Hydrophosphorylation of terminal alkynes catalyzed by palladium

Article abstract of DOI:10.1023/B:RUJO.0000003155.15312.f4

A series of new 1-aryl-, 1-heteroaryl-, and 1-alkylethenylphosphonates was prepared by hydrophosphorylation of terminal acetylenes catalyzed by palladium. A stable in air complex Pd₂(dba)₃·CHCl₃ was applied as catalyst. The reaction mechanism is discussed.

Full text of DOI:10.1023/B:RUJO.0000003155.15312.f4

Russian Journal of Organic Chemistry, Vol. 39, No. 6, 2003, pp. 797 807 . Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 6, 2003,
pp. 847 856.
Original Russian Text Copyright
2003 by Gulykina, Dolgina, Bondarenko, Beletskaya.
Hydrophosphorylation of Terminal Alkynes
Catalyzed by Palladium
N. S. Gulykina, T. M. Dolgina, G. N. Bondarenko, and I. P. Beletskaya
Moscow State University, Moscow, 119899 Russia
Received September 27, 2002
Abstract A series of new 1-aryl-, 1-heteroaryl-, and 1-alkylethenylphosphonates was prepared by hydro-
phosphorylation of terminal acetylenes catalyzed by palladium. A stable in air complex Pd (dba) CHCl
2
3
3
was applied as catalyst. The reaction mechanism is discussed.
,
-Unsaturated phosphonates are of significant
of palladium complexes dimethyl- and diethylphos-
phoric acids added to aromatic and aliphatic terminal
acetylenes [35]. In contrast to Pudovik reaction
proceeding along ionic or radical mechanism [36] the
hydrophosphorylation of terminal acetylenes catalyz-
ed by palladium occurrs in keeping with Markowni-
koff rule affording prevailingly -substituted ethenyl-
phosphonates. At the use as catalyst of cis-
PdMe (PPh Me) the regioselectivity of the process
interest for they have found wide application both in
industry and medical chemistry [1, 2]. They underlie
preparation, e.g., of incombustible and self-ex-
tinguishing polymers [3], antibiotics [4], cersatile
biologically active compounds [5]. We showed recent-
ly that 1-arylethenylphosphonic acids and their esters
are convenient intermediates for preparation of
1
-arylethylphosphonates which exhibit immunosup-
2
2
2
pressor properties of central type action [6, 7]. A lot
of preparation procedures for , -unsaturated phos-
phonates are published but they mostly concern the
synthesis of vinylphosphonates with a stong electron-
withdrawing group in the -position [8]. Among the
synthetic methods for ethenylphosphonates with an
aryl or alkyl substituent in the -position may be
cited dehydration of saturated -hydroxyphosphonic
acids [3, 9 11] or their esters [12 17], catalyzed by
Cu(I)- [18, 19] or Ni(II) [20] Arbuzov reaction of
trialkylphosphites with vinyl halides, catalyzed by
Pd(0) Michaelis Becker reaction of phosphorous acid
dialkyl esters with vinyl bromides [21, 22] or with
vinyl triflates [23], addition of trialkyl phosphites
attains 90% [35]. In this paper we report on continua-
tion of the study of the new promising synthetic
method for -aryl- and -alkyl-ethenylphosphonates
in order to find a convenient catalytic system for pre-
parative procedures. A range of substrates was also
extended to include in particular heteroarylacetylenes
and arylacetylenes containing in the ring strong
electron-withdrawing substituents. The preliminary
results of our studies were published before [37].
In the selection of an optimal catalytic system
phenylacetylene (Ia) was used as model substrate.
As catalyst was applied stable in air complex
Pd (dba) CHCl in the presence of mono- or
2
3
3
bidentate phosphine ligands, or Pd(PPh ) . A mixture
3
4
[
24] or phosphorous acid dialkyl esters [25] to
nitroolefins followed by elimination of nitrous acid
26, 27], addition of potassium diethylphosphite to
of 1.1 mmol of phenylacetylene, 1 mmol of diethyl-
phosphorous acid, palladium catalyst (3 mol% of Pd),
and phosphine in 1 ml of anhydrous THF was heated
to 67 C in a sealed ampule. The reaction progress
-
[
phenyl- -styryl sulfone with subsequent elimination
of benzenesulfinic acid [28], thermal decomposition
of alkyl (1-diethoxyphosphoryl-1-phenylalkyl) sulf-
oxides [29], olefination of acylphosphonates with
methylenetriphenylphosphorane by Wittig reaction
3
1
was monitored by
P
NMR measuring the
HP(O)(OEt) conversion by decrease in the signal at
2
6.9 ppm and the formation of two regioisomers of
[
30, 31], photolysis of dimethyl 1-diazo-2-phenyl-
ethylphosphonate [32], addition of trimethylsilyldi-
azomethane to phosphorylated aryl- and vinylketenes
followed by decarbonylation [33], and the reaction of
Ivanov reagent prepared from diethyl 1-benzylphos-
phonate with formaldehyde [34]. In 1996 L. -B. Han
and T. M. Tanaka demonstrated that in the presence
1
070-4280/03/3906-0797$25.00 2003 MAIK Nauka/Interperiodica

7
98
GULYKINA et al.
the reaction product IIa and IIIa by increase in the
signals at 16.5 and 18.8 ppm respectively [38].
CH CN (used as solvent), and also Ni(acac) that
3 2
catalyzed diphenylphosphine addition to phenylacetyl-
ene [39].
