Reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water: Stereoselective synthesis of functionalized pyridylvinylphosphine oxides

Article abstract of DOI:10.1002/ejoc.201301453

The reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water proceeds under mild conditions (40-45 °C, without catalyst, 4-5 h) with liberation of pyridine to give (E)-pyridylvinylphosphine oxides in 45-56 % yields, the only exception being the reaction with cyanophenylacetylene, which affords the corresponding vinylphosphine oxide of Z-configuration in 40 % yield. The reaction is likely triggered by the zwitterion, the adduct of tri(2-pyridyl)phosphine to the electrophilic acetylenes, the carbanionic center of which is then neutralized by a proton from water. The intermediate phosphonium hydroxide finally decomposes to the product. The one-pot stereoselective synthesis of functionalized pyridylvinylphosphine oxides has been elaborated through the straightforward reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water. The reaction is accompanied by liberation of the pyridine molecule. Copyright

Full text of DOI:10.1002/ejoc.201301453

FULL PAPER
DOI: 10.1002/ejoc.201301453
Reaction of Tri(2-pyridyl)phosphine with Electron-Deficient Alkynes in Water:
Stereoselective Synthesis of Functionalized Pyridylvinylphosphine Oxides
Svetlana N. Arbuzova,[a] Nina K. Gusarova,[a] Tatyana E. Glotova,[a] Igor A. Ushakov,[a]
Svetlana I. Verkhoturova,[a] Anastasiya O. Korocheva,[a] and Boris A. Trofimov*[a]
Keywords: Stereoselective synthesis / Nitrogen heterocycles / Alkynes / Phosphanes / Zwitterions
The reaction of tri(2-pyridyl)phosphine with electron-de-
ficient alkynes in water proceeds under mild conditions (40–
45 °C, without catalyst, 4–5 h) with liberation of pyridine to
give (E)-pyridylvinylphosphine oxides in 45–56% yields, the
only exception being the reaction with cyanophenylacetyl-
ene, which affords the corresponding vinylphosphine oxide
of Z-configuration in 40% yield. The reaction is likely
triggered by the zwitterion, the adduct of tri(2-pyridyl)-
phosphine to the electrophilic acetylenes, the carbanionic
center of which is then neutralized by a proton from water.
The intermediate phosphonium hydroxide finally decom-
poses to the product.
water at room temperature to afford (E)-1-acyl-2-phenyleth-
Introduction
enes in high yields (83–91%; Scheme 1).[7]
Generating zwitterionic species by the addition of terti-
ary phosphines to electron-deficient acetylenes and their
further transformations is a general and convenient strategy
for the synthesis of a diverse range of organic compounds.[1]
In these reactions, tertiary phosphines behave as both cata-
lysts and reactants.
Thus, nucleophilic phosphine organocatalysis is success-
fully employed in Michael β-addition of C-,[1c] N-,[2] O-,[1c,3]
and S-[1c] centered nucleophiles to electron-deficient acetyl-
enes. This strategy has also been used to direct the nucleo-
philic attack to the α- and γ-positions of the alkynes.[1a–1c,4]
The tertiary phosphines actively initiate isomerization of
conjugated alkynes to conjugated dienes[1a–1c,5] as well as
cycloaddition reactions of electron-deficient acetylenes with
dipolarophiles leading to carbocycles and heterocycles.[1]
As reactants,[6] tertiary phosphines in most cases react
with electron-deficient acetylenes to deliver stable phos-
phorus ylides.[6b–6j] Commonly, in all the above reactions,
the set of tertiary phosphines is limited to the most available
and stable triphenylphosphine and trialkylphosphines are
involved quite rarely.
Scheme 1. Synthesis of (E)-1-acyl-2-phenylethenes from 1-acyl-2-
phenylacetylenes in the system Ph3P/H2O.
