Silver-catalyzed synthesis of 2-arylvinylphosphonates by cross-coupling of β-nitrostyrenes with: H -phosphites

Article abstract of DOI:10.1039/c6ra19002b

An efficient protocol for stereoselective synthesis of 2-arylvinylphosphonates has been developed via AgNO₃-catalyzed cross-coupling of β-nitrostyrenes with dialkyl H-phosphites under mild conditions. By losing the nitro group of β-nitrostyrene

Full text of DOI:10.1039/c6ra19002b

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Silver-catalyzed synthesis of 2-arylvinylphosphonates by cross-
coupling of -nitrostyrenes with H-phosphites
β
Received 00th January 20 xx,
Accepted 00th January 20xx
Jin-Wei Yuan,* Liang-Ru Yang, Pu Mao, and Ling-Bo Qu*
An efficient protocol for stereoselective synthesis of 2-arylvinylphosphonates has been developed via AgNO3-catalyzed
DOI: 10.1039/x0xx00000x
cross-coupling of
β-nitrostyrenes with dialkyl H-phosphites under mild conditions. With losing nitro group of β-
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nitrostyrenes, the reaction proceeds smoothly and could provide the desired products with moderate to good yield.
been reported that trialkyl phosphates react with 1-bromoalkenes
and vinylboronate esters catalyzed by transition metal Pd, and Cu
(Scheme 1, c).10 Moreover, 2-arylvinylphosphonates are formed by
Introduction
Vinylphosphonates are important molecules known for their
interesting properties spanning across chemistry as well as
biology.1 They are suitable substrates for various name
reactions such as Michael additions, cycloaddition, and
Horner-Wadsworth-Emmons reactions.2 They have been also
extensively used in polymer sciences as additives or flame-
retardants.3 In medical chemistry, vinylphosphonates often
exhibit interesting biological properties such as antiviral,
antibacterial, anticancer implications.4 For these reasons, the
development of simple and stereoselective methods to
prepare vinylphosphonates has become important in organic
synthesis.
the Mizoroki-Heck reaction of arylboronic acids with dialkyl
vinylphosphonates catalyzed by Pd(OAc)2, and via nucleophilic
substitution of benzyl bromides with Bestmann-Ohira reagents.11
Although these approaches are available for the synthesis of 2-
arylvinylphosphonates, most of them suffer from several drawbacks
such as lack of stereoselectivity (a mixture of E/Z products), the
need to use a rather expensive catalyst, drastic conditions being not
compatible with molecules containing sensitive functional groups.
As a result, there is still a strong need for alternative methods that
would
allow
the
stereoselective
synthesis
of
2-
arylvinylphosphonates from readily available starting materials and
catalysts under mild reaction conditions.
In recent years, a wide variety of transition metal catalyzed cross-
coupling reactions for the construction of C−P bond have been
developed.5 As a significant motif in organic chemistry, the alkenyl
Csp2−P bond formation has attracted much attention. There are two
main strategies applicable in forming the alkenyl Csp2−P bond: the
phosphorylation of alkynes or terminal alkynes, and functionalized
alkenes. Dialkyl H-phosphites are coupled with functionalized
alkenes including styrene, 2,2-dibromostyrenes, alkenyl acids,
vinyliodonium tetrafluoroborates to form 2-arylvinylphosphonates
using Cu as a catalyst.6 Transition-metals such as Ni, and Ni/Zn-
catalyzed reactions of alkenyl acids, 2,2-dibromostyrenes with
dialkyl phosphites have been reported.7 In 2015, Zou has described
that Mn(III)-mediated alkenyl C(sp2)-P bond formation from the
reaction of 2-nitrostyrenes with dialkyl phosphites, and Tan found
an efficient Ag-catalyzed reaction of styrenes with dialkyl
phosphites using K2S2O8 as the oxidant, and TEMPO as the additive8
(Scheme 1, a). Transition metals such as Zr/Cu, Pd and Rh catalysts
were employed for the reaction of terminal alkynes with Dialkyl H-
phosphites and dialkyl chlorophosphates (Scheme 1, b).9 It has also
Previous works:
R2
O
O
P
P
P
Y
R2
Cu, Ni/Zn
Mn, Ag
H
P
R2
R2
R1
(a) R1
+
X
X = H, Br, COOH, NO2, IC6H5 (BF4-);
Y = H, Br,
R2
R2
O
O
Zr/Cu, Pd
X
P
R2
R2
(b)
R1
+
R1
Rh
X= H, Cl
R2
O
OR2
X
Pd, Cu
(c)
R2
R1
P
OR2
OR2
R1
+
X = B(OR)2, Br
This work:
(d)
O
OR2
OR2
α
O
Ag
P
NO2
+
H
P
OR2
OR2
R1
R1
β
Scheme 1 Strategies for synthesis of 2-arylvinylphosphonates
(E)- -Nitrostyrenes are useful intermediates in organic
School of Chemistry and Chemical Engineering, Henan University of Technology;
Academician Workstation for Natural Medicinal Chemistry of Henan Province,
Zhengzhou 450001, P.R. China. E-mail: yuanjinweigs@126.com, Fax: +86-371-
67756718; Tel: +86-371-67756718
† Electronic Supplementary Informaꢀon (ESI) available. Part of the experimental
dedail and NMR spectra data See DOI: 10.1039/x0xx00000x
β
synthesis and are important structural units that can be used
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ARTICLE
as starting material for many classes of compounds.12 In Furthermore,
Journal Name
various
reaction
temperatures
were
general, the nitro group activates
substrate, and in the reaction the nitro group is either oC could enhance the reaction efficacy, and a good yield of
α- and/or β-position of a investigated, and increasing the temperature from 40 to 100
o
-Nitrostyrenes are good radical 56% could be obtained at 90 C (Table 1, entries 1, 11-14).