The results obtained listed in Table 1 show that at
the use as catalyst of Pd(PPh ) the reaction is
The attempt to replace diethyl phosphite as phos-
phorylating agent by HP(O)(OSiMe ) failed likely by
3
4
completed in 9 h and affords products IIa) and IIIa
in 90 and 10% yield respectively (run no. 1). The
same selectivity of reaction was observed at the use
of Pd (dba) CHCl in the presence of triphenyl-
3
2
sterical reasons. The successful modification in this
case promised easy conversion under very mild condi-
tions of the trimethylsilyl esters obtained into the
corresponding , -unsaturated phosphonic acids by
mere methanolysis. To our regret, in reaction of
phenylacetylene with HP(O)(OSiMe ) in the pres-
2
3
3
phosphine (runs nos. 2 and 3); therewith the catalytic
activity of Pd (dba) CHCl depended on the amount
2
3
3
of the added ligand. In the presence of 1.5 mol% of
3
2
Pd (dba) CHCl and 12 mol% of PPh (P/Pd = 4)
ence of Pd(PPh ) under standard conditions after
2
3
3
3
3 4
in 9 h the overall yield of products IIa and IIIa was
7% (run no. 2), i.e. the efficiency of this system was
comparable with that of Pd(PPh ) . The reduction of
triphenylphosphine amount to 6 mol% (P/Pd = 2)
resulted in decrease of the overall product yield
within the same time to 76% (run no. 3). The same
trend was observed at the use of a bidentate ligand
9.5 h we observed formation of no more than 26% of
8
the product [
0.8 ppm (THF)]; further heating
resulted in separation of a colorles flocculent pre-
cipitate, and the reaction stopped.
3
4
We involved into the hydrophosphorylation reac-
tion aromatic and aliphatic acetylenes Ia i.
dppp: in the presence of 1.5 mol% of Pd (dba)3
2
CHCl and 6 mol% of dppp (P/Pd = 4) the overall
3
yield of products IIa and IIIa in 9 h was 79% (run
no. 4) and considerably decreased (52% in 35 h) at
reduction by half of the ligand amount (P/Pd = 2)
(
run no. 5); therewith the hydrophosphorylation was
stereospecifical: Regioisomer IIIa formed only in
trace amount. The reaction is highly regiospecific at
the use of dppe, but the process is very slow (runs
nos. 6 and 7).
Pd(0) = Pd(PPh ) (3 mol%) or Pd (dba) CHCl
3
3
4
2
3
(
1.5 mol%) and PPh (12 mol%); R = Ph (a),
3
Totally inactive as catalysts were the following
4-MeOC6H4 (b), 6-MeO-2-Nf (c), ferrocenyl (d),
3-pyridyl (e), 3-quinolyl (f), 6-quinolyl (g), Bu
(h24)), t-Bu (i).
complexes: (PhCN) PdCl , p-NO C H PdI(PPh ) ,
2
2
2
6
4
3 2
Pd (dba) CHCl in the presence of AsPh3 or
2
3
3
a
Table 1. Hydrophosphorylation of phenylacetylene (Ia)
Run no.
Catalyst
Time, h
Overall products yield
(IIa and IIIa), % ( P NMR)
Selectivity (IIa)/(IIIa)
3
1
31
(
amount)
( P NMR)
1
2
3
4
5
6
7
Pd(PPh3)4
6
9
6
9
6
9
9
91
100
71
87
60
90/10
90/10
89/11
>98/2
>98/2
(
3 mol%)
Pd2(dba)3 CHCl /PPh
1.5 mol%)/(12 mol%)
Pd (dba)3 CHCl /PPh
1.5 mol%)/(6 mol%)
3
3
(
2
3
3
(
76
79
Pd2 dba) CHCl /dppe
(
3
3
(
1.5 mol%)/(6 mol%)
Pd (dba) CHCl /dppe
18
3
9
37
52
6
2
3
3
(
1.5 mol%)/(3 mol%)
Pd (dba) CHCl /dppe
2
3
3
(
1.5 mol%)/(6 mol%)
Pd (dba) CHCl /dppe
15
35
41
56
95/5
2
3
3
(
1.5 mol%)/(3 mol%)
a
1
.1 mmol of PhC CH, 1 mmol of HP(O)(OEt) , 1 ml of THF, 67 C.
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

HYDROPHOSPHORYLATION OF TERMINAL ALKYNES
799
Table 2. Hydrophosphorylation of terminal alkynes RC CH Ia i with diethyl phosphite catalyzed by palladium
a
Compd.
no.
R
Catalyst
Reaction HP(O)(OEt) conversion, Isomer ratio (II)/(III) Preparative yield
2
3
1
31
time, h
% ( P NMR)
( P NMR)
of II, %
Ia
Ib
Ph
A
B
9
10
100
84
91
91
78
88
88
89
83
77
89
89
44
73
100
100
79
97
90/10
94/6
75
4-MeOC H
6
4
1
2
4
9
65
Ic
6-MeO-2-Nf
B
17
2
3
8
7
93/7
91/9
80/20
73
59
Id
Ie
If
Ferrocenyl
3-Pyridyl
3-Quinolyl
B
B
B
39
26
30
68
114
80/20
58
Ig
6-Quinolyl
B
45
1
17
12
27
73
82/18
100/0
100/0
48
82
76
Ih
Ih
Ii
Bu
Bu
t-Bu
A
B
C
120
34/66b
a
A is Pd(PPh ) (3 mol%); B is Pd (dba)3 CHCl (1.5 mol%), PPh (12 mol%); C is Pd(PPh ) (10 mol%).
According to H NMR.
