An efficient synthesis of 2-(1-(E)-alkenyl)phenylphosphonates via Suzuki reaction of aryl nonaflates with (E)-1-alkenylboronates

Article abstract of DOI:10.1016/j.jfluchem.2013.03.015

An efficient and general Suzuki coupling reaction between 2-phosphonylaryl nonaflates and (E)-1-alkenylboronic pinacol esters using Pd(OAc) ₂/PPh₃ as catalysts, K₂CO₃ as base and DMF as solvent has been develope

Full text of DOI:10.1016/j.jfluchem.2013.03.015

Journal of Fluorine Chemistry 151 (2013) 58–62
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Short communication
An efficient synthesis of 2-(1-(E)-alkenyl)phenylphosphonates via
Suzuki reaction of aryl nonaflates with (E)-1-alkenylboronates
*
Ai-Yun Peng , Ba-Tian Chen, Pei-Jiang Chen
School of Chemistry & Chemical Engineering, Sun Yat-sen University, 135 Xingangxi Lu, Guangzhou 510275, China
A R T I C L E I N F O
A B S T R A C T
Article history:
An efficient and general Suzuki coupling reaction between 2-phosphonylaryl nonaflates and (E)-1-
alkenylboronic pinacol esters using Pd(OAc)2/PPh3 as catalysts, K2CO3 as base and DMF as solvent has
been developed. This strategy allows for convenient synthesis of twelve 2-(1-(E)-alkenyl)phenylpho-
sphonates in good to excellent yields, most of which are not readily available by the previously reported
Heck reaction of the same aryl nonaflates and terminal alkenes.
Received 9 February 2013
Received in revised form 16 March 2013
Accepted 20 March 2013
Available online 28 March 2013
Crown Copyright ß 2013 Published by Elsevier B.V. All rights reserved.
Keywords:
Aryl nonaflates
Suzuki reaction
Hydroboration
(E)-1-Alkenylboronates
Phosphonates
1. Introduction
2. Results and discussion
The palladium-catalyzed cross-coupling reaction of aryl/vinyl
nonaflates is one of the most powerful, economical and
convenient methods to construct carbon–carbon bonds [1]. In
recent years, we prepared a series of 2-(1-alkynyl)phenylpho-
sphonates via the Sonogashira reaction of the 2-phosphonylaryl
nonaflates with terminal alkynes [2] and examined their
applications in the synthesis of a class of phosphorus hetero-
cycles (i.e. phosphaisocoumarins) [3]. In continuation of our
research programs, we need to synthesize various 2-(1-alke-
nyl)phenylphosphonates as key intermediates for the following
cyclization reactions. However, the Heck reaction of 2-phospho-
nylaryl nonaflates and terminal alkenes has very limited
generality and only five 2-(1-(E)-alkenyl)phenylphosphonates
were obtained in low to moderate yields [4]. In many cases, such
Heck reaction only led to inseparable regioisomer and/or
stereoisomer mixtures. It is highly desirable to develop a more
efficient, general and stereoselective method to the target
alkenes. Herein, we investigated the palladium-catalyzed Suzuki
coupling reaction [5] of the aryl nonaflates with (E)-1-alkenyl-
boronates in the present study.
We first examined the synthesis of (E)-1-alkenylboronic acids
as the following Suzuki coupling reaction partners via the
hydroboration of terminal alkynes according to the literature
known procedures [6]. Unfortunately, the reaction of phenylace-
tylene with catecholborane followed by in situ hydrolysis afforded
the desired product 2 only in 25% yield (Scheme 1). The low yield of
2 was mainly caused by the losses upon purification, since we
conducted the reaction only in
a small scale and it was
troublesome to separate 2 from the air-sensitive byproduct
catechol.
Due to the inconvenience and low yield of the above reaction,
we turned our attention to the synthesis of (E)-1-alkenylboronic
pinacol esters. Based on Shirakawa’s method [7] with some
modifications, four (E)-1-alkenylboronic pinacol esters 3a–d
were prepared in good yields via the hydroboration of terminal
alkynes with catecholborane followed by the transesterification
with pinacol (Table 1). The lipophilic compounds 3a–d, that is
not sensitive to air and moisture, could be obtained very
conveniently and pure enough for the subsequent coupling
reaction by simple washing off the by-product catechol and
excess pinacol with water.
The Suzuki reaction of (E)-1-phenylethenylboronic pinacol
ester 3a and 2-phosphonylphenyl nonaflate 4a [2b] in DMF using
K2CO3 as the base was then investigated. All these reactions were
detected by 31P NMR and thin-layer chromatography (TLC) and the
* Corresponding author. Tel.: +86 020 84110383; fax: +86 020 84112245.
E-mail address: cespay@mail.sysu.edu.cn (A.-Y. Peng).
0022-1139/$ – see front matter. Crown Copyright ß 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2013.03.015

A.-Y. Peng et al. / Journal of Fluorine Chemistry 151 (2013) 58–62
59
Scheme 1. Synthesis of (E)-phenylethenyl boronic acid 2.