Recently, the close heteroanalogue of triphenyl-
phosphine, tri(2-pyridyl)phosphine (1), has become avail-
able through the straightforward reaction between elemen-
tal phosphorus and 2-bromopyridine (Scheme 2).[8] This
tetradentate phosphine might be expected to interact with
electron-deficient alkynes in water in quite a different way
to that of triphenylphosphine.
Scheme 2. Synthesis of tri(2-pyridyl)phosphine (1) from elemental
phosphorus and 2-bromopyridine in the system KOH/DMSO.
Results and Discussion
Recently, we have shown that 1-acyl-2-phenylacetylenes
are stereoselectively reduced with triphenylphosphine in
Indeed, the reaction of 1 with a range of electron-de-
ficient alkynes 2a–e in water (40–45 °C, 4–5 h) takes an un-
usual direction to form stereoselectively functionalized (E)-
pyridylvinylphosphine oxides 3a–d in 45–56% yields, except
for cyanophenylacetylene (2e) which gives the correspond-
ing vinylphosphine oxide 3e of Z-configuration in 40%
yield. The reaction is accompanied by liberation of the pyr-
idine molecule (Table 1).
[a] A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences,
1 Favorsky Str., 664033 Irkutsk, Russian Federation
E-mail: boris_trofimov@irioch.irk.ru
http://www.irkinstchem.ru
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201301453.
Eur. J. Org. Chem. 2014, 639–643
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B. A. Trofimov et al.
FULL PAPER
Table 1. Three-component reaction between 1, electron-deficient plausible. The liberation of pyridine and the appearance of
alkyne 2 and water.[a]
amphiphilic phosphine oxides may also autocatalyze the re-
action.
The reaction was monitored by 31P NMR and IR spec-
troscopic analysis of the solid phase particles dissolved in
CDCl3 prior to the analysis because both reactants and
products (except for pyridine) were almost insoluble in
water (liquid phase). 31P NMR spectra showed reduction in
the intensity of peaks of the initial tri(2-pyridyl)phosphine
(1) at –1 ppm and an increase in the intensity of new peaks
at ca. 20 ppm corresponding to vinylphosphine oxides 3a–
e. In the IR spectra, a reduction in the intensity of the ab-
sorption band of the acetylenic CϵC bond (2198–
2200 cm–1) in the case of acylacetylenes 2a–d or the inten-
sity of the absorption band corresponding to CϵC and
CϵN bonds of initial cyanophenylacetylene (2e) (2270 cm–1
with a shoulder) was observed. The optimal process dura-
tion was found to be 4–5 h; no change was observed in the
spectra after additional heating of the reaction mixture for
a further 1–2 h.
Configurational assignment of the synthesized vinyl-
1
phosphine oxides 3 was performed on the basis of H spec-
tra and 2D NOESY data. Thus, doublets of ethenyl protons
3
at 7.45–7.50 ppm with JHP ca. 20 Hz and the cross-peaks
between the ethenyl and pyridine protons reliably support
the E-configuration of phosphine oxides 3a–d. A doublet at
3
δ = 6.20 ppm with JHP 32 Hz and the cross-peak between
the ethenyl and ortho-phenyl protons, observed in the spec-
tra of phosphine oxides 3e, indicate its Z-configuration.
A tentative mechanism for the reaction involves nucleo-
philic addition of 1 as a neutral nucleophile to the triple
bond to give zwitterionic intermediate A with a carbanionic
center trans to the phosphorus (according to classic nucleo-
philic addition to acetylenes[9]) (Scheme 3, Scheme 6). In
the case of acylacetylenes, the equilibrium between zwitter-
ions of E- (A) and Z- (B) configuration should exist, which
interconvert via allenic intermediate C (Scheme 3). Evi-
dently, the most stable intermediate should be zwitterion
B due to the attractive intramolecular interaction between
carbanionic center and the positively charged phosphorus
atom. Therefore, the reaction is expected to proceed via in-
termediate B because the equilibrium (Scheme 3) should be
shifted mostly to the right. After neutralizing the carban-
[a] Reaction conditions: phosphine 1 (1 mmol), alkyne 2 (1 mmol),
H2O (8 mL), 40–45 °C, 4–5 h. [b] The yield was calculated on the
basis of alkyne consumed.