3
4
2
3
3
3 4
b
1
1
31
Table 3. H and P NMR spectra of -substituted diethyl ethenylphosphonates CH =C(R)P(O)(OEt) IIa i
2
2
1
31
R
H NMR spectrum (CDCl ), , ppm (J, Hz)
P NMR
3
spectrum,
trans-
PC=CH, PC=CH,
cis-
OCH CH
, ppm
(solvent)
2
3
R
d.d (1H) d.d (1H)
CH ,m
CH , t
2
3
(
4H)
(6H)
IIa
Ph
6.16
6.34
7.34 m (3H, Harom), 7.53 m (2H, Harom)
4.11 1.29
16.5 (THF),
2
2
3
(
JHH 1.4, ( J 1.4,
JHP 45.7) JHP 22.2)
6.06 6.20
JHH 1.3, ( J 1.3, JAB 8.8), 7.44 d.d (2H, C H+C H,
HH
3 3 4
JHP 45.8) JHP 21.6) J 8.8, 3J 1.2)
( J 7.2) 17.0 (MeOH),
HH
HH
3
3
16.8 (CDCl3)
3
5
IIb 4-MeOC H
3.76 s(3H, OCH ), 6.83 d(2H, C H+C H, 4.05
1.24
16.9 (THF),
( J 7.0) 17.8 (MeOH)
6
4
3
2
2
3
2
6
3
(
HH
3
AB
HP
5
4
IIc 6-MeO-2-
6.27
6.38
3.93 s(3H, OCH ), 7.12 d(1H, C H, 4J 4.13
1.30
16.7 (THF),
( J 7.0) 17.3 (MeOH)
3
HH
2
2
7
3
4
3
(
JHH 1.4, ( J 1.4, 2.4), 7.16 d.d (1H, C H, J 8.8, 4J 2.4),
JHP 45.8) J 21.9) 7.62 m(1H, C H, J 8.8), 7.72 d(1H, C H,
HH
HH
HH
HH
3
3
3
3
4
HP
HH
3
8
3
JHH 8.8), 7.75 d(1H, C H, J 8.8),
HH
1
7
.98 br.s (1H, C H)
IId
IIe
Fc
6.08 br.
3
6.05 br. 4.02 br. (5H, C H ), 4.16 br. (2H, Harom), 4.02 br. 1.26 br. 16.8 (THF),
5
5
(
(
JHP 43.9)
JHP 21.1)
6.21
4.49 br. (2H, H arom)
17.2 (MeOH),
16.1 (Et2O)
15.6 (THF),
3
5
3
3
3-Pyridyl
6.42
7.30 d.d (1H, C H, J 8.0, J 4.8), 7.89 m 4.13
1.31
3
HH
HH
4
3
6
(
1H, C H, J 8.0), 8.59 br.d (1H, C H,
( J 7.0) 15.45 (CDCl3)
HH
HH
3
2
JHH 4.8), 8.72 br.s (1H, C H)
2
2
(
JHH 1.4, ( J 1.4,
HH
3
3
JHP 45.2) J 21.8)
HP
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

8
00
GULYKINA et al.
Table 3. Contd.
1
31
R
H NMR spectrum (CDCl ), , ppm (J, Hz)
P NMR
spectrum,
, ppm
3
trans-
cis-
OCH CH
2 3
PC=CH, PC=CH,
d.d (1H) d.d (1H)
R
(solvent)
CH ,m
CH , t
2
3
(
4H)
(6H)
3
3
IIf 3-Quinolyl
IIg 6-Quinolyl
6.35
6.51
7.58 d.d.d (1H, C6H, J 8.0, J 7.0,
4.17
1.32
15.7 (THF),
HH
HH
2
2
4
7
3
3
(
JHH 1.2, ( J 1.2, 4JHH 1.2), 7.74 d.d.d (1H, C H, J 8.4,
JHP 45.2) JHP 22.0) J 7.0, 4J 1.2), 7.86 br.d (1H, C H,
( J 7.0) 15.6 (CDCl3)
HH
HH
HH
3
3
3
4
5
HH
HH
3
3
JHH 8.0), 8.11 br.d (1H, C8H, J 8.4),
HH
2
8
.39 s(1H, C4H), 9.03 s (1H, C H)
3 3 3
6.32
6.46
7.43 d.d (1H, J 8.4, J 4.4, C H), 4.16
1.31 16.0 (THF),
HH
HH
2
2
7
3
4
3
(
JHH 1.4, ( J 1.4, 7.88 d.d.d (1H, C H, J 8.8, 4J 2.0,
( J 7.0) 16.3 (CDCl3)
HH
HH
HH
HH
3
3
4
5
JHP 45.2) J 22.0) 3J
1.0), 8.06 m (1H, C H), 8.11 d(1H,
C H, J 8.8), 8.20 d.d (1H, C H, J 8.4,
JHH 1.6), 8.93 d.d (1H, C H, J 4.4,
HP
HP
8
3
4 3
HH
HH
4
4
2
3
4
4
HH
JHH 1.6)
a
a
3
IIh
Bu
5.72
5.99
0.88 t (3H, CH3, J 7.4), 1.32 m (2H,
4.04
3.98
1.29
18.7 (THF),
( J 7.0) 21.9 (MeOH)
HH
2
4
3
3
(
JHH 1.4,
J
1.6) C H ), 1.47 quintet (2H, C2H2, J 7.5),
3 2 HH
3 4
HH
HH
3
2
JHP 49.0, ( J 1.4, 2.20 m (2H, C1H2, J 7.5, 4J 1.6,
HH
HH
HH
3
3
JHP 22.9)
JHP 13.3)
1.15 s(9H, CH3)
b
b
IIi
t-Bu
5.77
5.95
1.24
3
18.9 (THF)
3
(
(
JHP 47.9)
JHP 23.3)
( J 7.2)
HH
3
a
b
Multiplet.
Doublet.
The results obtained are compiled in Table 2. The
In the IR spectra of compounds IIa c, h a char-
acteristic group of strong bands is observed cor-
responding to the vibrations of the diethoxyphos-
phoryl fragments [41]: a broad band of (P=O) in
hydrophosphorylation of aryl- and heteroarylacetyl-
enes Ib g was carried out using as catalyst the stable
in air Pd (dba) CHCl in the presence of triphenyl-
2
3
3
1
phosphine. We did not attain a complete conversion
of the diethylphosphite: The reaction stopped when
the region 1234 1255 cm , usually two bands in the
region 1024 1055 cm 1 from O C vibrations, and a
1
conversion of HP(O)(OEt) reached 73 91%. As in
band of C C vibrations at 962 968 cm .
2
the case of phenylacetylene (Ia) the main reaction
products were diethyl 1-arylethenylphosphonates
IIa g which were isolated in 49 75% yield. Their
structure and composition were confirmed by NMR
and IR spectra and by elemental analyses.