Table 1
results are summarized in Table 2. Among the different catalysts
examined, Pd(PPh3)4 provided the highest yield of the desired
product 5a, that was slightly better than the combination of
Pd(OAc)2 and PPh3 (Entries 1–5). Taking into account that
Pd(PPh3)4 is air-sensitive and more expensive, we chose
Pd(OAc)2/PPh3 as the catalysts in the subsequent reactions. Further
reaction optimization suggested that heating is required and the
best temperature is 90 8C. When the reaction temperature was
raised from 70 8C to 90 8C, the yield of 5a was improved from 57%
to 74% (Entries 5 and 6), but further increasing the temperature to
100 8C led to decreased yield and some undesirable byproducts
were observed (Entries 7 and 8). In addition, increasing the amount
of the boronate 5a was found to be beneficial to this reaction
(Entries 6 and 7).
Synthesis of alkenylbronic pinacol esters 3.a
.
Entry
Product 3 (R1)
Isolated yield (%)
1
2
3
4
3a (Ph)
73
73
68
77
3b(p-FC6H4)
3c (c-C3H5)
3d (n-Bu)
a
1 (1.0 equiv.) and catechol borane (1.1 equiv.) were reacted at 70 8C for 4–5 h,
then added pinacol (1.6 equiv.).
Table 2
Optimization of the Suzuki reaction conditions of 3a and 4a.a
.
Entry
3a (equiv.)
Catalyst (equiv.)
Temp. (time)
Conversion (%)b
Yield 5a (%)b
1
2
3
4
5
6
7
8
1.2
1.2
1.2
1.2
1.2
1.2
1.5
1.5
PdCl2(PPh3)2 (0.05)
70 8C (5 h)
70 8C (5 h)
70 8C (5 h)
70 8C (7 h)
70 8C (5 h)
90 8C (5 h)
90 8C (5 h)
100 8C (5 h)
51
74
45
63
5
Pd(PPh3)4 (0.05)
Pd(OAc)2 (0.05)
5
CuI(0.1), DABCO(0.2), TBAB(1)
Pd(OAc)2 (0.05), PPh3 (0.2)
Pd(OAc)2 (0.05), PPh3 (0.2)
Pd(OAc)2 (0.05), PPh3 (0.2)
Pd(OAc)2 (0.05), PPh3 (0.2)
100
68
0c
57
70
85
65d
85
100
100
a
General reaction conditions unless otherwise specified: 4a (30–50 mg, 1.0 equiv.), 3a, K2CO3 (1.0 equiv.) in DMF.
Determined by 31P NMR.
b
c
Unidentified compound.
d
Some unidentified compounds with strong polarity were detected.
Table 3
Synthesis of 5 via the Suzuki reaction of 3 and 4.a
.
Entry
3 (R1)
4 (R2)
Conversion (%)b
Isolated yield (%)
1
2
3a (Ph)
4a (H)
100
100
100
100
100
100
100
100
86
5a (74)
5b (84)
5c (93)
5d (59)
5e (94)
5f (57)
5g (80)
5h (79)
5i (65)
5j (64)
5k (84)
5l (60)
3b (p-FC6H4)
3c (c-C3H5)
3d (n-Bu)
3a (Ph)
4a (H)
3
4a (H)
4
4a (H)
5
4b (Cl)
4b (Cl)
4b (Cl)
4b (Cl)
4c (OMe)
4c (OMe)
4c (OMe)
4c (OMe)
6
3b (p-FC6H4)
3c (c-C3H5)
3d (n-Bu)
3a (Ph)
7
8
9
10
11
12
3b (p-FC6H4)
3c (c-C3H5)
3d (n-Bu)
83
100
100
a
General reaction conditions: 4 (1.0 equiv.), 3 (1.5 equiv.), Pd(OAc)2 (0.05 equiv.), PPh3 (0.2 equiv.), K2CO3 (1.0 equiv.), in DMF at 90 8C for 6 h.
Determined by 31P NMR.
b

60
A.-Y. Peng et al. / Journal of Fluorine Chemistry 151 (2013) 58–62
To explore the scope of this reaction, three arylnonaflates (4a–
precipitate was filtered, washed with water and recrystallized
from hot water to afford white crystals 333 mg, yield, 25%. Mp:
c) were treated with the (E)-1-alkenylboronates (3a–d) under the
optimized conditions (Pd(OAc)2/PPh3, K2CO3, 90 8C, in DMF) and
the results are shown in Table 3. Compared with the Heck reaction
of 4a–c with alkenes [4], the present reaction is more general and
twelve 2-(1-(E)-alkenyl)phenylphosphonates 5 could be obtained
in good to excellent yields. Functionalities, for example, R1 = n-
butyl, cyclopropyl, phenyl and 4-fluorophenyl, R2 = methoxy,
chlorine, hydrogen, were able to withstand the reaction conditions.