ionic center by a proton from water, phosphonium hydrox-
Because both phosphine 1 and acetylene 2 are solids that ide D is formed, which is in equilibrium with intermediate
are almost insoluble in water, the reaction actually initiates hydroxyphosphorane E. The latter then decomposes to the
in the three-phase solid-solid-liquid system. The crude final product to release the pyridine molecule.
products are also insoluble in water, which allows them to
be easily separated from the aqueous phase. The products molecular proton transfer from the OH group of phos-
are purified by the extraction of impurities by acetone. phorane E to the basic nitrogen atom of the pyridine ring.
The elimination step (Scheme 3) could involve an intra-
Notably, homogenization of the reaction system with This makes the latter a much better leaving group. Such
tetrahydrofuran (THF) resulted in lower yields (ca. 20%) a protonation would also explain the unexpected reaction
of phosphine oxide 3a, with the major product being tri(2- outcome as compared to the reaction of PPh3 with electron-
pyridyl)phosphine oxide (4; 55%), as exemplified by the re- deficient acetylenes in water. With PPh3, no intramolecular
action of phosphine 1 with acetylene 2a.
Whereas the formation of the corresponding phosphon- reaction thus proceeds through a different route.[7]
ium hydroxide is expected (see below), a contribution of However, under similar conditions, in the case of di-
phase-transfer catalysis by this species to this reaction is methyl acetylene dicarboxylate (5), the elimination of pyr-
protonation can occur (as there is no basic site) and the
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Stereoselective Synthesis of Pyridylvinylphosphine Oxides
Scheme 5. Tentative scheme for the formation of dimethyl fumarate
(6).
oxide, which does not comply with the above rationale.
Clearly, the equilibrium between the zwitterions of A and
B types (see Scheme 3) is not as fast as with acylacetylenes
and, hence, this cyano derivative remains as the kinetic
product (Scheme 6).
Scheme 3. Tentative scheme for the formation of (E)-vinylphos-
phine oxides 3a–d.
idine does not occur. Instead, competitive C–P bond cleav-
age in the intermediate phosphorane between tripyridyl-
phosphine and the acetylene counterparts takes place fol-
lowed by elimination of tri(2-pyridyl)phosphine oxide (4)
and proton transfer from the hydroxyl group to the ethyl-
enic moiety to afford dimethyl fumarate (6) in 25% yield
(Scheme 4).
Scheme 6. Tentative scheme for the formation of (Z)-vinylphos-
phine oxide 3e.
Scheme 4. Three-component reaction between tri(2-pyridyl)-
phosphine (1), dimethyl acetylene dicarboxylate (5), and water.
The stage of pyridine elimination from tri(2-pyridyl)-
phosphine oxides under the action of organometallic com-
pounds, water, and alcohols has also been observed.[10]
In other words, the stereoselective reduction of the triple
bond under the action of the tri(2-pyridyl)phosphine/water
system, as previously found for the reaction of acetylenes
with PPh3/water,[7] is observed. The different reactivity of
electron-deficient acetylenes 2a–e and acetylene 5 in this re-
Conclusions
The one-pot stereoselective synthesis of functionalized
action is likely due to a better distribution of the negative dipyridylphosphine oxides has been elaborated through the
charge of carbanion-like counterpart of the transition state straightforward reaction of available tri(2-pyridyl)phos-
D (Scheme 5) in the case of acetylene 5.
phine with electron-deficient alkynes in water. The reaction
The above stated E-stereochemistry of the products 3a–d highlights novel facets of phosphine and acetylene chemis-
derived from acylacetylenes is consistent with the proposed try that paves an ecologically benign way to a new family
mechanism (Scheme 3). However a puzzle remains regard- of promising ligands[11] and building blocks for organic syn-
ing the Z-stereochemistry of the cyanoethenylphosphine thesis.[12] Among such compounds are retardants,[13] drug
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B. A. Trofimov et al.