remaining or leaving.13 (E)-
β
acceptors and react with alkyl radicals from different sources Based on these
to generate (E)-alkenes under a variety of conditions and the
reaction mechanism appears to involve a free-radical addition- Table 1 Optimization of reaction conditionsa
elimination reaction.14 Although Zou has described that 2-
arylvinylphosphonates could be synthsized by Mn(III)-catalyzed
reaction of 2-nitrostyrenes with dialkyl phosphites,8a and Tan
has found that Ag-catalyzed reaction of styrenes with dialkyl
phosphites,8b these methodologies need use expensive and
unstable catalysts, acid circumstance, strong oxidants, or with
Oxidant
(eq.)
Temp
(oC)
Time Yieldb
low yield. Drawing inspiration from recent studies15 that
dialkyl phosphites could be utilized as a phosphoryl radical
precursor,16 we wonder that 2-arylvinylphosphonates can be
Entry
Solvent
(min)
20
(%)
56
1
AgNO3 (0.1)
AgNO3 (0.1)
AgNO3 (0.1)
AgNO3 (0.1)
AgNO3 (0.1)
AgNO3 (0.1)
AgNO3 (0.1)
CH3CN
H2O
90
90
90
90
90
90
90
90
90
90
40
60
80
100
90
90
90
90
90
90
90
synthesized by cross-coupling of
phosphites. Herein, we describe a new silver-catalyzed cross-
coupling reaction between readily available -nitrostyrenes
β-nitrostyrenes with dialkyl H-
2
20
<5
0
3
Dioxane
CH3OH
DMSO
DCE
20
β
with dialkyl H-phosphites, leading to 2-arylvinylphosphonates
in moderate to excellent yields. Some notable features of this
protocol are high efficiency, wide functional group tolerance,
4
20
40
<5
54
30
45
60
55
trace
44
49
55
<5
<5
65
70
78
76
nrc
5
20
6
20
readily available and stable β-nitrostyrenes with dialkyl H-
phosphites as starting materials, no oxidants and high
7
THF
20
stereoselectivity (Scheme 1, d).
8
AgNO3 (0.05) CH3CN
AgNO3 (0.15) CH3CN
20
9
20
10
11
12
13
14
15
16
17
18
19
20
21
AgNO3 (0.2)
CH3CN
20
Results and discussion
AgNO3 (0.15) CH3CN
AgNO3 (0.15) CH3CN
AgNO3 (0.15) CH3CN
AgNO3 (0.15) CH3CN
20
Our previous studies showed that the phosphoryl radicals
could be easily generated from H-phosphites with a catalytic
amount of silver salts.16 Based on this achievement, the model
20
20
reaction of (E)-β-nitrostyrenes (1a) and diisopropyl H-
phosphite (2a) was carried out in the presence of AgNO3 (0.1
o
eq) in CH3CN at 90 C for 20 min. Much to our delight, the
20
AgOTf (0.15)
CH3CN
20
Ag2CO3 (0.15) CH3CN
AgNO3 (0.15) CH3CN
AgNO3 (0.15) CH3CN
AgNO3 (0.15) CH3CN
AgNO3 (0.15) CH3CN
20
desired product (3a) was indeed obtained, and the isolated
yield was 56% (Table 1, entry 1). The E or Z stereochemistry of
1
3a is easily established by the H NMR analysis. Indeed, the
40
1.0 h
2.0 h
3.0 h
1.0 h
report in the literature has shown that the chemistry shift of β-
H proton is 6.10-6.30 ppm with a coupling constant 17.0 Hz
typical of trans positioned protons, while that of cis isomer
gives 5.60-5.80 ppm with a coupling constant 15.0 Hz.9a The
β-
proton of 3a at δH=6.27 ppm appears as a triplet with a
coupling constant, J = 17.6 Hz, which proves that configuration
−
CH3CN
a
Reaction conditions: (E)-β-nitrostyrene 1a (0.3 mmol, 44.7 mg), diisopropyl H-
phosphite 2a (0.45 mmol, 74.7 mg), AgNO3 as the catalyst in solvent (3.0 mL).
b Isolated yield.
of 3a is an E stereoisomer.