Compound 4c with an electron-donating methoxy group was very
difficult to react with the alkenes in the Heck reaction, while 4c
exhibited good reactivity in the present reaction (Entries 9–12).
Using the present strategy, many compounds, that are not readily
available (i.e. 5i) or can be synthesized but in relatively low
yields (i.e. 5a, 5e) in the Heck reaction, can be obtained
conveniently in improved yields. For some reactions, the isolated
yields were quite lower than their conversions (Entries 4, 6
and 12), which were mainly caused by the losses upon column
chromatography since the polarity of these products are very close
to the by-product triphenylphosphine oxide.
It should be noted that we only isolated the desired trans
isomers with retention of the configuration of the (E)-1-
alkenylboronates, no or trace amount of the cis isomers were
detected in all cases. In contrast, mixtures of cis, trans and branched
isomer mixtures were observed and in many cases these products
produced by the Heck reaction cannot be separated [4]. The
structures of all products were determined spectroscopically.
The configuration of compounds 3 and 5 was determined by the
analysis of their 1H NMR spectra. In the alkenyl region of all these
compounds, the proton-proton coupling constant of the two vinyl
hydrogen is larger than 15.0 Hz (see Section 4), strongly indicating
the trans configuration of them.
164–167 8C. Lit. 162–164 8C [6a]. 1H NMR (300 MHz, CDCl3):
d 7.79
(d, J = 18.1 Hz, 1H), 7.67–7.58 (m, 2H), 7.46–7.31 (m, 3H), 6.36 (d,
J = 18.1 Hz, 1H), 4.30 (s, 2H).
4.3. Typical procedure for the synthesis of 3
To catecholborane (2.28 g, 19 mmol) in a flame-dried flask
(under vacuum) under
a nitrogen atmosphere, was added
dropwise the terminal alkyne (18.2 mmol) at 0 8C. After stirred
at 70 8C for 4–5 h, the reaction mixture was added dropwise with
the solution of pinacol (4.73 g, 40 mmol) in THF (20 mL) at 0 8C,
and then stirred for 12 h at room temperature. After concentrated
in vacuo, the residue was diluted with hexane and washed with
water and brine, dried (Na2SO4), and evaporated in vacuo to
provide slightly yellow oil. The products obtained were pure
enough for the subsequent step.
4.3.1. (E)-2-Phenylethenylboronic acid pinacol ester (3a) [7]
Yellow oil. Yield, 73%. 1H NMR (300 MHz, CDCl3):
d 7.52–7.47
(m, 2H), 7.41 (d, J = 18.4 Hz, 1H), 7.37–7.28 (m, 3H), 6.18 (d,
J = 18.4 Hz, 1H), 1.34 (s, 12H); 13C NMR (75 MHz, CDCl3):
d 149.5,
137.4, 128.9, 128.6, 127.1, 109.8, 83.5, 25.1.
4.3.2. (E)-2-(4-Fluorostyryl)boronic acid pinacol ester (3b) [8]
Yellow solid, mp: 57–60 8C. Yield, 73%. 1H NMR (300 MHz,
CDCl3):
d 7.50–7.42 (m, 2H), 7.35 (d, J = 18.4 Hz, 1H), 7.06–6.98 (m,
2H), 6.08 (d, J = 18.4 Hz, 1H), 1.33 (s, 12H); 13C NMR (75 MHz,
CDCl3):
d 163.1 (d, JC–F = 247.9 Hz), 148.2, 133.7, 128.8, 128.7,
115.6 (d, JC–F = 21.2 Hz), 83.5, 25.0; 19F NMR (282 MHz, CDCl3):
À112.71.
d
3. Conclusions
4.3.3. ((E)-2-Cyclopropylethenyl)boronic acid pinacol ester (3c) [9]
Colorless oil. Yield, 68%. 1H NMR (300 MHz, CDCl3)
d 6.05 (dd,
We have developed a general and efficient palladium-catalyzed
Suzuki reaction of the arylnonaflates and (E)-1-alkenylboronic
pinacol esters for the synthesis of 2-(1-(E)-alkenyl)phenylpho-
sphonates. In the presence of Pd(OAc)2, PPh3 and K2CO3, twelve
target compounds were prepared in good to excellent yields. The
cyclization of these coupling products is currently underway and
the results will be reported in due course.
J = 18.0, 9.3 Hz, 1H), 5.52–5.42 (m, 1H), 1.57–1.44 (m, 1H), 1.24 (s,
12H), 0.84–0.75 (m, 2H), 0.56–0.49 (m, 2H); 13C NMR (75 MHz,
CDCl3):
d 158.6, 83.0, 25.0, 17.2, 8.1 [10].