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2JP,C = 7.3 Hz, Ci, Ph), 136.2 (d, 3JP,C = 9.6 Hz, C-4, Py), 137.4 (d,
precursors,[14] and ligands for the design of metallocomplex
catalysts applied particularly for hydrogenation of cyclohex-
ene, acetone, and cyclohexanone.[11b]
1
2JP,C = 9.2 Hz, =CH), 146.4 (d, JP,C = 87.0 Hz, =CP), 147.3 (C-5,
3
Fur), 150.3 (d, JP,C = 19.2 Hz, C-6, Py), 152.5 (C-2, Fur), 154.1
(d, 1JP,C = 132.2 Hz, C-2, Py), 178.8 (d, 3JP,C = 18.8 Hz, C=O) ppm.
31P NMR (161.98 MHz, CDCl3): δ = 19.8 ppm. 15N NMR
(40.55 MHz, CDCl ) δ = –56.8 ppm. IR (KBr): νmax = 1644 (C=O),
˜
3
Experimental Section
1197 (P=O) cm–1. C23H17N2O3P (400.37): calcd. C 69.00, H 4.28,
General Remarks: 1H, 13C, 15N, 31P NMR and 2D NMR spectra
were recorded with an AV-400 Bruker BioSpin spectrometer and
referenced to HMDS (1H, 13C), MeNO2 (15N) and H3PO4 (31P).
All 2D NMR spectra were recorded by using standard gradient
Bruker pulse programs. IR spectra were recorded with a Bruker
Vertex 70 instrument. GLC analysis was carried out with an
Agilent 6890 N chromatograph, HP-5 column (5% phenyl methyl
siloxane phase), column length of 30 m, vaporizer temperature
250 °C, column temperature 125–270 °C, temperature increase rate
of 30 °C/min. Acetylenes 2a and 2e are commercial reagents (Alfa
Aesar), acylacetylenes 2b–d were prepared by reported methods.[15]
N 7.00, P 7.74; found C 68.62, H 4.07, N 6.84, P 7.76.
(E)-3-(Di-2-pyridinylphosphoryl)-3-phenyl-1-(2-thienyl)-2-propen-1-
one (3c): Yield 220 mg (53%); yellowish powder; m.p. 156–158 °C.
3
3
1H NMR (400.13 MHz, CDCl3): δ = 7.02 (dd, J4–5 = 4.9, J4–3
=
3.9 Hz, 1 H, H-4, thienyl), 7.09 (m, 1 H, Hp, Ph), 7.11 (m, 2 H,
Hm, Ph), 7.17 (m, 2 H, Ho, Ph), 7.41 (m, 2 H, H-5, Py), 7.52 (d,
3
4
3JP,H = 20.3 Hz, 1 H, =CH), 7.58 (dd, J5–4 = 4.9, J5–3 = 1.0 Hz,
3
4
1 H, H-5, thienyl), 7.71 (dd, J3–4 = 3.9, J3–5 = 1.0 Hz, 1 H, H-3,
thienyl), 7.80 (m, 2 H, H-4, Py), 8.15 (m, 2 H, H-3, Py), 8.83 (d,
3J6–5 = 4.5 Hz, 2 H, H-6, Py) ppm. 13C NMR (100.62 MHz,
CDCl3): δ = 125.8 (d, JP,C = 2.9 Hz, C-5, Py), 127.9 (Cm, Ph),
128.2 (Cp, Ph), 128.2 (C-4, thienyl), 129.2 (d, JP,C = 21.3 Hz, C-3,
4
2
General Procedure for the Synthesis of Phosphine Oxides 3: A sus-
pension of finely divided tri(2-pyridyl)phosphine 1 (1 mmol) and
acetylene 2 (1 mmol) in water (8 mL) was blown with argon and
stirred at 40–45 °C for 4–5 h. The aqueous layer was decanted from
the dark solid obtained, the solid was solved in chloroform (3 mL)
and the solution was dried with MgSO4. After evaporation of the
solvent, the crude product was washed with acetone (5ϫ0.5 mL)
and dried in vacuo to give vinylphosphine oxides 3 as white or
yellowish powders.