To achieve the optimal conditions, a variety of reaction c nr = no reaction.
conditions were employed. Initial screening of different
solvents including H2O, dioxane, CH3OH, DMSO, DCE and THF
joyful results, various catalysts of silver salts such as AgOTf and
Ag2CO3 were further investigated. It was found that they
proved to be less effective compared with AgNO3 (Table 1
were applied instead of CH3CN. The result revealed that
solvents such as H2O and CH3OH are not suitable for this
,
reaction, and CH3CN was clearly the best choice (Table 1
,
entries 1, 15 and 16). In addition, various reaction times were
also examined. The yield of 3a dramatically increased if the
reaction time was increased, 2.0 h was found to be
appropriate choice and the yield was 78% (Table 1, entries 1,
17-20). In the absence of AgNO3, the desired product 3a was
not produced, which indicated that AgNO3 as a catalyst played
an important role in this transformation (Table 1, entry 21).
entries 1-7). The ratio of substrates (E)-β-nitrostyrenes and
diisopropyl H-phosphite was investigated, and the ratio of 1 :
1.5 could provide the best result (Table S1, ESI). The screening
of the amount of the catalyst AgNO3 showed that a good yield
(60%) of the product 3a was obtained when 0.15 equiv of
AgNO3 was employed, and excessive or less amount of the
catalyst caused decreased yield (Table 1, entries 1, 8-10).
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Table
2
Synthesis of 2-arylvinylphosphonates from
β
-
the results are summarized in Table 2. A range of β-
nitrostyrene derivatives were found to undergo denitration
nitrostyrenes with dialkyl H-phosphitesa,b
phosphonation in good to excellent yields ranging from 48-
91% with high stereoselectivity (Table 2, entries 3a-3l, 3m-
3zz). Substituents such as methyl, methoxy, methylenedioxy,
fluoro, chloro, bromo, and iodo groups are well tolerated on
the aromatic ring and their reactions afforded the target
products in good to excellent yields, showing the broad scope
of this reaction. β-Nitrostyrenes with electron-donating groups
Table 2, entries 3b-3e) could give slightly better yields than
(
analogues with electron-withdrawing groups (Table 2, entries
3f-3j). The results indicated that electron-donating groups on
the phenyl ring contributed to
β-position carbon electron
density, which made it more susceptible to an electrophilic
attack by the phosphonyl radical. Notably, sterically
demanding substrates like (E)-3,4-dimethoxyl-
and (E)-2,6-dichloro- -nitrostyrenes could be phosphorylated
in 91% and 70% yields (Table 2, entries 3d and 3g). However,
steric hindrance will lead to lower yield when -methyl-
nitrostyrene is employed (Table 2, entry 3l). It was gratifying to
find that heterocyclic -nitroalkene ((E)-2-(2-
β-nitrostyrenes
β
β
β-
β
nitrovinyl)thiophene) also reacted smoothly with diisopropyl
H-phosphite, leading to the corresponding product 3k in
moderated yield (65%). Unfortunately, aliphatic nitroalkenes
failed to deliver the desired products with the current catalytic
system.
Subsequently, the scope for various dialkyl H-phosphites was
also investigated. The reaction could proceed smoothly using
different dialkyl H-phosphites to form the desired products in
moderate to excellent yields in 60-78% with high
stereoselectivity (Table 2, entries 3a, 3m-3q). It is gratifying to
see that the reaction not only worked with dialkyl H-
phosphites but also with diphenylphosphine oxide as well
(
Table 2, entry 3r). Using the standard reaction condition, the
corresponding products were produced in moderate to good
yields (Table 2, entries 3s-3zz). However, the yields of products
3y and 3z were lower when dibenzyl H-phosphite was
employed, which was possible that partial product was
hydrolyzed. Bisphosphonate drugs are used to treat a variety
of bone resorption diseases, such as osteoporosis, Paget’s
disease, and hypercalcemia due to malignancy.17 In the study
of using (E)-5-(2-nitrovinyl)benzo[d][1,3]dioxole and diethyl H-
phosphite as the coupling partners, we found that this resulted
in a mixture of mono- 3w (yield: 50%) and bis-phosphorylated
products 3w’ (yield: 24%) when 3.0 eq. diethyl H-phosphite
was employed at 90 oC for 10 h (Scheme 2).
a Reaction conditions: (E)-
β-nitrostyrenes 1 (0.3 mmol), dialkyl H-phosphites 2
(0.45 mmol), AgNO3 (0.045 mmol, 7.6 mg), in CH3CN (3.0 mL) at 90 oC for 2.0 h.
b Isolated yields.
With the optimized conditions in hand, we next set out to
examine the scope of β-nitrostyrenes and H-phosphites, and
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Scheme 2 Synthesis of mono- and bis-phosphorylated products arylvinylphosphonates starting from (E)-
β
-nitrostyrene
through a tandem radical addition-denitration process. This
To clarify the reaction mechanism, some controlled process features a broad substrate scope and functional group
experiments were designed to investigate this transformation tolerance. The reaction proceeded under mild conditions to
(Scheme 3). When the reaction of (E)-β-nitrostyrene 1a with afford the selective (E)-2-arylvinylphosphonates in moderate
diisopropyl H-phosphite 2a was performed under the standard to good yields.
conditions by the addition of 3.0 eqivalents radical scavengers,
such as TEMPO and BHT, and the target product 3a decreased
Experimental
dramatically. These results indicated that the reaction might
proceed via a radical pathway.
