, Ch.L., and Marks, T.J.,
2
3
cis-H, JHH < 1, JPH = 7.7 Hz), 5.77 d.d (1H, trans-
2
3
H, JHH < 1, JPH = 17.7 Hz), 7.35 m (10H, Harom).
13C NMR spectrum, C, ppm: 44.96 s (NCH3),
64.40 d (NCH2, JPC = 21.4 Hz), 130.32 d ( CCH2N),
2JPC = 12.2 Hz), 143.95 d ( CP, JPC = 27.5 Hz),
1
137.15 d (Ci, JPC = 10.7 Hz).
1
Phosphine E-IIIf. 31P NMR spectrum:
P
1
14.83 ppm. H NMR spectrum, , ppm: 2.17 s (6H,
NCH3), 2.99 d (2H, NCH2, JPH = 6.0 Hz), 6.16 m
(1H, CH), 6.43 m (1H, PCH), 7.21 m (10H, Harom).
13C NMR spectrum, C, ppm: 44.98 s (NCH3),
3
63.12 d (NCH2, JPC = 12.3 Hz), 129.85 d ( CHCH2N,
2JPC = 10.0 Hz), 146.32 d ( CHP, JPC = 16.8 Hz),
1
137.95 d (Ci, JPC = 10.7 Hz).
1
Phosphine Z-IIIf. 31P NMR spectrum:
P
1
31.73 ppm. H NMR spectrum, , ppm: 2.16 s (6H,
NCH3), 2.93 d (2H, NCH2, JPH = 6.6 Hz), 6.16 m
J. Am. Chem. Soc., 2001, vol. 123, p. 10221.
3
17. Douglass, M.R., Ogasanara, M., Hang, S.,
Metz, M.R., and Marks, T.J., Organometallics, 2002,
vol. 21, p. 283.
(1H, CHCH2N), 6.43 m (1H, CHP), 7.21 m (10H,
Harom). 13C NMR spectrum, C, ppm: 45.0 s (NCH3),
58.50 d (NCH2, JPC = 21.4 Hz), 130.32 d ( CHCH2N,
18. Weber, L., Kaminski, O., Boese, R., and Blaser, D.,
2JPC = 12.2 Hz), 143.95 d ( CHP, JPC = 21.3 Hz),
1
Organometallics, 1995, vol 14, p. 820.
138.6 d (Ci, JPC = 9.1 Hz).
1
19. Soulivong, D., Wieser, C., Marcellin, M., Matt, D.,
Harriman, A., and Toupet, L., J. Chem. Soc., Dalton
Trans., 1997, p. 2257.
20. Fruzuk, M.D., Gal, X., and Rettig, S.G., Can.
J. Chem., 1985, vol. 73, p. 1175.
21. Gilheany, D.C. and Mitchell, S.M., The Chemistry
of Organophosphorus Compounds, Hartley, F.R.,
Ed., New York: Wiley, 1990, vol. 1, chap. 7,
pp. 151 190.
22. Trost, B.M., Science, 1991, vol. 254, p. 1471.
23. Sheldon, R.A., CHEMTECH, 1994, vol. 24, p. 38.
Reaction of diphenylphosphine with diphenyl-
acetylene. An ampule was purged with argon and
charged with 0.28 g (0.28 ml, 1.5 mmol) of diphenyl-
phosphine, 0.27 g (1.5 mol) of diphenylacetylene (Ig),
and 10 mg (1 mol %) of bis(acetylacetonato)nickel(II)
in 2 ml of dry benzene. The ampule was sealed and
heated for 10 h at 80 C. As a result, 0.56 g (100%) of
(E)-diphenyl(1,2-diphenylethenyl)phosphine (IIIg)
was isolated. 31P NMR spectrum:
mp 114 115 C [45].
10.02 ppm.
P
24. Trost, B.M., Angew. Chem., Int. Ed., 1995, vol. 34,
p. 259.
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