Synthesis of stannylated allyl- and vinylphosphonates via molybdenum-catalyzed hydrostannations

Article abstract of DOI:10.1002/ejoc.200800418

Syntheses of stannylated allyl and vinylphosphonates by molybdenum-catalyzed hydrostannation of the corresponding propargyl- and alkynylphosphonate derivatives proceed with high regioselectivities. The stannylated phosphonates obtained are versatile build

Full text of DOI:10.1002/ejoc.200800418

FULL PAPER
DOI: 10.1002/ejoc.200800418
Synthesis of Stannylated Allyl- and Vinylphosphonates via Molybdenum-
Catalyzed Hydrostannations
Nivedita Jena[a] and Uli Kazmaier*[a]
Keywords: Allylphosphonates / Cross couplings / Hydrostannations / Molybdenum / Vinylphosphonates
Syntheses of stannylated allyl and vinylphosphonates by mo- tained are versatile building blocks for further modifications,
lybdenum-catalyzed hydrostannation of the corresponding
propargyl- and alkynylphosphonate derivatives proceed with
high regioselectivities. The stannylated phosphonates ob-
such as iodinations or cross coupling reactions.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
selective hydrostannations of functionalized alkynes (1) (see
Scheme 1) preferentially affording the α-stannylated prod-
ucts 2.[11]
Introduction
Functionalized unsaturated phosphonates are of great
interest as key intermediates in the synthesis of complex
molecules.[1] Vinylphosphonates can undergo Michael ad-
dition followed by a Horner–Wadsworth–Emmons (HWE)
olefination[1a] and α-metallated derivatives can be coupled
with a wide range of electrophiles.[1b] Allyl- and propargyl-
phosphonates, easily obtained via Arbuzov reaction,[2] can
be used for the synthesis of highly functionalized dienes[3]
and enynes.[4] While α-metallated vinylphosphonates can be
obtained from the corresponding vinylphosphonates by de-
protonation with LDA[5] or via 1,4-addition of organome-
tallics towards alkynylphosphonates,[6] the corresponding
metallated allylphosphonates are by far less available. The
most straightforward approach would be a hydrometalla-
tion, e.g. hydrostannation of propargylphosphonates. The
resulting stannylated phosphonates would be interesting
building blocks and suitable precursors for further modifi-
cations via Stille coupling.[7]
Scheme 1. Hydrostannation of alkyne 1. Reaction conditions: a)
Bu3SnH (3 equiv.), hydroquinone (10 mol-%), Mo(CO)3(CNtBu)3
(2 mol-%), THF, 60 °C, 4 h.
We now report on our investigations of MoBI3-catalyzed
hydrostannations of alkynyl and propargylphosphonates,
leading to the corresponding phosphorylated vinyl stann-
anes and their subsequent modifications via Stille coup-
lings.
It is well known, that hydrostannations of acetylenes are
induced either by radical initiators, Lewis acids or transis-
tion metal catalysts.[8] The major drawbacks of these meth-
ods result from difficulties in controlling the regioselectivity
of the tinhydride addition to unsymmetrical alkynes al-
though the transistion metal catalyzed version has the ad-
vantage of a clean cis addition, based on the reaction
mechanism.[9] In the case of terminal alkynes, hydro-
metallation in general gives rise to the terminal vinyl metal
species.
Results and Discussion
We began our studies with the reactions of two propar-
gylic phosphonates (4a,b) to see if the substituents on the
phosphorus have any influence on the outcome of the hy-
drostannation (Scheme 2). As expected, an increase in the
steric demand of the substituents decellerated the reaction,
what resulted in longer reaction times (16 h vs. 6 h) and
lower yields. The moderate yields observed for both propar-
gylic substrates 4 may be attributed to the instability of
these terminal alkynes as they are known to isomerize
under these conditions (into mixture of allenes and 2-al-
kynes)[12a] which gives rise to other products or leads to
decomposition.
Recently, our group has developed a new catalyst based
on molybdenum.[10] Mo(CO)3(CNtBu)3 (MoBI3) was found
to be an excellent catalyst for highly regio- and stereo-
[a] Universität des Saarlandes, Institut für Organische Chemie,
Universitaetscampus, Geb. C4.2, 66123 Saarbrücken
Fax: +49-6813022409
E-mail: u.kazmaier@mx.uni-saarland.de
3852
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 3852–3858

Molybdenum-Catalyzed Hydrostannations
Table 1. MoBI3-catalyzed hydrostannations of alkynylphosphona-
tes 11.
Scheme 2. Hydrostannation of propargylic phosphonates 4. Reac-
tion conditions: Bu3SnH (3 equiv.), hydroquinone (10 mol-%),
MoBI3 (2 mol-%), THF, 55 °C, (R = Me, 6 h; R = iPr, 16 h).
Entry Alkyne
R
Time
% Yield[a]
12/13[b]
92:8
Ͼ95(E):5
Ͼ95(E):5
93(Z):7
93(E):7
Ͼ95(E):5
Ͼ95(E):5
1
2
3
4
5
6
7
11a
11b
11c
11d
11d
11e
11f
H
Me
Pr
Ph
Ph
12 h
8 h
12 h
6 h
57
67
61
74
77
59
51
The regioselectivities (ratio 5/6) with these substrates
were also lower than other terminal alkynes,[11] but still in
the range of 80/20. Here, the influence of the substituents
can be neglected.
15 h
CH2CH2Ph 12 h
cyclohexyl 12 h
[a] Isolated yields. [b] Determined by 1H NMR and 31P NMR spec-
tra of crude reaction product.
The regioisomeric products could easily be separated via
flash chromatography. With pure stannylated phosphonates
5a in hand, we subjected it to several cross coupling reac-
tions (Scheme 3). Excellent yields were obtained with allyl
and benzyl bromide furnishing products 7 and 8. Surpris-
ingly, coupling with cinnamoyl chloride resulted only in 5%
of the expected coupling product 9a, the major one was the
reduced unsaturated ketone 9b with an E/Z-ratio of 88:12.
Obvoiously, the primarily formed dienone, which is the ex-
pected coupling product, undergoes reduction of the meth-
ylene group either by Bu3SnH or a molybdenum hydride
intermediate. Iodination of 5a was a very clean reaction,
and the iodide 10 obtained is an interesting substrate for
further modification.