The formation of isomeric trans-diethyl-2-aryl-
ethenylphosphonates IIIa g was registered by
spectral methods. In the P NMR spectra of the
31
reaction mixtures the minor isomers IIIa g are ob-
served in the region 17.8 19.8 ppm, whereas the
signals of the major isomers IIa g are displaced
upfield by 2.2 2.9 ppm (in all likelihood due to the
anisotrotic effect of the aromatic ring) and appear in
the region 15.5 16.9 ppm. For acetylenes Ia d the
fraction of minor isomers amounted to 6 10% and
increased up to 18-20% for acetylenes Ie g contain-
ing electron-withdrawing heteroaromatic substituents.
In the 1H NMR spectra of compounds IIa g
(
Table 3) vinyl protons signals appear as doublets of
2
doublets with the geminal coupling constant J 1.2
HH
1
.4 Hz and characteristic coupling constants with
3
3
phosphorus nucleus: JHP cis 21.1 22.2 and J
trans.
HP
In the 13C NMR spectra of compounds IIa c, h
the characteristic doublet of the carbon directly linked
Compounds IIIe g were isolated and characterized
1
31
to the phosphorus appears in the region 138.7
by H and P NMR spectra (Table 4). The vinyl
protons appear in the spectra as doublet of doublets;
their assignment was done basing on the coupling
1
1
1
39.6 ppm; the coupling constant J amounts to
70.8 178.2 Hz.
CP
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

HYDROPHOSPHORYLATION OF TERMINAL ALKYNES
801
1
31
a
Table 4. H and P NMR spectra of -substituted diethyl ethenylphosphonates trans-RCH=CHP(O)(OEt) IIIe g, i
2
1
31
H NMR spectrum (CDCl ), , ppm (J, Hz)
P NMR
3
spectrum,
, ppm
R
trans-
cis-
OCH CH
2 3
C=CHP, HC=CP,
d.d (1H) d.d (1H)
R
(solvent)
CH ,m
CH , t
2
3
(
4H)
(6H)
3
3
IIIe 3-Pyridyl
IIIf 3-Quinolyl
6.37
7.50
7.34 d.d (1H, C5H, J 7.8, J 4.8),
4.16
1.37
HH
HH
3
3
3
4
3
(
JHH 17.6, ( J 17.6, 7.82 d.t (1H, C4H, J 7.8, 4J 1.8),
( J 7.2) 17.8 (THF),
HH
HH
HH
HH
2
3
3
4
JHP 16.8) J 22.5) 8.61 d.d (1H, C6H, J 4.8, 4J 1.8),
17.6 (CDCl3)
HP
HH
HH
2
8
.74 br. (1H, C H)
3
3
6.52
7.67
7.59 d.d.d (1H, C6H, J 8.0, J 7.2, 4.19
JHH 17.6, ( J 17.6 4JHH 0.6), 7.76 d.d.d (1H, C H, J 8.8, ( J 7.2, ( J 7.2) 17.8 (CDCl3)
HH HH HH HH
3 3 4 5 3
JHP 16.8) J 22.8) J 7.2, 4J 1.4), 7.86 br.d (1H, C H, JHP 8.0)
1.39
3
18.0 (THF),
HH
HH
3
3
4
7
3
3
(
2
HP
HH
HH
3
3
JHH 8.0), 8.12 br.d (1H, C8H, J 8.8),
HH
4
2
8
.22 s (1H, C H), 9.09 br. (1H, C H)
3 3 3
IIIg 6-Quinolyl
6.42
7.68
7.45 d.d (1H, C H, J 8.0, J 4.0),
4.18
3.98
1.38
3
18.5 (THF),
HH
HH
3
3
5
7
3
(
JHH 17.2, ( J 17.2 7.89 s(1H, C H), 7.90 d(1H, C H, J 8.4),
JHP 17.2) J 22.4) 8.12 d(1H, C H, J 8.4), 8.19 d(1H,
( J 7.0) 18.6 (CDCl3)
HH
HH
HH
2
3
8
3
HP
HH
4
3
2
3
C H, J 8.0), 8.94 d.d (1H, C H, J 4.0,
HH
HH
4
4
JHH 2.0)
IIIi
t-Bu
5.46
6.69
0.98 s (9H, CH3)
1.24
3
19.1 (THF)
3
3
(
JHH 17.5, ( J 17.5,
( J 7.2)
HH
HH
2
3
JHP 20.0) JHP 22.9)
P NMR spectrum (THF), , ppm: 18.8 (IIIa), 19.8 (IIIb), 19.4 (IIIc), 19.7 (IIId).
a
31
constants with the phosphorus nucleus [40]. The ob-
ence between the corresponding chemical shifts in
P NMR spectra (Tables 3 and 4): The respective
3
31
served constant J equals to 22.4 22.8 Hz and is
HP
3
close to the J cis value in compounds IIa g. trans-
chemical shifts differ only by 0.2 ppm. This fact sup-
ports the assumption on the aninisotropic effect of
aromatic rings on the phosphorus resonance in the
pairs (IIIa g)/(IIa g). The vinyl protons signals
belonging to isomer IIi (Table 3) appear as doublets
HP
Configuration was unambiguously proved by the
3
value of the vicinal coupling constant J
17.2
HH
1
7.6 Hz [42].
Aliphatic 1-hexyne Ih cleanly reacted with diethyl-
3
with characteristic coupling constants JHP. No
phosphorous acid: 100% conversion of HP(O)(OEt)2
was reached at the use as catalyst both Pd(PPh ) and
coupling of geminal protons revealed in compounds
IIa h was observed in the spectrum of compound IIi
apparently due to decrease in the HCH bond angle
caused by the bulky tert-butyl substituent [40].
3
4
Pd (dba) CHCl in the presence of PPh . The reac-
3
2
3
3
tion in both cases was regiospecific and afforded
O,O-diethyl)-1-butylethenylphosphonate IIh as the
(
It was noted before [40], that the presence of
electron-withdrawing substituents in -substituted
ethenylphosphonates reduced the value of coupling
sole reaction product isolated in 82 and 76% yield
respectively. The structure and composition of com-
pound IIh were confirmed by spectral data and ele-
mental analysis (see Table 3 and EXPERIMENTAL).