General information
Anhydrous solvents were obtained by standard procedure. All
substrates purchased from J & K Scientific Ltd. were used
without further purification. Column chromatography was
performed using 300-400 mesh silica with the indicated
solvent system according to standard techniques. Nuclear
magnetic resonance spectra were recorded on Bruker Avance
400 MHz spectrometer. Chemical shifts for 1H NMR spectra are
recorded in parts per million from tetramethylsilane. Data
were reported as follows: chemical shift, multiplicity (s =
singlet, d = doublet, t = triplet, m = multiplet and br = broad),
coupling constant in Hz and integration. Chemical shifts for 13C
NMR spectra were recorded in parts per million from
tetramethylsilane. Chemical shift for 31P NMR spectra are
Scheme 3 Controlled experiments
Previous works have shown that silver salts can react with H-
phosphites to form the active (RO)2P(O)Ag complexes which
subsequently generate the phosphoryl radical.16 Based on our
controlled experimental results and literature precedents,8b, 18
the following plausible mechanism can be proposed for the
recorded relative to 85% H3PO4 (δ = 0 ppm) as external
standard. High resolution mass spectra (HR MS) were obtained
on Q-TOF instrument using the ESI technique. IR spectra were
recorded on Shimadazu IR-408 Fourier transform infrared
spectrophotometer using a thin film supported on KBr pellets.
Melting points were measured on an XT4A microscopic
apparatus uncorrected.
transformation (Scheme 4). The phosphoryl radical
generated from the complex which itself is formed by the
reaction of AgNO3 catalyst with H-phosphites . Subsequently,
the radical selectively adds to the -position of (E)-
nitrostyrene to form a carbon-centered radical , which
undergoes an elimination reaction by the leaving NO2 radical
C may be
B
A
General procedure for synthesis of 2-arylvinylphosphonates (3)
C
β
β-
D
(E)-β-nitrostyrenes 1 (0.3 mmol), dialkyl H-phosphites 2 (0.45
mmol), and AgNO3 (0.045mmol, 7.6 mg) in CH3CN (3.0 mL)
to form the desired product E. Ag(0) could be oxidized back to
Ag(I) by HNO3,16a, 18a thus closing the catalytic cycle.
were added to a 25 mL Schlenk tube. The mixture was heated
o
at 90 C for 2.0 h (monitored by TLC). After completion of the
reaction, the solvent was distilled under vacuum. 10 mL
ethylacetate was added to the residuum, 15 mL 5% NaHCO3
was added to wash two times, and 10 mL saturated NaCl
solution washed one time. The organic phase was dried over
anhydrous NaSO4 and concentrated under vacuum. The crude
product was purified by silica gel column chromatography to
give the desired products
ether (1:3 to 2:1) as eluant.
3 using ethyl acetate/petroleum
(E)-Diisopropyl styrylphosphonate (3a)8b
Colorless viscous liquid. IR (KBr) ν(cm-1): 2978, 2933 (-CH3), 1614,
1450 (Ar-), 1246 (P=O), 1105 (P-O). 1H NMR (CDCl3) δ: 7.53-7.43 (m,
3H), 7.39-7.31 (m, 3H), 6.27 (t, J = 17.6 Hz, 1H), 4.75-4.67 (m, 2H),
1.36 (d, J = 6.2 Hz, 6H), 1.31 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ:
147.8 (d, JP-C = 6.6 Hz), 134.9 (d, JP-C = 22.9 Hz), 130.0, 128.7, 127.6,
115.5 (d, JP-C = 190.9 Hz), 70.4 (d, JP-C = 5.5 Hz), 24.0 (d, JP-C = 4.1 Hz),
23.9 (d, JP-C = 4.8 Hz). 31P NMR (CDCl3) δ: 17.4. MS (ESI) m/z: 269.3
Scheme 4 Proposed reaction mechanism for the formation of
2-arylvinylphosphonates
Conclusions
[M + H]+ (calcd for C14H22O3P+ 269.1)
.
In conclusion, we have developed a novel and highly
stereoselectivity protocol for the synthesis of 2-
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(E)-Diisopropyl 4-methylstyrylphosphonate (3b)7b
(m, 1H), 7.31-7.27 (m, 2H), 6.31 (t, J = 17.6 Hz, 1H), 4.79-4.70 (m,
2H), 1.36 (dd, J = 12.7 Hz, J = 6.2 Hz, 12H). 13C NMR (CDCl3) δ: 143.0
(d, JP-C = 7.8 Hz), 134.4, 133.2 (d, JP-C = 23.7 Hz), 130.8, 130.0 (d, JP-C
= 1.0 Hz), 127.3, 127.0, 119.8, 117.9, 70.7 (d, JP-C = 5.7 Hz), 24.1 (d,
JP-C = 4.0 Hz), 24.0 (d, JP-C = 4.8 Hz). 31P NMR (CDCl3) δ: 16.0. HR MS
(ESI) m/z: 303.0914 [M + H]+ (calcd for C14H21ClO3P+ 303.0911).