The regioselectivities for the α-substituted products 12
were excellent with all substrates, independent on the sub-
stitution pattern of the triple bond.[13] The (E)-configured
products were formed preferentially, except for the phenyl-
substituted derivative, which gave rise to the (Z)-product
(entry 4). This is not completely surprising, because phenyl-
ated alkynes often show a special reaction behaviour in hy-
drostannations.[14] It is worth mentioning, that both isomers
could be synthesized by simply varying the reaction time.
The α-(Z) derivative was formed preferentially within 6 h,
while the α-(E) isomer was formed on heating the reaction
mixture for 15 h. The isomers could be identified via their
1H NMR and 31P NMR spectra. The α-(Z) isomer showed
a signal at δ = 26.2 ppm and α-(E) derivative gave a peak
at δ = 21.6 ppm in the 31P NMR spectroscopy. The (Z)-
isomer showed a coupling of JP–H = 33.2 Hz in the 1H
NMR spectrum, while the coupling constant for the α-(E)
isomer was JP–H = 62.4 Hz, which is in accordance with
the large coupling constants typically observed for vinylic
protons trans to phosphonate.[13]
To investigate the reaction behaviour of these stannylated
vinylphosphonates, we subjected the (E)-configured stan-
nane 12c and the (Z)-configured isomer of 12d also to cross
coupling reactions (Scheme 4).
The Stille coupling of 12c with iodobenzene gave the
coupling product 14 with high regioselectivity and complete
retention of the olefin geometry. Electron-withdrawing
groups (such as NO2) at the aromatic ring system increased
the yield (15) compared to the unsubstituted iodobenzene.
Benzyl bromide also reacted with complete retention of the
olefin geometry (16). These coupling reactions were always
accompanied by some protodestannylation. The formation
Scheme 3. Cross coupling reactions of stannated phosphonate 5a.
Reaction conditions: a) Allyl bromide, [(allyl)PdCl]2/PPh3, THF,
60 °C, 16 h; b) Benzyl bromide, [(allyl)PdCl]2/PPh3, PPh3, THF,
60 °C, 16 h; c) cinnamoyl chloride, [(allyl)PdCl]2/PPh3, THF, 60 °C,
16 h; d) I2, CHCl3, room temperature, 1 h.
Next, we focused on the alkynylphosphonates 11, where of alkenes by this process was more tremendous in reactions
the electron-withdrawing group is directly located at the tri- with acyl halides, e.g. benzoyl chloride,[15] and when the re-
ple bond (Table 1). Our previous work showed, that elec- actions were conducted in polar solvent such as acetonitrile.
tron-poor alkynes give better yields and regioselectivities in Therefore, the yields in these cross couplings were moderate.
the MoBI3-catalyzed hydrostannation step, and indeed, this In contrast, iodination of 12c proceeded smoothly furnish-
was also true with these phosphonates.
ing 17 in good yield.
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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3853

N. Jena, U. Kazmaier
FULL PAPER
the olefin geometry. The unexpected outcome of coupling
reactions with acyl halides such as benzoyl chloride (19) or
cinnamoyl chloride (9) is subject of further investigations.
Experimental Section
General Remarks: All reactions were carried out in oven-dried
glassware (100 °C) under argon. All solvents were dried before use.
THF was distilled from LiAlH4, NMP was dried with KOH, aceto-
nitrile from calcium hydride. The products were purified by flash
chromatography on silica gel. Mixtures of EtOAc and hexanes were
generally used as eluents. TLC: commercially precoated Polygram®
SIL-G/UV 254 plates. Visualization was accomplishhed with UV
light, iodine and KMnO4 solution. NMR spectra were recorded
in CDCl3 using a Bruker DRX 500 or a Bruker AV 400 NMR
spectrometer. Selected signals in the NMR spectra for the minor
isomers are extracted from the spectra of the isomeric mixture. CI-
MS analyses were performed using a Finnigan MAT 95. Elemental
analyses were carried out at the Department of Chemistry, Saar-
land University.
General Procedure for MoBI3-Catalyzed Hydrostannations: In a
oven dried Schlenk tube the corresponding phosphonoalkyne
(1 mmol) and the catalyst MoBI3 (8.6 mg, 20 µmol) were dissolved
together with hydroquinone (10 mg) in dry THF (2 mL) under ar-
gon. The solution was heated to 55 °C for 10 min before Bu3SnH
(0.8 mL, 3 mmol) was added. The reaction mixture was stirred for
6–15 h based on the consumption of the starting material. After
cooling to room temperature, the solvent was evaporated in vacuo
and the crude product was purified by flash chromatography on
silica gel using hexane/ethyl acetate mixtures containing 1% NEt3.
Dimethyl [2-(Tributylstannyl)allyl]phosphonate (5a): Stannylated al-
lylphosphonate 5a was prepared from propargylphosphonate 4a
(148 mg, 1.0 mmol) in 6 h according to the general procedure for
MOBI3-catalyzed hydrostannations as a colourless oil (228 mg,
0.52 mmol, 52%). 1H NMR (400 MHz, CDCl3): δ = 0.90 (t, J =
7.3 Hz, 9 H), 0.93–0.97 (m, 6 H), 1.28–1.37 (m, 6 H), 1.46–1.54 (m,
6 H), 2.80 (d, J = 22.2 Hz, 2 H), 3.73 (d, J = 10.8 Hz, 6 H), 5.35
(dd, J = 5.1, 2.3, Hz, 1 H), 5.89 (dd, J = 5.5, 2.2 Hz, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 10.0, 13.7, 27.4, 29.0, 36.2, 37.5,
52.4, 52.5, 130.8 (d, J = 13.9 Hz), 143.8 (d, J = 11.9 Hz) ppm. 31P
NMR (162 MHz, CDCl3): δ = 29.8 ppm. 119Sn NMR (149 MHz,
CDCl3): δ = –38.1 (d, J = 31.9 Hz) ppm. HRMS (CI) m/z calcd.
for C17H38O3PSn [M + H]+: 440.1502, found 440.1520; m/z calcd.
for C13H29O3PSn [M – Bu]+: 383.0798, found 383.0783.
Scheme 4. Cross coupling reaction of stannated vinylphosphonates.