3
2
Py), 129.2 (d, JP,C = 5.1 Hz, Co, Ph), 133.9 (d, JP,C = 7.3 Hz, Ci,
3
Ph), 134.5 (C-3, thienyl), 135.0 (C-5, thienyl), 136.2 (d, JP, C
=
=
2
4
9.5 Hz, C-4, Py), 138.8 (d, JP,C = 8.8 Hz, =CH), 144.0 (d, JP,C
1
2.9 Hz, C-2, thienyl), 144.9 (d, JP,C = 87.3 Hz, =CP), 150.4 (d,
3JP,C = 19.1 Hz, C-6, Py), 154.1 (d, 1JP,C = 132.8 Hz, C-2, Py), 184.3
3
(d, JP,C = 18.3 Hz, C=O) ppm. 31P NMR (161.98 MHz, CDCl3):
δ = 20.0 ppm. IR (KBr): ν
= 1631 (C=O), 1196 (P=O) cm–1.
˜
max
C23H17N2O2PS (416.43): calcd. C 66.34, H 4.11, N 6.73, P 7.44;
found C 65.96, H 4.09, N 6.72, P 7.42.
The relative content of the Z isomers of 3a–d or the E isomer of
3e in the crude product did not exceed 10%, with the total conver-
sion being 90–95% (1H, 31P NMR analysis; acetylene 2 could be
recovered by extraction with hexane). Pyridine was quantified by
titration of the aqueous layer against aqueous HCl or by GLC
analysis (after extraction of the aqueous layer with chloroform).
(E)-3-[Di(2-pyridinyl)phosphoryl]-3-phenyl-1-(3-pyridinyl)-2-propen-
1-one (3d): Yield 200 mg (49%); white powder; m.p. 166–168 °C.
1H NMR (400.13 MHz, CDCl3): δ = 7.02 (m, 3 H, Hm, Hp, Ph),
7.08 (m, 2 H, Ho, Ph), 7.21 (m, 1 H, H-5, PyC=O), 7.41 (m, 2 H,
3
H-5, PyP=O), 7.43 (d, JP,H = 20.1 Hz, 1 H, =CH), 7.80 (m, 2 H,
H-4, PyP=O), 8.06 (m, 1 H, H-4, PyC=O), 8.13 (m, 2 H, H-3,
3
(E)-3-(Di-2-pyridinylphosphoryl)-1,3-diphenyl-2-propen-1-one (3a):
Yield 230 mg (56%); white powder; m.p. 159–161 °C. 1H NMR
(400.13 MHz, CDCl3): δ = 6.98 (m, 3 H, Hm, Hp, PhC=), 7.09 (m,
2 H, Ho, PhC=), 7.28 (m, 2 H, Hm, PhC=O), 7.34 (m, 2 H, H-5,
PyP=O), 8.59 (m, 1 H, H-6, PyC=O), 8.83 (d, J6–5 = 4.5 Hz, 2 H,
H-6, PyP=O), 9.04 (d, 4J2–4 = 2.5 Hz, 1 H, H-2, PyC=O) ppm. 13
C
NMR (100.62 MHz, CDCl3): δ = 123.4 (C-5, PyC=O), 126.0 (d,
4JP,C = 3.0 Hz, C-5, PyP=O), 128.1 (Cm, Ph), 128.5 (Cp, Ph), 129.3
3
2
3