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3126, 2978 (-CH3), 1616,
1
1400 (Ar-), 1246 (P=O), 1107 (P-O). H NMR (CDCl3) δ: 7.46 (dd, J =
22.6 Hz, J = 17.4 Hz, 1H), 7.39 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 8.0 Hz,
2H), 6.20 (t, J = 17.5 Hz, 1H), 4.75-4.66 (m, 2H), 2.36 (s, 3H), 1.36 (d,
J = 6.2 Hz, 6H), 1.31 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ: 147.8 (d,
JP-C = 6.7 Hz), 140.4, 132.3 (d, JP-C = 23.3 Hz), 129.5, 127.6, 114.2 (d,
JP-C = 191.5 Hz), 70.4 (d, JP-C = 5.6 Hz), 24.1 (d, JP-C = 4.1 Hz), 24.0 (d,
JP-C = 4.7 Hz), 21.4. 31P NMR (CDCl3) δ: 17.8. MS (ESI) m/z: 283.2 [M
+ H]+ (calcd for C15H24O3P+ 283.1).
(E)-Diisopropyl 2,6-dichlorostyrylphosphonate (3g)
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3120, 3020 (-CH3), 1610,
1589 (Ar-), 1252 (P=O), 1153 (P-O) , 756 (C-Cl). 1H NMR (CDCl3) δ:
7.51 (dd, J = 23.6 Hz, J = 17.8 Hz, 1H), 7.34 (d, J = 8.0 Hz, 2H), 7.18 (t,
J = 8.0 Hz, 1H), 6.43 (t, J = 18.0 Hz, 1H), 4.80-4.72 (m, 2H), 1.38 (d, J
= 6.2 Hz, 6H), 1.31 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ: 141.3 (d, JP-
(E)-Diisopropyl 4-methoxystyrylphosphonate (3c)7b
Colorless viscous liquid. IR (KBr) ν(cm-1): 2980, 2923 (-CH3), 1610,
1455 (Ar-), 1244 (P=O), 1103 (P-O). 1H NMR (CDCl3) δ: 7.49-7.32 (m,
3H), 6.89 (d, J = 8.7 Hz, 2H), 6.10 (t, J = 17.4 Hz, 1H), 4.74-4.66 (m,
= 7.8 Hz), 134.5 (d, JP-C = 1.5 Hz), 132.8 (d, JP-C = 23.4 Hz), 129.6,
C
128.7, 125.8 (d, JP-C = 183.2 Hz), 70.5 (d, JP-C = 5.4 Hz), 24.1 (d, JP-C
=
4.0 Hz), 23.9 (d, JP-C = 4.5 Hz). 31P NMR (CDCl3) δ: 14.6. HR MS (ESI)
m/z: 337.0518 [M + H]+ (calcd for C14H20Cl2O3P+ 337.0522).
2H), 3.82 (s, 3H), 1.36 (d, J = 6.2 Hz, 6H), 1.31 (d, J = 6.2 Hz, 6H). 13
C
=
NMR (CDCl3) δ: 161.1, 147.5 (d, JP-C = 6.8 Hz), 129.2, 127.7 (d, JP-C
(E)-diisopropyl 4-fluorostyrylphosphonate (3h)7b
23.5 Hz), 114.1, 112.2 (d, JP-C = 192.4 Hz), 70.3 (d, JP-C = 5.4 Hz), 55.3,
24.0 (d, JP-C = 4.0 Hz), 23.9 (d, JP-C = 4.5 Hz). 31P NMR (CDCl3) δ: 18.3.
MS (ESI) m/z: 299.2 [M + H]+ (calcd for C15H24O4P+ 299.1).
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3082, 2930 (-CH3), 1614,
1457 (Ar-), 1248 (P=O), 1108 (P-O). 1H NMR (CDCl3) δ: 7.45-7.34 (m,
3H), 7.02 (d, J = 8.6 Hz, 2H), 6.14 (t, J = 17.2 Hz, 1H), 4.71-4.63 (m,
2H), 1.32 (d, J = 6.2 Hz, 6H), 1.28 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3)
δ: 163.7 (d, JF-C = 249.1 Hz), 146.4 (d, JP-C = 6.9 Hz, CH), 131.2 (dd, JF-C
(E)-Diisopropyl 3,4-dimethoxystyrylphosphonate (3d)19
Light yellow solid, m.p. 75-76 oC (from chloroform). IR (KBr) ν(cm-1):
2989, 2954 (-CH3), 1613, 1458 (Ar-), 1233(P=O), 1074 (P-O). 1H NMR
(CDCl3) δ: 7.36 (dd, J = 22.5 Hz, J = 17.4 Hz, 1H), 7.03 (dd, J = 8.2 Hz,
J = 1.8 Hz, 1H), 6.98 (d, J = 1.8 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 6.06
(t, J = 17.4 Hz, 1H), 4.70-4.62 (m, 2H), 3.86 (s, 6H), 1.32 (d, J = 6.2
Hz, 6H), 1.28 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ: 150.8, 149.1,
147.6 (d, JP-C = 6.9 Hz, CH), 128.0 (d, JP-C = 23.5 Hz), 121.9 (CH), 112.8
(d, JP-C = 192.5 Hz, CH), 110.9 (CH), 109.3 (CH), 70.3 (d, JP-C = 5.4 Hz),
55.9 (CH3), 55.8 (CH3), 24.1 (d, JP-C = 4.2 Hz, CH3), 24.0 (d, JP-C = 4.2
Hz, CH3). 31P NMR (CDCl3) δ: 18.0. MS (ESI) m/z: 329.2 [M + H]+
(calcd for C16H26O5P+ 329.1).