Reaction conditions: a) PhI, CuI, Pd2(dba)3 (2 mol-%), P(fur)3
(15 mol-%), NMP, room temp., 16 h; b) p-NO2-PhI, CuI, Pd2-
(dba)3 (2 mol-%), P(fur)3 (15 mol-%), N-methylpyrrolidinone
(NMP), room temp., 16 h; c) BnBr, Pd2(dba)3 (2 mol-%), AsPh3
(15 mol-%), toluene, 90 °C, 15 h; d) I2, CHCl3, room temp. 1 h; e)
PhCOCl, [(allyl)PdCl]2/PPh3, THF, 60 °C.
Dimethyl [(3E)-3-(Tributylstannyl)allyl]phosphonate (6a): Stannane
6a was obtained as the minor regioisomer in the hydrostannation
of 4a. 1H NMR (400 MHz, CDCl3): δ = 0.87–0.94 (m, 15 H), 1.28–
1.35 (m, 6 H), 2.71 (dd, J = 6.8, 1.3 Hz, 1 H), 2.76 (dd, J = 6.8,
1.3 Hz, 1 H), 3.73 (d, J = 10.8 Hz, 6 H), 5.84–5.93 (m, 1 H), 6.18
(ddt, J = 18.8, 4.5, 1.3 Hz, 1 H) ppm. 31P NMR (162 MHz,
CDCl3): δ = 29.5 ppm. 119Sn NMR (149 MHz, CDCl3): δ = –49.5
(d, J = 24.2 Hz) ppm.
The same effects were observed with (Z)-configured 12d.
While the iodination furnished the expected product 18 in
good yield as a single isomer, the coupling with benzoyl
chloride in THF resulted mainly in protodestannylation,
furnishing alkene 19 as the major product in high yields
with complete retention of geometry. Stille reaction with p-
nitroiodobenzene gave rise to 20.
Diisopropyl [2-(Tributylstannyl)allyl]phosphonate (5b): Stannylated
allylphosphonate 5b was prepared from propargylphosphonate 4b
(204 mg, 1.0 mmol) in 16 h according to the general procedure for
MOBI3-catalyzed hydrostannations as a colourless oil (169 mg,
0.35 mmol, 35%). 1H NMR (400 MHz, CDCl3): δ = 0.89 (t, J =
7.3 Hz, 9 H), 0.94–0.98 (m, 6 H), 1.28–1.36 (t, J = 6.2 Hz, 18 H),
1.47–1.54 (m, 6 H), 2.73 (d, J = 22.3 Hz, 2 H), 4.68 (sept, J =
6.2 Hz, 2 H), 5.31 (dd, J = 5.1, 2.4 Hz, 1 H), 5.86 (dd, J = 5.4,
Conclusions
In conclusion, we have shown that molybdenum-cata-
lyzed hydrostannations of propargyl and alkynylphos-
phonates gave rise to stannylated phosphonates. Palladium-
catalyzed cross coupling reactions of these phosphonates
with alkyl and aryl halides occur with clean retention of 2.4 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.2, 13.7,
3854
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Eur. J. Org. Chem. 2008, 3852–3858

Molybdenum-Catalyzed Hydrostannations
24.0 (q, J = 7.5 Hz), 27.4, 29.0, 38.5, 39.9, 69.9 (d, J = 6.7 Hz), added and the mixture stirred vigorously for 2 h. The reaction mix-
130.2 (d, J = 14 Hz), 144.5 (d, J = 11.4 Hz) ppm. 31P NMR ture was extracted with diethyl ether and the precipitated tin fluo-
(162 MHz, CDCl3) : δ = 25.5 ppm. 119Sn NMR (149 MHz, CDCl3) ride was filtered off. The residue obtained after evaporation was
δ = –40.7 (d, J = 32.8 Hz) ppm. HRMS (CI) m/z calcd. for
C21H46O3PSn [M + H]+: 496.2128, found 496.2151. HRMS (CI)
m/z calcd. for C17H37O3PSn [M – Bu]+: 439.1424, found 439.1429.
purified by flash chromatography to yield 9 as a colourless oil
(112 mg, 0.40 mmol, 86%). (E)-9: H NMR (400 MHz, CDCl3): δ
1
= 1.30 (d, J = 7.1 Hz, 3 H), 1.80 (ddd, J = 15.6, 6.6, 2.2 Hz, 1 H),
2.39 (ddd, J = 15.6, 6.6, 2.2 Hz, 1 H), 3.26–3.34 (m, 1 H), 3.70 (dd,
J = 10.9, 2.7 Hz, 6 H), 6.80 (d, J = 16.0 Hz, 1 H), 7.38–7.40 (m, 3
H), 7.55–7.57 (m, 2 H), 7.65 (d, J = 16.0 Hz, 1 H) ppm. 13C NMR
(100 MHz, CDCl3) δ = 18.8 (d, J = 10.2 Hz), 27.1 (d, J = 141.4 Hz),
38.8 (d, J = 3.3 Hz), 52.3 (dd, J = 6.6, 3.1 Hz), 124.3, 128.4, 128.5,
128.9, 130.6, 134.4, 143.6, 201.1 (d, J = 10.3 Hz) ppm. 31P NMR
(162 MHz, CDCl3): δ = 33.1 ppm. Selected signal for minor isomer
(Z)-9: 1H NMR (400 MHz, CDCl3): δ = 1.15 (d, J = 7.1 Hz, 3 H),
1.67 (ddd, J = 15.6, 6.6, 2.2 Hz, 1 H), 2.3 (ddd, J = 15.6, 6.6,
2.2 Hz, 1 H), 2.80–2.93 (m, 1 H), 3.65 (dd, J = 10.9, 2.7 Hz, 6 H),
6.25 (d, J = 12.7 Hz, 1 H), 6.80 (d, J = 12.7 Hz, 1 H), 7.16–7.19
(m, 3 H), 7.24–7.28 (m, 2 H) ppm. HRMS (CI) m/z calcd. for
C14H19O4P (mixture of isomers) [M]+: 282.1021, found 282.1044.