2
1
constant J . Actually, in the H NMR spectrum of
HP
2
isomer IIIi (Table 4) the constant J amounts to
HP
With the sterically overloaded tert-butylacetylene
Ii the reaction rate was significantly slower, and the
amount of Pd(PPh3)4 required was increased to
2
0.0 Hz against 16.8 17.2 Hz for ethenylphos-
phonates IIIe g which contain a heteroaromatic
substituent in the -position.
1
0 mol%. The reaction afforded predominantly IIIi
In contrast to hydrophosphorylation of arylacetyl-
enes Ib, c containing a -donor group MeO in the
ring, the reaction of aliphatic 3-methoxy-1-propyne
with diethyl phosphite proceeds very slowly. We
isomer.
The interesting feature in the spectral character-
istics of isomers IIi and IIIi consists in small differ-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

8
02
GULYKINA et al.
obtained less than 10% of reaction product [ 16.6
ppm (THF)] after heating the reaction mixture for
by palladium were isolated as side products the cor-
responding 2-arylethynylphosphonates. This fact is a
serious argument supporting the insertion mechanism
into the Pd P bond for the only possibility of 2-aryl-
3
0 h under standard conditions in the presence of
Pd(PPh ) .
3
4
ethynylphosphonate formation is the
elimination from the corresponding intermediate.
-hydride
The experimental material collected by now is not
sufficient for formulation of a detailed reaction
mechanism. The key stages of the reaction are
evidently oxidative addition of dialkylphosphorous
acid to the zero-valent palladium, insertion of acetyl-
ene, and reductive elimination of the product. The
oxidative addition of a P-H bond to complexes
Pd(PCy ) , Pt(PEt ) and RhCl(PPh ) was established
in [35, 43, 44]. The question is still open whether
acetylene inserts into Pd-H or Pd-P bond. In hydro-
phosphorylation of olefins catalyzed by palladium the
participation of the P H bond was proved [43]. It was
established [44] that hydrophosphorylation of
terminal acetylenes catalyzed by rhodium occurred
with alkyne insertion into the Rh H bond. However
in this case the main reaction product was a -sub-
stituted ethenylphosphonate (regioselectivity over
Regretfully in neither of reaction we studied we
detected formation of RC CP(O)(OEt) likely because
2
of using milder conditions in carrying out the
processes. Nonetheless, the assumed scheme is in
agreement with the found in our study deceleration
of reaction at increased bulk of a substituent not only
in the initial acetylene but also at the phosphorus
atom [at the use of HP(O)(OSiMe ) ].
3
2
3 3
3 3
3
2
In the framework of this scheme the introduction
into the molecule of acetylene RC CH of electron-
withdrawing substituents causing formation of a
partial positive charge on the -carbon should
decrease both the reaction rate and selectivity.
This assumption was confirmed at the use of
heteroarylacetylenes Ie g.
9
8%) whose formation was expected by steric reasons.
The possibility of the alternative path, insertion
EXPERIMENTAL
into the metal phosphorus bond was demonstrated on
hydrophosphination of acrylonitrile catalyzed by
platinum [45, 46]. This notion was suggested in dis-
cussing the mechanism of diphenylphosphine oxide
addition to acetylenes in the presence of diphenyl-
phosphinic acid catalyzed by palladium [47]. The
possibility of acetylene insertion into the Pd P bond
is directly proved by results obtained in [48] on addi-
tion of Ph P PPh to terminal acetylenes catalyzed by
1H and 13C NMR spectra were registered on
spectrometer Varian VXR-400 at operating frequ-
encies 400 and 101 MHz respectively. 31P NMR
spectra were recorded on spectrometers Varian FT-
8
3
0A or Brucker 80-WP at operating frequency
2.4 MHz. Chemical shifts are given in the -scale
relative to TMS or 85% H PO . In some cases the
3
4
chemical shifts were measured from the signals of
2
2
residual protons or the carbon atom of CDCl (7.25
Pd(PPh ) .
3
3
4
and 77.0 ppm respectively). IR spectra were measur-
ed on a Fourier spectrometer IKAR (ZAO Mikro-
It was reported in [49] that at bis-hydrophosphor-
ylation of arylacetylenes in boiling toluene catalyzed
1
tekh , Russia), resolution 1 cm , number of scans 30.
THF was boiled and distilled in succession from
KOH and Na and then stored on sodium benzo-
phenone ketyl. Before use it was degassed and distil-
led through a vacuum manifold into a cooled reaction
ampule. The preparative column chromatography was
carried out using silica gel L40/100 or Silpearl
(
Chemapol) and aluminum oxide (neutral, Brockmann
activity II grade, Reanal).
3
-Ethynylquinoline (If). To a solution of 1.0 ml
7.4 mmol) of 3-bromoquinoline, 107mg (0.15mmol)
of Pd(PPh3)2Cl2, 59 mg (0.31 mmol) of CuI, 1.6 ml
11.5 mmol) of Et N (freshly distilled from NaOH) in
(
(
3
3
.8 ml of anhydrous THF while stirring under atmo-
sphere of dry argon was slowly added dropwise a
solution of 1.3 ml (9.2 mmol) of trimethylsilylacetyl-
ene in 0.7 ml of THF. The reaction mixture gradually
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

HYDROPHOSPHORYLATION OF TERMINAL ALKYNES
803
turned dark, and a voluminous precipitate separated.
After the stirring at room temperature was continued
for 24 h the reaction mixture was evaporated in a
vacuum, the residue was diluted with water and ex-
NaCl, and dried on MgSO . The solvent was distilled
off in a vacuum, and the residue was submitted to
4
chromatography on silica gel using as eluent Et O.