= 3.4 Hz, JP-C = 23.5 Hz), 129.4 (d, JP-C = 8.4 Hz, CH), 115.8 (d, JP-C
=
21.8 Hz, CH), 115.3 (dd, JF-C = 2.0 Hz, JP-C = 191.7 Hz, CH), 70.5 (d, JP-C
= 5.5 Hz, CH), 24.0 (d, JP-C = 4.0 Hz, CH3), 23.9 (d, JP-C = 4.0 Hz, CH3).
31P NMR (CDCl3) δ: 17.0. 19F NMR (CDCl3) δ: -110.2. MS (ESI) m/z:
287.3 [M + H]+ (calcd for C14H21FO3P+ 287.1).
(E)-diisopropyl 4-bromostyrylphosphonate (3i)8b
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3325, 2960 (-CH3), 1616
1
(Ar-), 1250 (P=O), 1116 (P-O). H NMR (CDCl3) δ: 7.51-7.39 (m, 3H),
7.34 (d, J = 8.4 Hz, 2H), 6.24 (t, J = 17.2 Hz, 1H), 4.76-4.66 (m, 2H),
1.35 (d, J = 6.2 Hz, 6H), 1.30 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ:
146.4 (d, JP-C = 7.0 Hz), 133.9 (d, JP-C = 23.5 Hz), 132.0, 129.0, 124.2,
116.2 (d, JP-C = 191.5 Hz), 70.5 (d, JP-C = 5.8 Hz), 24.0 (d, JP-C = 4.0 Hz),
23.9 (d, JP-C = 4.5 Hz). 31P NMR (CDCl3) δ: 16.6. MS (ESI) m/z: 347.2
[M + H]+ (calcd for C14H21BrO3P+ 347.0).
(E)-Diisopropyl (2-(benzo[d][1,3]dioxol-5-yl)vinyl)phosphonate
(3e)6c
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3120, 2978, 2933 (-CH3,
-CH2), 1601, 1491, 1448 (Ar-), 1254 (P=O), 1105 (P-O). 1H NMR
(CDCl3) δ: 7.37 (dd, J = 22.4 Hz, J = 17.4 Hz, 1H), 7.00 (d, J = 1.1 Hz,
1H), 6.96 (d, J = 9.3 Hz, 1H), 6.79 (d, J = 8.0 Hz, 1H), 6.07 (t, J = 17.2
Hz, 1H), 5.99 (s, 2H), 4.74-4.65 (m, 2H), 1.36 (d, J = 6.2 Hz, 6H), 1.31
(E)-diisopropyl 4-iodostyrylphosphonate (3j)
(d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ: 149.3, 148.2, 147.3 (d, JP-C
=
Yellow viscous liquid. IR (KBr) ν(cm-1): 3028, 2965 (-CH3), 1624, 1547
(Ar-), 1246 (P=O), 1109 (P-O). 1H NMR (CDCl3) δ: 7.70 (d, J = 8.4 Hz,
2H), 7.37 (dd, J = 17.6 Hz, J = 22.6 Hz, 1H), 7.20 (d, J = 8.4 Hz, 2H),
6.25 (t, J = 17.2 Hz, 1H), 4.73-4.65 (m, 2H), 1.35 (d, J = 6.2 Hz, 6H),
1.30 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ: 146.4 (d, JP-C = 6.7 Hz),
138.0, 134.5 (d, JP-C = 23.3 Hz), 129.1, 127.6, 116.6 (d, JP-C = 191.0
Hz), 70.6 (d, JP-C = 5.7 Hz), 24.1 (d, JP-C = 4.0 Hz), 24.0 (d, JP-C = 4.5
Hz). 31P NMR (CDCl3) δ: 16.6. HR MS (ESI) m/z: 395.0270 [M + H]+
(calcd for C14H21IO3P+395.0268).
7.2 Hz, CH), 129.4 (d, JP-C = 23.8 Hz), 123.7 (CH), 113.0 (d, JP-C = 192.1
Hz, CH), 107.2 (d, JP-C = 225.5 Hz, CH), 101.4 (CH), 70.3 (d, JP-C = 5.5
Hz), 24.0 (d, JP-C = 4.0 Hz, CH3), 23.9 (d, JP-C = 4.2 Hz, CH3). 31P NMR
(CDCl3) δ: 17.8. MS (ESI) m/z: 313.3 [M + H]+ (calcd for C15H22O5P+
313.1).