Diisopropyl [(3E)-3-(Tributylstannyl)allyl]phosphonate (6b): Stann-
ane 6b was obtained as the minor regioisomer in the hydrostann-
ation of 4b. 1H NMR (400 MHz, CDCl3): δ = 0.87–0.90 (m, 15 H),
1.26–1.33 (m, 18 H), 1.45–1.53 (m, 6 H), 2.66 (dd, J = 6.8, 1.2 Hz,
1 H), 2.71 (dd, J = 6.8, 1.2 Hz, 1 H), 4.68 (sept, J = 6.2 Hz, 2 H),
5.85–5.95 (m, 1 H), 6.12 (ddt, J = 18.8, 4.4, 1.2 Hz, 1 H) ppm.
31P NMR (162 MHz, CDCl3): δ = 25.1 ppm. 119Sn NMR (149 Hz,
CDCl3): δ = –49.8 (d, J = 23 Hz) ppm.
Dimethyl (2-Methylenepent-4-enyl)phosphonate (7): A mixture of
dimethyl 2-[(tributylstannyl)allyl]phosphonate (5a) (123 mg,
0.28 mmol) and allyl bromide (84.6 mg, 0.70 mmol) was dissolved
in dry THF (1 mL) in a Schlenk tube under argon. A solution of
[(allyl)PdCl]2 (1 mg, 2.8 µmol) and PPh3 (3.3 mg, 0.12 mmol) in dry
THF (1 mL) was added and the reaction mixture was warmed up
to 55 °C overnight. The solution was cooled to room temperature,
before a saturated aqueous solution of KF was added and mixture
stirred vigorously for 2 h. The reaction mixture was extracted with
diethyl ether and the precipitated tin fluoride was filtered. The resi-
due obtained after evaporation was purified by flash chromatog-
raphy to yield phosphonate 7 as a colourless oil (52 mg, 0.27 mmol,
91%). 1H NMR (400 MHz, CDCl3): δ = 2.61 (d, J = 22.3 Hz, 2
H), 2.93 (d, J = 6.7 Hz, 2 H), 3.74 (d, J = 10.8 Hz, 6 H), 4.98–5.03
(m, 2 H), 5.07–5.12 (m, 2 H), 5.71–5.81 (m, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 32.2 (d, J = 137.9 Hz), 41.2 (d, J = 3.4 Hz),
53.7 (d, J = 6.9 Hz), 115.8 (d, J = 11.6 Hz), 117.1, 135.4, 138.2 (d,
J = 10.4 Hz) ppm. 31P NMR (162 MHz, CDCl3): δ = 29.5 ppm.
HRMS (CI) m/z calcd. for C8H16O3P [M + H]+: 191.0837, found
191.0835.
Dimethyl (2-Iodoallyl)phosphonate (10): Iodine (62 mg, 0.24 mmol)
dissolved in CHCl3 (0.7 mL) was added to a solution of dimethyl
[2-(tributylstannyl)allyl]phosphonate 5a (100 mg, 0.23 mmol) in
CHCl3 (0.5 mL) at room temperature. After 1 h, saturated KF solu-
tion (1 mL) and ethyl acetate were added and the mixture was al-
lowed to stir for 2 h. The organic layer was separated and dried
with Na2SO4. After evaporation of the solvent, the crude product
was purified by flash chromatography to yield 10 as yellow liquid
1
(47 mg, 0.17 mmol, 75%). H NMR (400 MHz, CDCl3): δ = 3.16
(dd, J = 21.5, 1.0 Hz, 2 H), 3.79 (d, J = 10.9 Hz, 6 H), 5.95 (dd, J
= 5.1, 1.8 Hz, 1 H), 6.30 (dd, J = 5.3, 1.6 Hz, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 42.2 (d, J = 139.7 Hz), 53.1 (d, J = 6.7 Hz),
92.7 (d, J = 12.6 Hz), 131.4 (d, J = 10.7 Hz) ppm. 31P NMR
(162 MHz, CDCl3): δ = 25.6 ppm. HRMS (CI) m/z calcd. for
C5H11IO3P [M + H]+: 276.9490, found 276.9501. C5H10IO3P
(276.01): calcd. C 21.76, H 3.65; found C 22.42, H 3.51.
Dimethyl (2-Benzylallyl)phosphonate 8: A mixture of dimethyl [2-
(tributylstannyl)allyl]phosphonate (5a) (100 mg, 0.23 mmol) and
benzyl bromide (94 mg, 0.55 mmol) was dissolved in dry THF
(1 mL) in a Schlenk tube under argon. A solution of [(allyl)PdCl]2
(1 mg, 2.8 µmol) and PPh3 (3.3 mg, 0.12 mmol) in dry THF (1 mL)
was added and the reaction mixture was warmed up to 55 °C over-
night. The solution was cooled to room temperature, before a satu-
rated aqueous solution of KF was added and the mixture was
stirred vigorously for 2 h. The reaction mixture was extracted with
diethyl ether and the precipitated tin fluoride was filtered. The resi-
due obtained after evaporation was purified by flash chromatog-
raphy to yield product 8 as a colourless oil (57 mg, 0.23 mmol,
99%). 1H NMR (400 MHz, CDCl3): δ = 2.54 (dd, J = 22.2, 0.8 Hz,
2 H), 3.52 (s, 2 H), 3.75 (d, J = 10.9 Hz, 6 H), 5.01 (d, J = 5.4 Hz,
1 H), 5.07 (d, J = 5.4 Hz, 1 H), 7.20–7.24 (m, 3 H), 7.28–7.32 (m,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 31.8 (d, J =
137.7 Hz), 43.3 (d, J = 3.4 Hz), 52.7 (d, J = 7.0 Hz), 116.6 (d, J =
11.6 Hz), 126.4, 128.4, 129.1, 138.7, 139.1 (d, J = 10.4 Hz) ppm.
31P NMR (162 MHz, CDCl3): δ = 29.5 ppm. HRMS (CI) m/z
calcd. for C12H18O3P [M + H]+: 241.0993, found 241.1005.
Diethyl [1-(Tributylstannyl)vinyl]phosphonate (12a): Stannylated vin-
ylphosphonate 12a was prepared from 11a (162 mg, 1.0 mmol)
according to the general procedure for MOBI3-catalyzed hydro-
stannations in 12 h as a colourless oil (258 mg, 0.57 mmol, 57%).