Py), 7.39 (m, 1 H, Hp, PhC=O), 7.45 (d, JP,H = 20.8 Hz, 1 H,
(d, JP,C = 21.0 Hz, C-3, PyP=O), 129.34 (d, JP,C = 4.4 Hz, Co,
Ph), 131.8 (d, 4JP,C = 1.8 Hz, C-3, PyC=O), 133.7 (d, 2JP,C = 7.6 Hz,
=CH), 7.74 (m, 2 H, H-4, Py), 7.83 (m, 2 H, Ho, PhC=O), 8.11 (m,
3
2 H, H-3, Py), 8.77 (d, J6–5 = 4.5 Hz, 2 H, H-6, Py) ppm. 13C
3
Ci, Ph), 136.2 (C-4, PyC=O), 136.4 (d, JP,C = 9.6 Hz, C-4,
NMR (100.62 MHz, CDCl3): δ = 125.7 (d, 4JP,C = 3.1 Hz, C-5, Py),
PyP=O), 139.3 (d, 2JP,C = 8.8 Hz, =CH), 145.4 (d, JP,C = 87.7 Hz,
1
=CP), 150.5 (d, 3JP,C = 19.2 Hz, C-6, PyP=O), 150.8 (C-2, PyC=O),
127.8 (Cm, PhC=), 128.1 (Cp, PhC=), 128.4 (Cm, PhC=O), 129.2
2
3
1
(d, JP,C = 20.9 Hz, C-3, Py), 129.2 (Co, PhC=O), 129.4 (d, JP,C
=
153.6 (C-6, PyC=O), 154.1 (d, JP,C = 132.2 Hz, C-2, PyP=O),
2
192.5 (d, JP,C = 18.0 Hz, C=O) ppm. 31P NMR (161.98 MHz,
3
4.5 Hz, Co, PhC=), 133.4 (Cp, PhC=O), 133.9 (d, JP,C = 7.9 Hz,
3
4
Ci, PhC=), 136.1 (d, JP,C = 9.3 Hz, C-4, Py), 136.3 (d, JP,C
=
CDCl ): δ = 20.1 ppm. IR (KBr): ν
= 1671 (C=O), 1199
˜
3
max
1.5 Hz, Ci, PhC=O), 140.8 (d, 2JP,C = 8.7 Hz, =CH), 143.8 (d, 1JP,C
= 88.7 Hz, =CP), 150.3 (d, 3JP,C = 19.5 Hz, C-6, Py), 154.3 (d, 1JP,C
(P=O) cm–1. C24H18N3O2P (411.39): calcd. C 70.07, H 4.41, N
10.21, P 7.53; found C 69.87, H 4.30, N 10.13, P 7.30.
= 132.5 Hz, C-2, Py), 193.1 (d, JP,C = 17.6 Hz, C=O) ppm. 31P
3
(Z)-3-[Di(2-pyridinyl)phosphoryl]-3-phenyl-2-propenenitrile
(3e):
NMR (161.98 MHz, CDCl3):
δ =
19.7 ppm. 15N NMR
Yield 132 mg (40%); yellowish powder; m.p. 176–178 °C. 1H NMR
(40.55 MHz, CDCl ) δ = –57.1 ppm. IR (KBr): νmax = 1665 (C=O),
˜
3
3
(400.13 MHz, CDCl3): δ = 6.20 (d, JP,H = 32.0 Hz, 1 H, =CH),
1199 (P=O) cm–1. C25H19N2O2P (410.40): calcd. C 73.16, H 4.67,
7.21 (m, 1 H, Hp, Ph), 7.23 (m, 2 H, Hm, Ph), 7.37 (m, 2 H, H-5,
Py), 7.49 (m, 2 H, Ho, Ph), 7.80 (m, 2 H, H-4, Py), 8.21 (m, 2 H,
N 6.83, P 7.55; found C 73.55, H 4.97, N 6.69, P 7.52.