4.3.4. (E)-1-Hexenylboronic acid pinacol ester (3d) [7]
Yield: 77%, colorless oil. 1H NMR (300 MHz, CDCl3):
d 0.91 (t,
J = 7.2 Hz, 3 H), 1.29 (s, 12 H), 1.28–1.44 (m, 4 H), 2.16 (q, J = 6.9 Hz, 2
H), 5.43 (d, J = 18.0 Hz, 1 H), 6.63 (dt, J = 18.0, 6.3 Hz, 1 H); 13C NMR
4. Experimental
(75 MHz, CDCl3): d 154.8, 83.0, 34.1, 32.0, 24.9, 22.4, 14.1 [10].
4.1. General
4.4. Typical procedure for the Suzuki reaction of 3 and 4
The 1H, 13C, 31P and 19F NMR spectra were recorded on a Varian
Mercury-Plus 300 NMR instrument. All melting points are
uncorrected. EI-mass spectra were recorded on a Thermo DSQ
EI-mass spectrometer. ESI-mass spectra were recorded on a LCMS-
2010A Liquid Chromatography mass spectrometer. HRMS were
To a mixture of Pd (OAc)2 (0.025 mmol) and PPh3 (0.1 mol) in a
flask under a nitrogen atmosphere, was added DMF (3.0 mL), 3
(0.75 mmol),
4 (0.5 mmol) and K2CO3 (0.5 mmol) at room
temperature. After stirring at 90 8C for 6 h, the reaction mixture
was diluted with EtOAc or CH2Cl2, washed with aqueous NH4Cl
until neutral and brine, dried (Na2SO4), and evaporated in vacuo.
The residue was chromatographed on silica gel using hexane/
EtOAc (8:1–1:1) as eluent to give the corresponding products 5. All
these compounds, except 5a and 5e [4], are new compounds.
determined by
a Thermo MAT95XP High Resolution mass
spectrometer. IR spectra were recorded as KBr pellets on a Bruker
Equinox 55 FT/IR spectrometer. Column chromatography was
performed on 200–300 mesh silica gel. Thin-layer chromatography
was conducted on Kieselgel 60 F254. The starting materials 4a, 4b
and 4c were prepared according to our previous procedures [2b].
4.4.1. [2-((E)-Styryl)-phenyl]-phosphonic acid diethyl ester (5a) [4]
Colorless oil. Yield, 74%. 1H NMR (300 MHz, CDCl3):
d 7.98 (ddd,
4.2. Procedure for the synthesis of (E)-phenylethenyl boronic acid (2)
J = 14.3, 7.7, 1.1 Hz, 1H), 7.88 (d, J = 16.1 Hz, 1H), 7.80–7.72 (m, 1H),
7.56–7.48 (m, 3H), 7.41–7.21 (m, 4H), 7.04 (d, J = 16.1 Hz, 1H),
4.27–3.99 (m, 4H), 1.30 (t, J = 7.2 Hz, 6H); 13C NMR (75 MHz,
To catecholborane (1.20 g, 10 mmol) in a flame-dried flask
(under vacuum) under
a
nitrogen atmosphere, was added
CDCl3): d 140.9 (d, JC–P = 9.4 Hz), 137.1, 134.3 (d, JC–P = 9.3 Hz),
dropwise phenylethynyl (9 mmol) at 0 8C. After stirred at 70 8C
for 4–5 h, the reaction mixture was added dropwise with water
(20 mL) at 0 8C, and was stirred at 80 8C for 1 h. The resultant
132.6, 131.4, 130.9, 128.7, 128.0, 127.0 (d, JC–P = 5.8 Hz), 126.8,
126.0 (d, JC–P = 13.8 Hz), 124.7, 62.2 (d, JC–P = 4.1 Hz), 16.5; 31P
NMR (121 MHz, CDCl3):
d 20.06.

A.-Y. Peng et al. / Journal of Fluorine Chemistry 151 (2013) 58–62
61
4.4.2. {2-[(E)-2-(4-Fluorostyryl]-phenyl}-phosphonic acid diethyl
ester (5b)
À113.39; MS (ESI): m/z: 369 [M+H]+, 391 [M+Na]+; Anal. Calcd. for
C
18H19ClFO3P: C, 58.63; H, 5.19. Found: C, 58.48; H, 5.38.