1H NMR (400 MHz, CDCl3): δ = 0.90 (t, J = 7.3 Hz, 9 H), 1.09–
1.04 (m, 6 H), 1.31 (t, J = 7.1 Hz, 6 H), 1.26–1.35 (m, 6 H), 1.47–
1.55 (m, 6 H), 4.00–4.10 (m, 4 H), 6.25 (dd, J = 62.2, 3.3 Hz, 1 H),
6.90 (dd, J = 34.6, 3.3 Hz, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 10.2 (d, J = 1.2 Hz), 13.6, 16.4 (d, J = 6.0 Hz), 27.2,
28.7, 61.2 (d, J = 6.0 Hz), 142.7 (d, J = 130.7 Hz), 144.1 (d, J =
2.7 Hz) ppm. 31P NMR (162 MHz, CDCl3): δ = 24.1 ppm. 119Sn
NMR (149 MHz, CDCl3): δ = –29.1 (d, J = 112 Hz) ppm. HRMS
(CI) m/z calcd. for C14H31O3PSn [M – Bu]+: 397.0955, found
397.0941.
Diethyl (E)-[1-(Tributylstannyl)prop-1-enyl]phosphonate (12b): Stann-
ylated vinylphosphonate 12b was prepared from 11b (176 mg,
1.0 mmol) according to the general procedure for MOBI3-catalyzed
hydrostannations in 8 h as a colourless oil (313 mg, 0.67 mmol,
1
67%). H NMR (400 MHz, CDCl3): δ = 0.90 (t, J = 7.3 Hz, 9 H),
Dimethyl (2-Methyl-3-oxo-5-phenylpent-4-enyl)phosphonate (9): A
mixture of dimethyl [2-(tributylstannyl)allyl]phosphonate 5a
(200 mg, 0.46 mmol) and cinnamoyl chloride (184 mg, 1.1 mmol)
was dissolved in dry THF (1 mL) in a Schlenk tube under argon.
A solution of [(allyl)PdCl]2 (2 mg, 5.6 µmol) and PPh3 (3.3 mg,
0.12 mmol) in dry THF (1 mL) was added and the reaction mixture
was warmed up to 55 °C overnight. The solution was cooled to
room temperature, before a saturated aqueous solution of KF was
0.95–0.99 (m, 6 H), 1.27–1.36 (m, 12 H), 1.46–1.54 (m, 6 H), 2.18
(dd, J = 6.8, 3.6 Hz, 3 H), 4.04 (quin, J = 7.2 Hz, 4 H), 6.66 (dq,
J = 64.5, 6.8 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
10.6 (d, J = 1.1 Hz), 13.6, 16.4 (d, J = 6.5 Hz), 20.6 (d, J =
14.5 Hz), 27.3, 28.8, 60.8 (d, J = 5.7 Hz), 132.2 (d, J = 132.4 Hz),
156.8 ppm. 31P NMR (162 MHz, CDCl3): δ = 22.9 ppm. 119Sn
NMR (149 MHz, CDCl3): δ = –20.8 (d, J = 127.4 Hz) ppm. HMRS
(CI) m/z calcd. for C19H42O3PSn [M + H]+: 468.1815, found
Eur. J. Org. Chem. 2008, 3852–3858
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3855

N. Jena, U. Kazmaier
FULL PAPER
468.1768; m/z calcd. for C15H32O3PSn [M – Bu]+: 411.1111, found
411.1089. C19H41O3PSn (467.19): calcd. C 48.84, H 8.85; found C
48.83, H 8.89.
[M]+: 557.2215, found 557.2206. C26H47O3PSn (557.32): calcd. C
56.03, H 8.50; found C 56.69, H 8.54.
Diethyl
(E)-[1-(Tributylstannyl)-2-cyclohexylvinyl]phosphonate
(12f): Stannylated vinylphosphonate 12f was prepared from 11f
(245 mg, 1.0 mmol) according to the general procedure for MOBI3-
catalyzed hydrostannations in 12 h as a colourless oil (273 mg,
0.51 mmol, 51%). 1H NMR (400 MHz, CDCl3): δ = 0.90 (t, J =
7.3 Hz, 9 H), 0.94–0.98 (m, 6 H), 1.01–1.72 (m, 28 H), 2.98–3.08
(m, 1 H), 4.02 (m, 4 H), 6.28 (dd, J = 64.8, 9.8 Hz, 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 10.6 (d, J = 1.0 Hz), 13.7, 16.4 (d,
J = 6.6 Hz), 25.3, 25.9, 27.3, 27.5, 28.8, 32.3 (d, J = 2.1 Hz), 42.8
(d, J = 12.4 Hz), 60.1 (d, J = 5.7 Hz), 127.0, 128.3 (d, J =
134.0 Hz), 167.6 ppm. 31P NMR (162 MHz, CDCl3): δ = 23.1 ppm.
119Sn NMR (149 MHz, CDCl3): δ = –20.0 (d, J = 134.4 Hz) ppm.
HRMS (CI) m/z calcd. for C20H40O3PSn [M – Bu]+: 479.1737,
found 479.1751.
Diethyl (E)-[1-(Tributylstannyl)pent-1-enyl]phosphonate (12c): Stann-
ylated vinylphosphonate 12c was prepared from 11c (205 mg,
1.0 mmol) according to the general procedure for MOBI3-catalyzed
hydrostannations in 12 h as a colourless oil (302 mg, 0.61 mmol,
1
61%). H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 7.3 Hz, 9 H),
0.93–0.97 (m, 9 H), 1.26–1.35 (t, J = 7.1 Hz, 14 H), 1.44–1.52 (m,
8 H), 2.56 (dq, J = 7.5, 3.3 Hz, 2 H), 4.01 (quin, J = 7.2 Hz, 4 H),
6.50 (dt, J = 64.2, 7.1 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 10.6 (d, J = 1.1 Hz), 13.6, 13.7, 16.4 (d, J = 6.6 Hz), 22.3, 27.3,
28.8, 36.1, 60.7 (d, J = 5.7 Hz), 130.6 (d, J = 233.4 Hz), 162.5 ppm.
31P NMR (162 MHz, CDCl3):
δ =
22.9 ppm. 119Sn NMR
(149 MHz, CDCl3): δ = –20.4 (d, J = 131.4 Hz) ppm. HRMS (CI)
m/z calcd. for C21H45O3PSn [M]+: 495.2058, found 495.2012.