2
We obtained 0.332 g (91%) of compound Ig. Rf 0.7
1
tracted with Et O. The ether extracts were washed
(Silufol UV-254, Et O). H NMR spectrum (CDCl ),
2
2
3
3
with saturated water solution of NaCl, and dried on
, ppm: 3.20 s (1H, C CH), 7.42 d.d (1H, C H,
3
3
7
3
MgSO . The solvent was distilled off in a vacuum,
JHH 48.4, J
4.4 Hz), 7.76 d.d (1H, C H, J
4
HH HH
5
4
and the residue was submitted to chromatography on
silica gel using as eluent a mixture of petroleum ether
and dichloromethane gradually increasing the eluent
polarity. We obtained 1.59 g (96%) of trimethylsilyl-
ethynylquinoline. Rf 0.25 (Silufol UV 254, CH Cl ).
8.8, J 2.0 Hz), 7.99 d (1H, C H, J 2.0 Hz),
HH HH
8.05 d (1H, C H, J 8.8 Hz), 8.11 d.d (1H, C H,
8
3
4
HH
3
4
2
3
JHH 48.4, J
1.6 Hz), 8.92 d.d (1H, C H, J
HH
HH
4.4, J
1.6 Hz).
HH
2
2
1
4-Methoxyphenylacetylene (Ib) [50], 6-methoxy-
2-ethynylnaphthalene (Ic) [51], ethynylferrocene (Id)
[52], 3-ethynylpyridine (Ie) [53], tert-butylacetylene
(Ii) [54], trimethylsilylacetylene [55], Pd(PPh ) [56],
H NMR spectrum (CDCl3), , ppm: 0.31 s (9H,
CH ), 7.56 m (1H, C H), 7.72 m (1H, C H), 7.77 d
6
7
3
5
3
8
3
(
1H, C H, J
8.4 Hz), 8.09 d (1H, C H, J
HH HH
2
3
4
8
.4 Hz), 8.26 s (1H, C4H), 8.92 s (1H, C H).
and Pd (dba) CHCl [57] were synthesized by
2
3
3
To a solution of 1.59 g (7.1 mmol) of 3-trimethyl-
silylethynylquinoline in 5 ml of anhydrous MeOH
under atmosphere of dry argon was added 1.93 g
published procedures. The other reagents that were
commercially available were purified before use by
distillation in a flow of dry argon or by recrystalliz-
(
14.0 mmol) of K CO . After stirring at room tempera- ation.
2 3
ture for 2 h the reaction mixture was filtered and
evaporated on a rotary evaporator. The residue was
diluted with ether and submitted to chromatography
on Al O . We obtained 0.71 g (66%) of compound If.
(
O,O-Diethyl)-1-phenylethenylphosphonate (IIa).
A mixture of 1.14 g (11.2 mmol) of phenylacetylene
Ia), 1.38 g (10.0 mmol) of diethyl phosphite, and
0.34 g (0.3 mmol) of Pd(PPh ) in 10 ml of an-
(
2
3
1
3
4
H NMR spectrum (CDCl ), , ppm: 3.30 s (1H,
3
6
5
hydrous THF was heated in a sealed evacuated
ampule at 67 C for 15 h. The ampule was opened, the
solvent was removed on a rotary evaporator, the
residue was distilled in a vacuum in an argon flow.
We obtained 1.80 g (75%) of phosphonate IIa as a
yellowish viscous fluid. bp 112 115 C (10 1 mm Hg)
C CH), 7.51 m (1H, C H), 7.69 m (2H, C H+
C H), 8.08 d (1H, C8H, J 8.0 Hz), 8.21 s (1H,
7
3
HH
4
2
C H), 8.93 s (1H, C H).
6
-Ethynylquinoline (Ig) was prepared in a way
similar to the synthesis of compound If. The 6-tri-
methylsilylethynylquinoline was obtained in 56%
yield from 1.043 g (5.01 mmol) of 6-bromoquinoline,
1
[20, 24, 26, 28]. IR spectrum (from film), , cm :
2981, 2906, 1494, 1444, 1392, 1261, 1234, 1162,
7
0
0
1 mg (0.10 mmol) of Pd(PPh ) Cl , 39 mg (
1099, 1051, 1024, 962, 846, 781, 713. 13C NMR
3
2
2
3
.20 mmol) of CuI, 1.05 ml (7.5 mmol) Et N, and
spectrum (CDCl3), , ppm: 16.1 d (CH , JCP
3
3
2
.85 ml (6.0 mmol) of trimethylsilylacetylene in 3 ml
6.3 Hz), 62.1 d (OCH , JCP 5.5 Hz), 127.3 d
2
2
6
3
4
of anhydrous THF. Reaction time 24 h. The product
was submitted to chromatography on silica gel using
as eluent a mixture of petroleum ether and ethyl
acetate gradually increasing the eluent polarity.
(C + C , JCP 5.1 Hz), 128.1 s (C ), 128.3 s
3
5
2
2
1
(C + C ), 131.6 d (C , J 8.1 Hz), 136.6 d (C ,
CP
2
1
JCP 12.1 Hz), 139.6 d (CP, J 174.2 Hz).
CP
(
O, O-Diethyl)-1-(4-methoxyphenyl)ethenyl-
Rf 0.4 (Silufol UV-254, petroleum ether EtOAc,
1
phosphonate (IIb) was prepared similarly to IIa
from 1.06 g (8.0 mmol) of 4-methoxyphenylacetylene
(Ib), 1.1 ml (8.5 mmol) of HP(O)(OEt) , 126 mg
122
0.96 mmol) of PPh in 8 ml of anhydrous THF.