Colorless oil. Yield, 84%. IR (film): 3059, 2984, 1635, 1395, 1235,
1152, 1023 cmÀ1
7.6 Hz, 1H), 7.81 (d, J = 16.1 Hz, 1H), 7.77–7.69 (m, 1H), 7.55–7.43
(m, 3H), 7.31 (td, J = 7.4, 3.5 Hz, 1H), 7.08–6.93 (m, 3H), 4.25–3.99
(m, 4H), 1.29 (t, J = 7.0 Hz, 6H); 13C NMR (75 MHz, CDCl3):
;
1H NMR (300 MHz, CDCl3):
d
7.96 (dd, J = 14.3,
4.4.7. [5-Chloro-2-((E)-2-cyclopropyl-vinyl)-phenyl]-phosphonic
acid diethyl ester (5g)
Slightly yellow oil. Yield, 80%. IR (film): 3073, 2986, 1643, 1385,
1246, 1153, 1024 cmÀ1 1H NMR (300 MHz, CDCl3):
; d 7.82 (dd,
d
162.3
(d, JC–F = 247.3 Hz), 140.6 (d, JC–P = 9.5 Hz), 134.1 (d, JC–P = 9.3 Hz),
133.3, 132.5, 130.1, 128.2 (d, JC–P = 7.9 Hz), 126.9, 126.8, 125.9 (d,
JC–P = 13.9 Hz), 124.5, 115.6 (d, JC–F = 21.7 Hz), 62.1 (d, JC–
J = 14.8, 2.3 Hz, 1H), 7.44–7.29 (m, 2H), 7.01 (d, J = 15.5 Hz, 1H), 5.64
(dd, J = 15.5, 8.9 Hz, 1H), 4.17–3.94 (m, 4H), 1.64–1.51 (m, 1H), 1.29
(t, J = 7.0 Hz, 6H), 0.85–0.77 (m, 2H), 0.52–0.45 (m, 2H); 13C NMR
(75 MHz, CDCl3): d 139.7 (d, JC–P = 9.6 Hz), 138.8, 133.6 (d, JC–
P = 10.3 Hz), 132.3, 131.8 (d, JC–P = 19.9 Hz), 127.2 (d, JC–P = 15.2 Hz),
126.4 (d, JC–P = 181.6 Hz), 124.5, 62.3 (d, JC–P = 3.6 Hz), 16.4 (d, JC–
P = 4.5 Hz), 16.4 (d, JC–P = 6.1 Hz); 19F NMR (282 MHz, CDCl3):
d
À113.87; 31P NMR (121 MHz, CDCl3)
d
19.97; MS (ESI): m/z: 335
[M+H]+, 357 [M+Na]+, 373 [M+K]+; Anal. Calcd. for C18H20FO3P: C,
64.67; H, 6.03. Found: C, 64.63; H, 5.95.
P = 5.3 Hz), 15.0, 7.7; 31P NMR (121 MHz, CDCl3):
d
18.04; MS (ESI):
m/z: 315 [M+H]+, 337 [M+Na]+, 353 [M+K]+; Anal. Calcd. for
C15H20ClO3P: C, 57.24; H, 6.40. Found: C, 57.19; H, 6.67.
4.4.3. [2-((E)-2-Cyclopropyl-vinyl)-phenyl]-phosphonic acid diethyl
ester (5c)
Slightly yellow oil. Yield, 93%. IR (film): 3068, 2984, 1641, 1385,
; d 7.78 (dd,
1242, 1135, 1024 cmÀ1 1H NMR (300 MHz, CDCl3):
4.4.8. {5-Chloro-2-[(E)-hex-1-en-1-yl]-phenyl}-phosphonic acid
diethyl ester (5h)
J = 14.3, 7.6 Hz, 1H), 7.44–7.24 (m, 2H), 7.15–7.07 (m, 1H), 7.03 (d,
J = 15.5 Hz, 1H), 5.59 (dd, J = 15.5, 8.8 Hz, 1H), 4.14–3.78 (m, 4H),
1.59–1.44 (m, 1H), 1.20 (t, J = 7.0 Hz, 6H), 0.77–0.67 (m, 2H), 0.45–
Slightly yellow oil. Yield, 79%. IR (film): 3428, 2958, 1642,
1384, 1289, 1149, 1023 cmÀ1; 1H NMR (300 MHz, CDCl3):
d 7.92–
7.81 (m, 1H), 7.55–7.43 (m, 1H), 7.38 (dd, J = 8.4, 1.1 Hz, 1H), 6.98
(d, J = 15.6 Hz, 1H), 6.11 (dt, J = 15.6, 6.9 Hz, 1H), 4.24–3.90 (m,
4H), 2.23 (q, J = 7.0 Hz, 2H), 1.60–1.19 (m, 11H), 0.91 (t, J = 7.0 Hz,
0.38 (m, 2H); 13C NMR (75 MHz, CDCl3):
d 140.9 (d, JC–P = 9.7 Hz),
137.5, 133.6 (d, JC–P = 9.5 Hz), 132.0, 125.4, 125.3 (d, JC–P = 3.1 Hz),
122.9, 61.5(d, JC–P = 4.9 Hz), 16.0(d, JC–P = 5.2 Hz), 14.5, 7.2;31PNMR
3H); 13C NMR (75 MHz, CDCl3):
d 140.2 (d, JC–P = 9.0 Hz), 135.2,
(121 MHz, CDCl3):
d
20.24; MS (ESI): m/z: 281 [M+H]+, 303 [M+Na]+;
133.8 (d, JC–P = 10.5 Hz), 132.6, 132.2, 127.9 (d, J = 15.4 Hz), 127.4
(d, JC–P = 3.4 Hz), 127.1 (d, JC–P = 181.5 Hz), 125.9, 62.5 (d, JC–
P = 4.5 Hz), 33.1, 31.5, 22.5, 16.6 (d, JC–P = 6.1 Hz), 14.3. 31P NMR
Anal. Calcd. forC15H21O3P: C, 64.27; H, 7.55. Found: C, 64.42; H, 7.61.