HRMS (CI) m/z calcd. for C17H36O3PSn [M – Bu]+: 439.1424,
found 439.1281. C21H45O3PSn (495.25): calcd. C 50.93, H 9.16;
found C 51.11, H 9.10.
Diethyl (Z)-(1-Phenylpent-1-enyl)phosphonate (14): diethyl (E)-[1-
(tributylstannyl)pent-1-enyl]phosphonate (12c) (247 mg, 0.5 mmol)
and iodobenzene (92 mg, 0.45 mmol) were dissolved in dry N-
methylpyrrolidinone (NMP) (3 mL). This solution was added to a
solution of Pd2(dba)3 (8.2 mg, 9 µmol) and tri(2-furyl)phosphane
(17 mg, 0.073 mmol) in dry NMP (1 mL) followed by addition of
CuI (95 mg, 0.5 mmol). The reaction mixture was stirred at room
temperature overnight. The reaction mixture was poured into 10%
aqueous KF solution (5 mL) stirred vigourously for 20 min before
it was filtered through celite. After evaporation of the solvent, the
residue was purified by flash chromatography to yield 14 as yellow
oil (57 mg, 0.20 mmol, 45%). 1H NMR (400 MHz, CDCl3): δ =
0.98 (t, J = 7.4 Hz, 3 H), 1.24 (t, J = 7.1 Hz, 6 H), 1.44–1.48 (m,
2 H), 2.58 (dq, J = 7.5, 3.2 Hz, 2 H), 4.09–4.19 (m, 4 H), 6.46 (dt,
J = 48.5, 7.7 Hz, 1 H), 7.24–7.34 (m, 5 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 13.8, 16.2 (d, J = 6.6 Hz), 22.6 (d, J =
1.7 Hz), 32.5 (d, J = 5.9 Hz), 61.5 (d, J = 5.7 Hz), 127.1, 128.0,
128.4, 128.4, 131.4 (d, J = 175.8 Hz), 140.2 (d, J = 12.1 Hz), 152.6
(d, J = 11.3 Hz) ppm. 31P NMR (162 MHz, CDCl3): δ = 16.5 ppm.
HRMS (CI) m/z calcd. for C15H23O3P [M]+: 282.1385, found
282.1368. C15H23O3P (282.32): calcd. C 63.82, H 8.21; found C
63.20, H 8.00.
Diethyl (E)-[1-(Tributylstannyl)-2-phenylvinyl]phosphonate (E)-12d:
Stannylated vinylphosphonate (E)-12d was prepared from 11d
(240 mg, 1.0 mmol) according to the general procedure for MOBI3-
catalyzed hydrostannations in 15 h as a colourless oil (408 mg,
0.77 mmol, 77%). 1H NMR (400 MHz, CDCl3): δ = 0.92 (t, J =
7.3 Hz, 9 H), 1.06–1.10 (m, 6 H), 1.17 (t, J = 7.1 Hz, 6 H), 1.31–
1.40 (m, 6 H), 1.53 (m, 6 H), 3.82–3.90 (m, 4 H), 7.28–7.36 (m, 3
H), 7.51 (d, J = 62.8 Hz, 1 H), 7.64–7.66 (m, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 11.3, 13.7, 16.1 (d, J = 6.6 Hz), 27.3, 28.9,
61.1 (d, J = 6.6 Hz), 127.9, 128.6, 129.2, 134.4 (d, J = 135 Hz),
138.0 (d, J = 14.1 Hz), 156.0 ppm. 31P NMR (162 MHz, CDCl3):
δ = 21.9 ppm. 119Sn NMR (149 MHz, CDCl3): δ = –10.5 (d, J =
114 Hz) ppm.
Diethyl (Z)-[1-(Tributylstannyl)-2-phenylvinyl]phosphonate (Z)-12d:
Stannylated vinylphosphonate (Z)-12d was prepared from 11d
(240 mg, 1.0 mmol) according to the general procedure for MOBI3-
catalyzed hydrostannations in 6 h as a colourless oil. (387 mg,
0.73 mmol, 73%). 1H NMR (400 MHz, CDCl3): δ = 0.84 (t, J =
7.3 Hz, 9 H), 0.85–0.89 (m, 6 H), 1.18–1.28 (m, 6 H), 1.35 (t, J =
7.0 Hz, 6 H), 1.33–1.40 (m, 6 H), 4.09–4.13 (m, 4 H), 7.27–7.37 (m,
5 H), 8.40 (d, J = 33.6 Hz, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 12.0 (d, J = 1.9 Hz), 13.6, 16.4 (d, J = 6.6 Hz), 27.2,
28.8, 61.3 (d, J = 5.9 Hz), 127.6, 128.2, 128.6, 134.2, 134.5, 139.9
(d, J = 31.4 Hz), 158.4 ppm. 31P NMR (162 MHz, CDCl3): δ =
26.2 ppm. 119Sn NMR (149 MHz, CDCl3): δ = –40.6 (d, J =
104.0 Hz) ppm. HRMS (CI) m/z calcd. for C24H44O3PSn
[M + H]+: 530.1972, found 530.1966. C24H43O3PSn (529.27): calcd.
C 54.46, H 8.19; found C 54.71, H 8.10.
Diethyl (Z)-[1-(4-Nitrophenyl)pent-1-enyl]phosphonate (15): A solu-
tion of diethyl (E)-[1-(tributylstannyl)pent-1-enyl]phosphonate
(12c) (247 mg, 0.5 mmol) and p-Iodonitrobenzene (113 mg,
0.45 mmol) in dry NMP (3 mL) was added to a solution of
Pd2(dba)3 (8.2 mg, 9 µmol) and tri-2-furyl phosphane (17 mg,
0.073 mmol) in dry NMP (1 mL), followed by the addition of CuI
(95 mg, 0.5 mmol). The reaction mixture was stirred at room tem-
perature overnight, before it was poured into 10% aqueous KF
solution (5 mL). After vigorous stirring for 20 min the solution was
filtered through celite, dried (Na2SO4) and concentrated. The resi-
due was purified by flash chromatography to yield 15 as yellow oil
(101 mg, 0.31 mol, 67%). 1H NMR (400 MHz, CDCl3): δ = 0.98
(t, J = 7.4 Hz, 3 H), 1.36 (t, J = 7.1 Hz, 6 H), 1.44–1.48 (m, 2 H),
2.58 (dq, J = 7.9, 2.7 Hz, 2 H), 4.09–4.19 (m, 4 H), 6.45 (dt, J =
47.3, 8.0 Hz, 1 H), 7.50 (dd, J = 12.0, 4.0 Hz, 2 H), 8.16 (d, J =
8.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 13.8, 16.2 (d,
J = 6.4 Hz), 22.4 (d, J = 1.4 Hz), 32.6 (d, J = 5.7 Hz), 61.9 (d, J =
5.8 Hz), 123.3, 129.2, 129.2, 130.4 (d, J = 178.0 Hz), 147.5 (d, J =
12.4 Hz), 154.6 (d, J = 10.2 Hz) ppm. 31P NMR (162 MHz,
CDCl3): δ = 14.7 ppm. HRMS (CI) m/z calcd. for C15H22NO5P
[M]+: 327.1236, found 327.1250. C15H22NO5P (327.32): calcd. C
55.04, H 6.77, N 4.28; found C 55.03, H 6.68, N 4.43.