Reaction time 29 h. We obtained 1.41 g (65%) of
2
(
4
: 1). H NMR spectrum (CDCl ), , ppm: 0.29 s
3
3
3
3
9H, CH3), 7.41 d.d (1H, C H, JHH 8.4, JHH
.0 Hz), 7.74 d (1H, C H, J 8.8 Hz), 7.97 s (1H,
7
3
2
HH
(
mol) of Pd (dba) CHCl , and 252 mg
5
8
3
2 3 3
C H), 8.03 d (1H, C H, J 8.8 Hz), 8.10 d (1H,
HH
(
4
3
2
3
C H, J
8.4 Hz), 8.90 br.d (1H, C H).
HH
phosphonate IIb as a yellowish viscous fluid. bp
To a solution of 0.535 g (2.37 mmol) of 6-tri-
1
33 135 C (10 1 mm Hg), Rf 0.5 (Silufol UV-254,
methylsilylethynylquinoline in 0.4 ml of Et O and
2
1
EtOAc). IR spectrum (from film), , cm : 2983,
1
0
.8 ml of MeOH under argon atmosphere was added
.149g (1.08 mmol) of K CO . After stirring at room
1
604, 1511, 1295, 1255, 1180, 1025, 968, 836, 792.
2
3
1
3
C NMR spectrum (CDCl ), , ppm: 16.1 d
temperature for 2.5 h the reaction mixture was diluted
3
3
(CH CH , J
6.1 Hz), 55.1 s (OCH ), 62.0 d
with water and extracted wuth Et O. The ether
2
3
CP 3
2
2
3
5
extracts were washed with saturated water solution of
(OCH , J 5.6 Hz), 113.6 s (C + C ), 128.5 d
2 CP
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

8
04
GULYKINA et al.
2
6
3
2 2
(
1
(
C + C , J 5.9 Hz), 129.9 d (C , J 8.1 Hz),
Besides 0.060 g (15%) of trans-(O,O-diethyl)-2-(3-
pyridyl)ethenylphosphonate (IIIe) [58] was isolated,
Rf 0.35 (Silufol UV-254, C H acetone, 1$^: 1).
CP
CP
1
1
33.5 d (C ), 138.7 d (CP, J 178.2 Hz), 159.5 s
COMe). Found, %: C 58.22; H 7.09; P 11.71.
CP
6
6
C H O P. Calculated, %: C 57.77; H7.09; P11.46.
1
3
19
4
(
O,O-Diethyl)-1-(3-quinolyl)ethenylphosphonate
(
O,O-Diethyl)-1-(6-methoxy-2-naphthyl)ethenyl-
(IIf) was prepared similarly to IIa from 0.173 g
(1.13 mmol) of 3-ethynylquinoline (If), 0.149 g
phosphonate (IIc) was prepared similarly to IIa from
.351 g (1.93 mmol) of 6-methoxy-2-ethynylnaphthal-
ene (Ic), 0.265 g (1.92 mmol) of HP(O)(OEt) , 31 mg
0
(1.08 mmol) of HP(O)(OEt) , 17 mg (16.4 mol) of
2
2
Pd (dba) CHCl , and 36 mg (137 mol) of PPh3
2
3
3
(
(
30
mol) of Pd (dba) CHCl , and 60 mg
2 3 3
in 1.1 ml of anhydrous THF. Reaction time 114 h.
The solvent was removed on a rotary evaporator, the
residue was submitted to chromatography on silica
gel using as eluent hexane ethyl acetate mixture
gradually increasing the eluent polarity. We obtained
0.23 mmol) of PPh3 in 1.9 ml of anhydrous THF.
Reaction time 37 h. The solvent was removed on a
rotary evaporator, the residue was submitted to
chromatography on silica gel using as eluent ether
hexane mixture gradually increasing the eluent
polarity. We obtained 0.448 g (73%) of phosphonate
0
.223 g (71%) of isomers IIf and IIIf mixture in the
31
ratio of 84: 16 ( P NMR). Rf 0.4 (Silufol UV-254,
IIc as viscous yellow fluid. Rf 0,25 (Silufol UV-254,
EtOAc).
1
Et O). IR spectrum (from film), , cm : 2985, 1627,
2
The separation of 133.5 mg of the isomer mixture
obtained was carried out by preparative thin layer
chromatography on Silufol plates (200 200 mm) at
repeated treating with eluent (C H acetone, 3: 1).
We obtained 110 mg (82%) of phosphonate IIf.
Besides 19 mg (14%) of trans-(O,O-diethyl)-2-(3-
quinolyl)ethenylphosphonate (IIIf) was isolated.
1
1
604, 1483, 1438, 1390, 1255, 1205, 1164, 1049,
1
3
025, 968, 856, 790, 754, 723. C NMR spectrum
3
(
CDCl ), , ppm: 16.2 d (CH CH , J 6.3 Hz),
3 2 3 CP
2
5
5.2 s (OCH ), 62.2 d (OCH , J 5.7 Hz), 105.6 s
6
6
3
2
CP
7
5
5
7
1
(
C or C ), 119.1 s (C or C ), 125.6 d (C3 or C ,
JCP 6.0 Hz), 126.6 d (C or C , J 6.0 Hz),
3
1
2
3
CP
4
C
C
2
1
26.8 s (C ), 128.6 s ( 9 ), 129.8s ( 8 ), 131.0d (C ,
2
4
2
J
8.0 Hz), 131.7 d (C , J 12.1 Hz), 134.2 s
(O,O-Diethyl)-1-(6-quinolyl)ethenylphosphonate
(IIg) was prepared similarly to compound IIa from
0.125 g (0.82 mmol) of 6-ethynylquinoline Ig,
CP
CP
1
0
1
(
C ), 139.6d (CP, J 175.0 Hz), 158.1s (COMe).
CP
Found, %: C 63.83; H 6.68; P 9.69. C H O P.
Calculated, %: C 63.74; H 6.61; P 9.67.
1
7
21
4
0.108 g (0.78 mmol) of HP(O)(OEt) , 13 mg
2
(
(
12.5 mol) of Pd (dba) CHCl , and 25 mg
(
O,O-Diethyl)-1-(ferrocenyl)ethenylphosphonate
2 3 3
95 mol) of PPh in 1 ml of anhydrous THF. Reac-
(
(
(
IId) was prepared similarly to IIa from 0.630 g
3.00 mmol) of ethynylferrocene (Id), 0.416 g
3.01 mmol) of HP(O)(OEt) , 47 mg (45 mol) of
3
tion time 117 h. The solvent was removed on a rotary
evaporator, the residue was submitted to chromato-
graphy on silica gel using as eluent hexane ethyl
acetate mixture gradually increasing the eluent
polarity. We obtained 0.155 g (68%) of isomers IIg
2
Pd (dba) CHCl , and 103 mg (0.39 mmol) of PPh
2
3
3
3
in 3.5 ml of anhydrous THF. Reaction time 39 h.