4.4.4. {2-[(E)-Hex-1-en-1-yl]-phenyl}-phosphonic acid diethyl ester
(5d)
(121 MHz, CDCl3):
Calcd. for C16H24ClO3P; C, 58.10; H, 7.31. Found: C, 58.39; H, 7.43.
d
18.04. MS (ESI): m/z: 330 [MÀH]À; Anal.
Slightly yellow oil. Yield, 59%. IR (film): 3433, 2958, 1646, 1390,
1246, 1139, 1024 cmÀ1
;
1H NMR (300 MHz, CDCl3):
d
7.90 (dd,
4.4.9. [5-Methoxy-2-((E)-styryl)-phenyl]-phosphonic acid diethyl
ester (5i)
Slightly yellow oil. Yield, 65%. IR (film): 3061, 2982, 1594, 1397,
1242, 1152, 1025 cmÀ1 1H NMR (300 MHz, CDCl3):
; d 7.80 (d,
J = 16.1 Hz, 1H), 7.72 (dd, J = 8.7, 6.7 Hz, 1H), 7.59–7.48 (m, 3H),
7.40–7.31 (m, 2H), 7.29–7.21 (m, 1H), 7.08 (dd, J = 8.7, 2.8 Hz, 1H),
6.94 (d, J = 16.1 Hz, 1H), 4.26–4.01 (m, 4H), 3.87 (s, 3H), 1.36–1.26
(m, 6H); 13C NMR (75 MHz, CDCl3):
d 158.5, 158.2, 137.5, 133.3 (d,
J = 14.2, 7.6 Hz, 1H), 7.56 (t, J = 6.5 Hz, 1H), 7.44 (t, J = 7.4 Hz, 1H),
7.25 (s, 1H), 7.05 (d, J = 15.6 Hz, 1H), 6.24–6.11 (m, 1H), 4.21–3.95
(m, 4H), 2.25 (q, J = 6.6 Hz, 2H), 1.54–1.23 (m, 10H), 0.93 (t,
J = 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3):
d
141.8 (d, JC–P = 9.6 Hz),
134.6, 134.3 (d, JC–P = 9.6 Hz), 132.7, 128.4 (d, JC–P = 3.8 Hz), 126.5,
126.3, 125.0 (d, JC–P = 186.6 Hz), 62.2 (d, JC–P = 4.3 Hz), 33.2, 31.7,
22.6, 16.6 (d, JC–P = 6.0 Hz), 14.3. 31P NMR (121 MHz, CDCl3):
d
20.32. MS (ESI): m/z: 297 [M+H]+; Anal. Calcd. for [C16H25O3PÁ1/
JC–P = 8.9 Hz), 129.5, 128.7, 127.6, 127.5, 127.0 (d, JC–P = 180.1 Hz),
126.6, 119.2, 118.6 (d, JC–P = 10.8 Hz), 62.3 (d, JC–P = 4.5 Hz), 55.7,
4H2O]: C, 63.88; H, 8.54. Found: C, 63.49; H, 8.21.
16.6 (d, JC–P = 5.8 Hz); 31P NMR (121 MHz, CDCl3):
d 19.90; MS (EI):
4.4.5. [5-Chloro-2-((E)-styryl)-phenyl]-phosphonic acid diethyl ester
(5e) [4]
Slightly yellow oil. Yield, 94%. IR (film): 3060, 2982, 1633, 1388,
1248, 1154, 1023 cmÀ1 1H NMR (300 MHz, CDCl3):
; d 7.96 (dd,
m/z (%) = 346 (M+, 4), 259 (40), 231 (22), 215 (26), 187 (100), 149
(80), 123 (10); HRMS (EI): calcd. for C19H23ClO4P (M+): 346.1328;
found: 346.1332.