Diethyl
(E)-[1-(Tributylstannyl)-4-phenylbut-1-enyl]phosphonate
(12e): Stannylated vinylphosphonate 12e was prepared from 11e
(267 mg, 1.0 mmol) according to the general procedure for MOBI3-
catalyzed hydrostannations in 12 h as a colourless oil (330 mg,
0.59 mmol, 59%). 1H NMR (400 MHz, CDCl3): δ = 0.94 (t, J =
7.3 Hz, 9 H), 0.98–1.02 (m, 6 H), 1.33 (t, J = 7 Hz, 6 H), 1.35–1.40
(m, 6 H), 1.47–1.60 (m, 6 H), 2.83 (t, J = 7.3 Hz, 2 H), 2.99 (dq, J
= 7.2, 3.2 Hz, 2 H), 3.97–4.06 (m, 6 H), 6.55 (dt, J = 64.4, 7.1 Hz,
1 H), 7.17–7.29 (m, 5 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
10.6, 13.6, 16.4 (d, J = 6.4 Hz), 27.3, 28.8, 35.3 (d, J = 1.9 Hz),
35.7 (d, J = 13.2 Hz), 60.1 (d, J = 5.7 Hz), 125.9, 128.3, 128.6,
131.9 (d, J = 133.5 Hz), 141.2, 161.1 ppm. 31P NMR (162 MHz,
CDCl3): δ = 22.7 ppm. 119Sn NMR (149 MHz, CDCl3): δ = –19.9
Diethyl (Z)-(1-Benzylpent-1-enyl)phosphonate (16): To a solution of
(d, J = 128 Hz) ppm. HRMS (CI) m/z calcd. for C26H47O3PSn diethyl
(E)-[1-(tributylstannyl)pent-1-enyl]phosphonate
(12c)
3856
www.eurjoc.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 3852–3858

Molybdenum-Catalyzed Hydrostannations
(247 mg, 0.5 mmol) in toluene (2 mL) benzyl bromide (214 mg, (100 mg, 0.18 mmol) in THF (1 mL) benzoyl chloride (28 mg,
1.25 mmol) was added at room temperature under argon. The cata-
lyst solution was prepared in another Schlenk tube by stirring
Pd2(dba)3 (11 mg, 0.0125 mmol) and triphenylarsane (80 mg,
0.1 mmol) in toluene (1 mL) for 15 min, before it was added to the
stannane solution. The mixture was warmed up to 90 °C for 15 h.
After cooling to room temperature, saturated KF solution (5 mL)
was added and the mixture was stirred for 2 h, before diethyl ether
was added. The aqueous layer was separated and the organic layer
0.2 mmol) was added, followed by a THF solution (1 mL) of
[(allyl)PdCl]2 (1 mg, 0.002 mmol) and PPh3 (2.2 mg, 0.08 mmol).
The reaction mixture was warmed to 60 °C overnight. After cooling
to room temperature, 10% KF solution was added and the mixture
was stirred for 2 h. After separation of the layers, the aqueous
phase was extracted with diethyl ether and the combined organic
solvents were evaporated in vacuo. The residue was dissolved in
ethyl acetate, and the precipitated tin fluoride was filtered. The resi-
was washed with water. The combined organic layers were evapo- due obtained after evaporation of the solvent was purified by flash
rated under reduced pressure and the residue obtained was dis-
solved in ethyl acetate. The insoluble tributyltin fluoride was fil-
tered off, the solvent was removed and the crude product was puri-
fied by flash column chromatography giving rise to 16 in 51% yield
chromatography to yield 19 (43 mg, 0.17 mmol, 94%) as a yellow
oil. 1H NMR (400 MHz, CDCl3): δ = 1.3 (t, J = 7.2 Hz, 6 H),
4.11–4.15 (m, 4 H), 6.25 (t, J = 17.6 Hz, 1 H), 7.36–7.38 (m, 3 H),
7.49 (d, J = 17.6, 4.4 Hz, 1 H), 7.45–7.51 (m, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 16.1 (d, J = 6.5 Hz), 61.7 (d, J = 5.3 Hz),
116.7 (d, J = 191.4 Hz), 128.1, 129.3, 129.6, 135.3 (d, J = 8.7 Hz),
148.3 ppm. 31P NMR (162 MHz, CDCl3): δ = 19.5 ppm. HRMS
(CI) m/z calcd. C12H17O3P [M]+: 240.0915, found 240.0921.
C12H17O3P (240.24): calcd. C 59.99, H 7.13; found C 59.47, H 7.23.
1
(75 mg, 0.25 mmol). H NMR (400 MHz, CDCl3): δ = 0.85 (t, J =
7.4 Hz, 3 H), 1.14 (t, J = 7.1 Hz, 6 H), 1.32–1.41 (m, 2 H), 2.58
(dq, J = 7.5, 3.2 Hz, 2 H), 3.46 (d, J = 13.3 Hz, 2 H), 3.73–3.93
(m, 4 H), 6.10 (dt, J = 49.7, 7.7 Hz, 1 H), 7.09–7.22 (m, 5 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 13.7, 16.2 (d, J = 6.6 Hz), 22.5
(d, J = 2.0 Hz), 32.1 (d, J = 6.6 Hz), 41.0 (d, J = 12.7 Hz), 61.1 (d,
J = 5.6 Hz), 126.2, 128.2, 129.1, 128.4 (d, J = 173.1 Hz), 139.3 (d,
J = 4.5 Hz), 149.9 (d, J = 12.5 Hz) ppm. 31P NMR (162 MHz,
CDCl3): δ = 18.8 ppm. HRMS (CI) m/z calcd. for C16H25O3P
[M]+: 296.1541, found 296.1526.