(E)-Diisopropyl 2-chlorostyrylphosphonate (3f)
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3128, 2979 (-CH3), 1614,
1450, 1367 (Ar-), 1248 (P=O), 1105 (P-O), 754 (C-Cl). 1H NMR (CDCl3)
δ: 7.83 (dd, J = 22.6 Hz, J = 17.5 Hz, 1H), 7.60-7.57 (m, 1H), 7.40-7.38
(E)-diisopropyl (2-(thiophen-2-yl)vinyl)phosphonate (3k)7b
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Colorless viscous liquid. IR (KBr) ν(cm-1): 3007, 2926 (-CH3), 1613, Light yellow viscous liquid. IR (KBr) ν(cm-1): 3128, 2962 (-CH3, -CH2),
1
1452 (Ar-), 1245 (P=O), 1103 (P-O). H NMR (CDCl3) δ: 7.49 (dd, J = 1526, 1415 (Ar-), 1248 (P=O), 1068 (P-O). 1H NMR (CDCl3) δ: 7.52-
22.6 Hz, J = 17.4 Hz, 1H), 7.28 (d, J = 5.0 Hz, 1H), 7.13 (d, J = 3.3 Hz, 7.42 (m, 3H), 7.36-7.33 (m, 3H), 6.24 (t, J = 17.6 Hz, 1H), 4.06-3.98
1H), 6.97 (t, J = 4.6 Hz, 1H), 5.95 (t, J = 16.8 Hz, 1H), 4.69-4.59 (m, (m, 4H), 1.67-1.60 (m, 4H), 1.43-1.35 (m, 4H), 0.89 (t, J = 7.4 Hz, 6H).
2H), 1.30 (d, J = 6.2 Hz, 6H), 1.26 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) 13C NMR (CDCl3) δ: 148.7 (d, JP-C = 6.6 Hz, CH), 134.8 (d, JP-C = 23.1
δ: 140.5 (d, JP-C = 26.7 Hz), 140.2 (d, JP-C = 7.6 Hz, CH), 129.9 (CH), Hz), 130.2 (CH), 128.8 (CH), 127.7 (CH), 113.8 (d, JP-C = 190.4 Hz,
127.9 (d, JP-C = 1.1 Hz, CH), 127.8, 114.1 (d, JP-C = 193.1 Hz, CH), 70.5 CH), 65.5 (d, JP-C = 5.7 Hz, CH2), 32.5 (d, JP-C = 6.3 Hz, CH2), 18.7
(d, JP-C = 5.5 Hz, CH), 24.0 (d, JP-C = 4.0 Hz, CH3), 23.9 (d, JP-C = 4.0 Hz, (CH2), 13.6 (CH3). 31P NMR (CDCl3) δ: 19.6. MS (ESI) m/z: 297.3 [M +
CH3). 31P NMR (CDCl3) δ: 16.7. MS (ESI) m/z: 275.2 [M + H]+ (calcd H]+ (calcd for C16H26O3P+ 297.1).
for C12H20O3PS+ 275.0).
(E)-Diisobutyl styrylphosphonate (3q)
(E)-diisopropyl (1-phenylprop-1-en-2-yl)phosphonate (3l)
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3124, 2969 (-CH3, -CH2),
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3125, 3018 (-CH3), 1612, 1608, 1410 (Ar-), 1167 (P=O), 1047 (P-O). 1H NMR (CDCl3) δ: 7.57-
1
1576 (Ar-), 1250 (P=O), 1132 (P-O). H NMR (CDCl3) δ: 7.47 (dd, J = 7.47 (m, 3H), 7.39-7.37 (m, 3H), 6.26 (t, J = 17.6 Hz, 1H), 3.85-3.80
24.8 Hz, J = 1.4 Hz, 1H), 7.38 (d, J = 4.4 Hz, 4H), 7.34-7.29 (m, 1H), (m, 4H), 2.00-1.93 (m, 2H), 0.95 (d, J = 6.8 Hz, 9H). 13C NMR (CDCl3)
4.71-4.68 (m, 2H), 2.06 (dd, J = 15.2 Hz, J = 1.4 Hz, 1H), 1.38 (d, J = δ: 148.9 (d, JP-C = 6.5 Hz), 134.8 (d, JP-C = 23.3 Hz), 130.3, 128.9,
6.2 Hz, 6H), 1.31 (d, J = 6.2 Hz, 6H). 13C NMR (CDCl3) δ: 141.9 (d, JP-C 127.7, 113.4 (d, JP-C = 191.7 Hz), 71.9 (d, JP-C = 6.1 Hz), 29.1 (d, JP-C
=
= 12.5 Hz, CH), 135.9 (d, JP-C = 23.4 Hz), 129.4 (CH), 128.4 (CH), 128.2 6.7 Hz), 18.7 (d, JP-C = 1.9 Hz). 31P NMR (CDCl3) δ: 19.4. HR MS (ESI)
(CH), 126.4, 70.3 (d, JP-C = 6.4 Hz, CH), 24.1 (d, JP-C = 4.2 Hz, CH3), m/z: 297.1618 [M + H]+ (calcd for C16H26O3P+ 297.1614).