The solvent was removed on a rotary evaporator, the
residue was submitted to chromatography on Al O3
using as eluent benzene ether mixture gradually in-
creasing the eluent polarity. We obtained unstable
yellow-brown oily fluid, Rf 0.44 (Alufol, Et O).
3
1
and IIIg mixture in the ratio of 4: 1 ( P NMR).
Rf 0.35 (Silufol UV-254, EtOAc).
2
The separation of 132.5 mg of the isomer mixture
obtained was carried out by preparative thin layer
chromatography on Silufol plates (200 200 mm) at
2
(
O,O-Diethyl)-1-(3-pyridyl)ethenylphosphonate
(
(
(
IIe) was prepared similarly to IIa from 0.197 g
1.91 mmol) of 3-ethynylpyridine (Ie), 0.236 g
1.71 mmol) of HP(O)(OEt) , 27 mg (26 mol) of
repeated treating with eluent (CCl acetone, 3: 1).
4
We obtained 94.4 mg (71%) of phosphonate IIg.
Besides 13 mg (10%) of trans-(O,O-diethyl)-2-(6-
quinolyl)ethenylphosphonate (IIIg) was isolated.
2
Pd (dba) CHCl , and 55 mg (0.21 mmol) of PPh in
2
3
3
3
1
.7 ml of anhydrous THF. Reaction time 26 h. The
(O,O-Diethyl)-1-butylethenylphosphonate (IIh)
solvent was removed on a rotary evaporator, the
residue was submitted to chromatography on silica
gel using as eluent benzene ethyl acetate mixture
gradually increasing the eluent polarity. We obtained
was prepared in the same way as compound IIa
from 0.91 g (11.1 mmol) of hexyne-1, 1.38 g
(10.0 mmol) of HP(O)(OEt) , and 0.38 g (0.3 mmol)
of Pd(PPh3) in 10 ml of anhydrous THF. Reaction
2
0
.242 g (59%) of phosphonate IIe as yellowish
4
viscous fluid. Rf 0.45 (Silufol UV-254, C H acetone,
time 12 h. We obtained 1.81 g (82%) of phosphonate
6
6
IIh as colorless fluid, bp 59 61 C (10 1 mm Hg).
1
: 1).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

HYDROPHOSPHORYLATION OF TERMINAL ALKYNES
805
1
IR spectrum (from film), , cm : 2970, 2935, 2880,
vol. 73, p. 487.
1
1
450, 1395, 1255, 1240, 1185, 1165, 1100, 1055,
13. Yamashita, M., Morizane, T., Fujita, K., Nakata-
ni, K., and Inokawa, S., Bull. Chem. Soc. Jpn., 1987,
vol. 60, p. 812.
14. Gomyo, T., Yoshida, H., Ogata, T., Inokawa, H.,
and Inokawa, S., Nippon Kagaku Kaishi., 1974,
p. 1093; Ref. Zh. Khim., 1975, 2Zh347.
15. Pudovik, A.N., Gozman, I.P., and Nikitina, V.I.,
Zh. Obshch. Khim., 1963, vol. 33, p. 3201.
1
3
030, 960, 795, 740. C NMR spectrum (CDCl ),
3
4
3
,
2
J
ppm: 13.4 s (C ), 15.9 d (OCH CH , J 6.1 Hz),
2 3 CP
3
2
3
1
1.8 s (C ), 29.7 d (C , J 5.2 Hz), 31.4 d (C ,
CP
2
2
10.8 Hz), 61.2 d (OCH , J 5.4 Hz), 128.4 d
CP
2 CP
2
2
1
(
C , J 6.7 Hz), 139.1 d (CP, J 170.8 Hz).
CP CP
Found, %: C 54.49; H 9.64. C H O P. Calculated,
1
0
21
3
%
: C 54.53; H 9.61.
1
1
1
1
2
2
2
6. PCT Int. Appl. Patent 9624599, 1996; Chem. Abstr.,
996, vol. 125, 222166x.
7. German Patent 1159443, 1963; Chem. Abstr., 1964,
vol. 60, 10718f.
8. Axelrad, G., Laosooksathit, S., and Engel, R., PCT
Int. Appl. J. Org. Chem., 1981, vol. 46, p. 5200.
9. Banerjee, S., Engel, R., and Axelrad, G., Phos-
phorus and Sulfur., 1983, vol. 15, p. 15.
0. Tavs, P. and Weitkamp, H., Tetrahedron, 1970,
vol. 26, p. 5529.
1. Hirao, T., Masunaga, T., Ohshiro, Y., and Agawa, T.,
Tetrahedron Lett., 1980, vol. 21, p. 3595.
2. Hirao, T., Masunaga, T., Yamada, N., Ohshiro, Y.,
and Agawa, T., Bull. Chem. Soc. Jpn., 1982, vol. 55,
p. 909.
Reaction of tert-butylacetylene with diethyl
1
phosphite. A mixture of 0.091 g (1.11 mmol) of tert-
butylacetylene, 0.138 g (1.0 mmol) of HP(O)(OEt)2,
1
16 mg (0.10 mmol) of Pd(PPh3)4 in 1 ml of
anhydrous THF was heated for 120 h in a sealed
evacuated ampule to 67 C. The ampule was opened,
the catalyst precipitated at cooling and was filtered
off. The solvent was removed in a vacuum, the
residue was analyzed by spectral methods. A mixture
was obtained of (O,O-diethyl)-1-(tert-butyl)ethenyl-
phosphonate IIi and trans-(O,O-diethyl)-2-(tert-
butyl)ethenylphosphonate (IIIi) in 34: 66 ratio
1
(
H NMR).
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2
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