Diethyl (E)-[1-(4-Nitrophenyl)-2-phenylvinyl]phosphonate (20):
A
mixture of diethyl (Z)-1-(tributylstannyl)-2-phenylvinylphos-
phonate (12d) (100 mg, 0.18 mmol) and p-iodo-nitrobenzene
(41.58 mg, 0.167 mmol) was dissolved in dry NMP (1 mL) before
it was added to a solution of Pd2(dba)3 (1 mg, 0.001 mmol) and
tri-(2-furyl)phosphane (2 mg, 0.08 mmol) in dry NMP (1 mL) fol-
lowed by addition of CuI (35.8 mg, 0.188 mmol) in the same sol-
vent (2 mL). The reaction mixture was stirred at room temperature
overnight and poured into 10% aqueous KF solution (3 mL). Stir-
ring was continued for 20 min and the mixture was then filtered
through celite. The filtrate was extracted twice with ether and the
combined organic layers were dried (Na2SO4) and concentrated in
vacuo. The residue obtained was purified by flash chromatography
Diethyl (E)-(1-Iodopent-1-enyl)phosphonate (17): Iodine (142 mg,
0.55 mmol), dissolved in CHCl3 (2 mL), was added to a solution
of diethyl (E)-[1-(tributylstannyl)pent-1-enyl]phosphonate (12c)
(247 mg, 0.5 mmol) in CHCl3 (1 mL) at room temperature. After
1 h, saturated KF solution (4 mL) and ethyl acetate were added,
and the suspension was allowed to stir for 2 h. After separation of
the layers, the organic layer was separated and dried with Na2SO4.
After evaporation of the solvent, the crude product was purified by
1
to yield 20 (36 mg, 0.1 mmol, 53%) as a colourless oil. H NMR
flash chromatography to yield 17 as
a yellow oil (136 mg,
0.41 mmol, 83%). 1H NMR (400 MHz, CDCl3): δ = 0.9 (t, J =
7.4 Hz, 3 H), 1.36 (t, J = 7.1 Hz, 6 H), 1.44–1.48 (m, 2 H), 2.58
(dq, J = 7.9, 2.6 Hz, 2 H), 4.09–4.19 (m, 4 H), 7.31 (dt, J = 43.3,
8.0 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 13.6, 16.2 (d,
J = 6.7 Hz), 22.0 (d, J = 1.7 Hz), 35.7 (d, J = 4.6 Hz), 62.7 (d, J =
5.5 Hz), 82.7 (d, J = 186.3 Hz), 163.5 (d, J = 12.6 Hz) ppm. 31P
NMR (162 MHz, CDCl3): δ = 8.90 ppm. HRMS (CI) m/z calcd. for
C9H18IO3P [M]+: 332.0038, found 331.9999. C9H18IO3P (332.12):
calcd. C 32.55, H 5.46; found C 32.63, H 5.18.
(400 MHz, CDCl3): δ = 1.30 (t, J = 7.3 Hz, 6 H), 4.16–4.11 (m, 4
H), 7.02 (d, J = 7.4 Hz, 2 H), 7.17–7.25 (m, 3 H), 7.46 (dd, J =
8.8, 1.8 Hz, 2 H), 7.71 (d, J = 24.4 Hz, 1 H), 8.21 (d, J = 8.9 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 16.7 (d, J = 6.2 Hz),
62.8 (d, J = 5.9 Hz), 124.5 (d, J = 1.6 Hz), 128.8, 129.9, 130.5 (d,
J = 1.0 Hz), 130.7, 130.8, 134.3 (d, J = 21.6 Hz), 143.5 (d, J =
8.1 Hz), 145.4 (d, J = 9.7 Hz), 147.8 (d, J = 2.4 Hz) ppm. 31P NMR
(162 MHz, CDCl3): δ = 16.4 ppm. HRMS (CI) m/z calcd. for
C18H20 NO5P [M]+: 361.1079, found 361.1078. C18H20NO5P: C
59.83, H 5.58, N 3.88; found C 60.25, H 5.62, N 3.77.
Diethyl
(Z)-(1-Iodo-2-phenylvinyl)phosphonate
(18):
Iodine
(53.2 mg, 0.206 mmol), dissolved in CHCl3 (0.7 mL), was added to
a solution of diethyl (Z)-[1-(tributylstannyl)-2-phenylvinyl]phos-
phonate (12d) (100 mg, 0.188 mmol) in CHCl3 (0.5 mL) at room
temperature. After 1 h, saturated KF solution (2 mL) and ethyl ace-
tate were, and the suspension was allowed to stir for 2 h. After
separation of the layers, the organic layer was separated and dried
with Na2SO4. Evaporation of the solvent and purification of the
crude product by flash chromatography yielded 18 (57 mg,
Acknowledgments
This work was supported by the Deutsche Forschungsgemeinschaft
(DFG) and by the Fonds der Chemischen Industrie. N. J. thanks
the Alexander von Humboldt Foundation for a postdoctoral fel-
lowship.
1
0.15 mmol, 83%) as a yellow oil. H NMR (400 MHz, CDCl3): δ
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(100 MHz, CDCl3): δ = 16.2 (d, J = 6.6 Hz), 63.0 (d, J = 5.5 Hz),
86.0 (d, J = 189.1 Hz), 128.3, 129.0, 130.0, 135.7 (d, J = 19.2 Hz),
151.4 (d, J = 13.0 Hz) ppm. 31P NMR (162 MHz, CDCl3): δ =
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Diethyl (E)-(2-Phenylvinyl)phosphonate (19): To a solution of di-
ethyl (Z)-[1-(tributylstannyl)-2-phenylvinyl]phosphonate (12d)
Eur. J. Org. Chem. 2008, 3852–3858
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3857

N. Jena, U. Kazmaier
FULL PAPER
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Received: May 27, 2008
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