J = 14.8, 2.3 Hz, 1H), 7.82 (d, J = 16.2 Hz, 1H), 7.71 (dd, J = 8.4, 6.2 Hz,
1H), 7.56–7.46 (m, 3H), 7.42–7.27 (m, 3H), 7.03 (d, J = 16.1 Hz, 1H),
4.30–3.99 (m, 4H), 1.33 (t, J = 7.0 Hz, 6H); 13C NMR (75 MHz, CDCl3):
4.4.10. {2-[(E)-2-(4-Fluoro-phenyl)-vinyl]-5-methoxy-phenyl}-
phosphonic acid diethyl ester (5j)
Yellow oil. Yield, 64%. IR (film): 3066, 2983, 1598, 1397, 1240,
1155, 1024 cmÀ1; 1H NMR (300 MHz, CDCl3):
d 7.77–7.66 (m, 2H),
d
139.3 (d, JC–P = 9.2 Hz), 136.9, 134.0 (d, JC–P = 10.1 Hz), 133.0 (d, JC–
P = 19.5 Hz), 132.6, 132.0, 129.1, 128.8, 128.3, 127.5 (d, JC–
P = 15.7 Hz), 126.9, 125.9 (d, JC–P = 4.2 Hz), 62.6 (d, JC–P = 4.4 Hz),
7.56–7.43 (m, 3H), 7.11–6.99 (m, 3H), 6.90 (d, J = 16.1 Hz, 1H),
4.26–4.01 (m, 4H), 3.88 (s, 3H), 1.32 (t, J = 7.0 Hz, 6H); 13C NMR
(75 MHz, CDCl3): d 162.1 (d, JC–F = 246.9 Hz), 158.3 (d, JC–
16.5 (d, JC–P = 6.2 Hz); 31P NMR (121 MHz, CDCl3):
d
17.84.
P = 18.2 Hz), 133.6 (d, JC–P = 2.3 Hz), 133.0 (d, JC–P = 8.9 Hz),
128.1, 127.9 (d, JC–P = 7.8 Hz), 127.4 (d, JC–P = 16.3 Hz), 126.3,
125.8, 119.0, 118.5 (d, JC–F = 10.8 Hz), 115.5 (d, JC–F = 21.5 Hz), 62.2
(d, JC–P = 4.2 Hz), 55.5, 16.4 (d, JC–P = 6.0 Hz); 31P NMR (121 MHz,
4.4.6. {5-Chloro-2-[(E)-2-(4-fluoro-phenyl)-vinyl]-phenyl}-
phosphonic acid diethyl ester (5f)
Colorless oil. Yield, 57%. IR (film): 3061, 2983, 1634, 1386, 1239,
1155, 1024 cmÀ1
;
1H NMR (300 MHz, CDCl3):
d
7.89 (dd, J = 14.8,
CDCl3):
d
19.70; 19F NMR (282 MHz, CDCl3):
d
À114.53. MS (EI): m/
2.3 Hz, 1H), 7.70 (d, J = 16.1 Hz, 1H), 7.62 (dd, J = 8.4, 6.2 Hz, 1H),
z (%) = 364 (M+, 100), 336 (16), 307 (17), 290 (20), 227 (50), 187
(30), 183 (45), 123 (17); HRMS (EI): calcd. for C19H22FO4P (M+):
364.1234; found: 364.1233.
7.48–7.38 (m, 3H), 7.02–6.89 (m, 3H), 4.21–3.97 (m, 4H), 1.27 (t,
J = 7.0 Hz, 6H); 13C NMR (75 MHz, CDCl3)
d 162.4 (d, JC–
F = 247.6 Hz), 139.0 (d, JC–P = 9.1 Hz), 133.7 (d, JC–P = 8.6 Hz),
133.0, 132.7, 132.5, 130.5, 128.3 (d, JC–P = 7.8 Hz), 127.7 (d, JC–
P = 181.5 Hz), 127.3 (d, JC–P = 15.1 Hz), 125.5, 115.6 (d, JC–
F = 21.3 Hz), 62.4 (d, JC–P = 3.9 Hz), 16.4 (d, JC–P = 5.7 Hz); 31P
4.4.11. [2-((E)-2-Cyclopropyl-vinyl)-5-methoxy-phenyl]-phosphonic
acid diethyl ester (5k)
Slightly yellow oil. Yield, 84%. IR (film): 3072, 2986, 1642, 1396,
1242, 1152, 1027 cmÀ1; 1H NMR (300 MHz, CDCl3):
d 7.40–7.30 (m,
NMR (121 MHz, CDCl3):
d
17.72; 19F NMR (282 MHz, CDCl3):
d

62
A.-Y. Peng et al. / Journal of Fluorine Chemistry 151 (2013) 58–62
2H), 6.94 (d, J = 15.5 Hz, 1H), 6.87 (dd, J = 8.7, 2.8 Hz, 1H), 5.49 (dd,
J = 15.5, 8.8 Hz, 1H), 4.12–3.87 (m, 4H), 3.71 (s, 3H), 1.57–1.44 (m,
1H), 1.23 (t, J = 7.0 Hz, 6H), 0.76–0.68 (m, 2H), 0.44–0.37 (m, 2H);
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.jfluchem.2013.
03.015.
13C NMR (75 MHz, CDCl3):
d 157.4 (d, JC–P = 18.3 Hz), 135.8 (d, JC–
P = 4.2 Hz), 133.7 (d, JC–P = 9.1 Hz), 127.1 (d, JC–P = 16.9 Hz), 125.2
(d, JC–P = 179.9 Hz), 124.9, 118.9 (d, JC–P = 6.1 Hz), 118.1 (d, JC–
P = 7.4 Hz), 61.9 (d, JC–P = 4.2 Hz), 55.3, 16.3 (d, JC–P = 5.3 Hz), 14.6,
7.3; 31P NMR (121 MHz, CDCl3): 20.09. MS (ESI): m/z: 311 [M+H]+,
d
References
333 [M+Na]+; Anal. Calcd. for C16H23O4P: C, 61.93; H, 7.47. Found:
C, 61.67; H, 7.52.