3
(E)-3-(Di-2-pyridinylphosphoryl)-1-(2-furanyl)-3-phenyl-2-propen-1-
H-3, Py), 8.76 (d, J6–5 = 4.5 Hz, 2 H, H-6, Py) ppm. 13C NMR
1
2
one (3b): Yield 180 mg (45%); white powder; m.p. 158–160 °C. H
(100.62 MHz, CDCl3): δ = 111.4 (d, JP,C = 3.1 Hz, =CH), 113.9
3
4
NMR (400.13 MHz, CDCl3): δ = 6.40 (m, 1 H, H-3, Fur), 7.08– (d, JP,C = 9.2 Hz, CN), 126.2 (d, JP,C = 3.0 Hz, C-5, Py), 127.9
3
7.14 (m, 6 H, H-4, Fur, Ph), 7.39 (m, 2 H, H-5, Py), 7.46 (d, JP,H (d, 3JP,C = 4.6 Hz, Co, Ph), 128.5 (Cm, Ph), 129.2 (d, 2JP,C = 21.4 Hz,
3
= 20.1 Hz, 1 H, =CH), 7.47 (m, 1 H, H-5, Fur), 7.77 (m, 2 H, H-
C-3, Py), 129.5 (Cp, Ph), 136.3 (d, JP,C = 9.9 Hz, C-4, Py), 136.8
(d, 2JP,C = 6.9 Hz, Ci, Ph), 150.7 (d, 3JP,C = 20.3 Hz, C-6, Py), 153.4
(d, 1JP,C = 135.8 Hz, C-2, Py), 156.3 (d, 1JP,C = 86.4 Hz, =CP) ppm.
3
4, Py), 8.14 (m, 2 H, H-3, Py), 8.80 (d, J6–5 = 4.3 Hz, 2 H, H-6,
Py) ppm. 13C NMR (100.62 MHz, CDCl3): δ = 112.4 (C-3, Fur),
4
4
119.9 (C-4, Fur), 125.8 (d, JP,C = 2.6 Hz, C-5, Py), 127.8 (d, JP,C 31P NMR (CDCl ): δ = 17.4 ppm. IR (KBr): ν
= 2210 (CϵN),
˜
3
max
= 1.3 Hz, Cm, Ph), 128.1 (d, 5JP,C = 1.8 Hz, Cp, Ph), 129.2 (d, 3JP,C
= 4.6 Hz, Co, Ph), 129.2 (d, JP,C = 21.1 Hz, C-3, Py), 134.0 (d,
1191 (P=O) cm–1. C19H14N3OP (331.31): calcd. C 68.88, H 4.26, N
2
12.68, P 9.35; found C 68.55, H 4.21, N 12.73, P 9.69.
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Stereoselective Synthesis of Pyridylvinylphosphine Oxides
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Reaction of Tri(2-pyridyl)phosphine (1) with Dimethyl Acetylene-
dicarboxylate (5) in Water: A mixture of phosphine 1 (150 mg,
0.56 mmol), acetylene 5 (80 mg, 0.56 mmol) and water (5 mL) was
blown with argon and stirred at 40–45 °C for 4 h. The aqueous
layer was decanted from the white solid obtained. The solid was
dried in vacuo to give dimethyl fumarate (6), yield 20 mg (25%);
m.p. 100–102 °C. 1H NMR (400.13 MHz, CDCl3): δ = 3.81 (s, 3
H, Me), 6.86 (s, 1 H, =CH) ppm.
The aqueous layer was extracted with chloroform (3ϫ3 mL) and
the extract was dried with MgSO4. After removal of the extractant,
the crude residue (120 mg) was analyzed by 1H and 31P NMR spec-
troscopy. Tri(2-pyridyl)phosphine oxide (4) was identified as the
major product in this residue (1H NMR spectra were consistent
with reported data[16]).
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Supporting Information (see footnote on the first page of this arti-
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Received: September 24, 2013
Published Online: November 21, 2013
Eur. J. Org. Chem. 2014, 639–643
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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