[1] (a) K. Manabe, T. Kimura, Org. Lett. 15 (2013) 374–377;
(b) S. Shekhar, T.B. Dunn, B.J. Kotecki, D.K. Montavon, S.C. Cullen, J. Org. Chem. 76
(2011) 4552–4563;
(c) J.B. Grimm, K.J. Wilson, D.J. Witter, J. Org. Chem. 74 (2009) 6390–6393;
(d) J. Hogermeier, H.U. Reissig, Adv. Synth. Catal. 351 (2009) 2747–2763.
[2] (a) A.-Y. Peng, B. Li, X. Yang, J. Lin, Synthesis (2008) 2412–2416;
(b) A.-Y. Peng, X. Zhang, Y.X. Ding, Heteroat. Chem. (2005) 529–534.
[3] (a) A.-Y. Peng, F. Hao, B. Li, Z. Wang, Y. Du, J. Org. Chem. 73 (2008) 9012–9015;
(b) A.-Y. Peng, Y.-X. Ding, Tetrahedron 61 (2005) 10303–10308;
(c) A.-Y. Peng, Y.-X. Ding, Org. Lett. 6 (2004) 1119–1121;
(d) A.-Y. Peng, Y.-X. Ding, J. Am. Chem. Soc. 125 (2003) 15006–15007.
[4] A.-Y. Peng, B.-T. Chen, Z. Wang, B. Wang, X.-B. Mo, Y.-Y. Wang, P.-J. Chen, J.
Fluorine Chem. 132 (2011) 982–986.
4.4.12. {5-Methoxy-2-[(E)-hex-1-en-1-yl]-phenyl}-phosphonic acid
diethyl ester (5l)
Slightly yellow oil. Yield, 60%. IR (film): 3473, 2979, 1600, 1392,
1245, 1144, 1025 cmÀ1; 1H NMR (300 MHz, CDCl3):
d 7.47 (m, 1H),
7.03–6.90 (m, 1H), 6.05 (dt, J = 15.5, 6.9 Hz, 1H), 4.24–3.93 (m, 2H),
3.81 (s, 1H), 2.22 (q, J = 6.9 Hz, 1H), 1.54–1.21 (m, 4H), 0.92 (t,
J = 7.1 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d 157.9 (d, JC–
P = 18.5 Hz), 134.3 (d, JC–P = 9.2 Hz), 132.5, 128.0, 127.7, 126.0 (d,
JC–P = 180.2 Hz), 119.2, 118.4 (d, JC–P = 11.1 Hz), 62.2 (d, JC–
P = 4.1 Hz), 55.7, 33.1, 31.8, 22.6, 16.7, 14.3; 31P NMR (121 MHz,
[5] Recent reviews about the Suzuki coupling reactions, see:
(a) M. Mora, C. Jimenez-Sanchidrian, J.R. Ruiz, Curr. Org. Chem. 16 (2012) 1128–1150;
´
´
(b) J.G. Vries, Top. Organomet. Chem 42 (2012) 1–34;
(c) M.M. Heravi, E. Hashemi, Tetrahedron 68 (2012) 9145–9178;
(d) R. Narayanan, Molecules 15 (2010) 2124–2138.
CDCl3):
d
20.15; MS (ESI): m/z: 327 [M+H]+, 349 [M+Na]+; Anal.
Calcd. for [C17H27O4Pꢀ1/4H2O]: C, 61.71; H, 8.38. Found: C, 61.90;
H, 8.50.
[6] (a) I.J.S. Fairlamb, L.R. Marrison, J.M. Dickinson, F.J. Lu, J.P. Schmidt, Bioorg. Med.
Chem. 12 (2004) 4285–4299;
(b) H.C. Brown, S.K. Gupta, J. Am. Chem. Soc. 94 (1972) 4370–4371;
(c) C.F. Lane, G.W. Kabalka, Tetrahedron 32 (1976) 981–990.
[7] K. Shirakawa, A. Arase, M. Hoshi, Synthesis (2004) 1814–1820.
[8] M.J. Geier, S.J. Geier, C.M. Vogels, F. Be´land, S.A. Westcott, Synlett (2009) 477–481.
[9] S. Hanessian, U. Soma, S. Dorich, B. Descheˆnes-Simard, Org. Lett. 13 (2011) 1048–
1051.
Acknowledgment
This work was supported by the research grants from the
National Natural Science Foundation of China (Grant No.
20602043).
[10] The other alkenyl carbon atom was not observed. This result is consistent with
Ref. [7].