23.8 (d, JP-C = 4.5 Hz, CH3), 14.4 (d, JP-C = 9.7 Hz, CH3). 31P NMR
(E)-diphenyl(styryl)phosphine oxide (3r)8b
(CDCl3) δ: 19.7. HR MS (ESI) m/z: 283.1456 [M + H]+ (calcd for
C15H24O3P+ 283.1458).
Light yellow solid, m.p. 145-146 oC (from chloroform). IR (KBr) ν(cm-
(E)-Dimethyl styrylphosphonate (3m)20
1
1): 1606, 1437, 1400 (Ar-), 1162 (P=O), 1120 (P-O). H NMR (CDCl3)
δ: 7.77-7.72 (m, 4H), 7.55-7.44 (m, 9H), 7.36-7.35 (m, 3H), 6.83 (dd,
Colorless viscous liquid. IR (KBr) ν(cm-1): 2952, 2850 (-CH3), 1616, J = 22.4 Hz, J = 17.4 Hz, 1H). 13C NMR (CDCl3) δ: 147.6 (d, JP-C = 3.5
1448 (Ar-), 1250 (P=O), 1053 (P-O). 1H NMR (CDCl3) δ: 7.58-7.48 (m, Hz, CH), 135.1 (d, JP-C = 17.8 Hz), 132.8 (d, JP-C = 105.5 Hz), 131.9 (d,
3H), 7.40-7.37 (m, 3H), 6.23 (t, J = 17.7 Hz, 1H), 3.78 (d, J = 11.1 Hz, JP-C = 2.5 Hz, CH), 131.4 (d, JP-C = 10.0 Hz, CH), 130.1, 128.8 (d, JP-C
=
6H). 13C NMR (CDCl3) δ: 149.6 (d, JP-C = 6.6 Hz), 134.6 (d, JP-C = 23.1 27.8 Hz, CH), 128.7 (CH), 127.8 (CH), 119.0 (d, JP-C = 103.9 Hz, CH).
Hz), 130.4, 128.9, 127.7, 112.3 (d, JP-C = 191.2 Hz), 52.4 (d, JP-C = 5.6 31P NMR (CDCl3) δ: 24.8. MS (ESI) m/z: 305.0 [M + H]+ (calcd for
Hz). 31P NMR (CDCl3) δ: 22.4. MS (ESI) m/z: 213.1 [M + H]+ (calcd for C20H18OP+ 305.1).
C10H14O3P+ 213.0).
(E)-Diethyl 4-methylstyrylphosphonate (3s)8b
(E)-Diethyl styrylphosphonate (3n)8b
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3128, 2969 (-CH3, -CH2),
Colorless viscous liquid. IR (KBr) ν(cm-1): 3107, 1985 (-CH3, -CH2), 1616, 1405 (Ar-), 1246 (P=O), 1026 (P-O). 1H NMR (CDCl3) δ: 7.47
1
1610, 1545, 1464 (Ar-), 1214 (P=O), 1134 (P-O). H NMR (CDCl3) δ: (dd, J = 22.6 Hz, J = 17.5 Hz, 1H), 7.39 (d, J = 8.1 Hz, 2H), 7.18 (d, J =
7.56-7.46 (m, 3H), 7.40-7.37 (m, 3H), 6.26 (t, J = 17.6 Hz, 1H), 4.17- 8.1 Hz, 2H), 6.19 (t, J = 17.7 Hz, 1H), 4.16-4.08 (m, 4H), 2.37 (s, 3H),
4.09 (m, 4H), 1.36 (t, J = 7.0 Hz, 6H). 13C NMR (CDCl3) δ: 148.7 (d, JP-C 1.35 (t, J = 7.0 Hz, 6H). 13C NMR (CDCl3) δ: 148.8 (d, JP-C = 6.6 Hz),
= 6.7 Hz), 134.8 (d, JP-C = 23.0 Hz), 130.2, 128.8, 127.7, 113.9 (d, JP-C 140.6, 132.1 (d, JP-C = 23.2 Hz), 129.5, 127.7, 112.4 (d, JP-C = 190.8
= 190.3 Hz), 61.8 (d, JP-C = 5.5 Hz), 16.4 (d, JP-C = 6.4 Hz). 31P NMR Hz), 61.8 (d, JP-C = 5.4 Hz), 21.4, 16.4 (d, JP-C = 6.5 Hz). 31P NMR
(CDCl3) δ: 19.5. MS (ESI) m/z: 241.3 [M + H]+ (calcd for C12H18O3P+ (CDCl3) δ: 19.9. MS (ESI) m/z: 255.0 [M + H]+ (calcd for C13H20O3P+
241.1).
255.1).
(E)-Dipropyl styrylphosphonate (3o)7a
(E)-Diethyl 4-methoxystyrylphosphonate (3t)8b
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3122, 2970 (-CH3, -CH2), Light yellow viscous liquid. IR (KBr) ν(cm-1): 3134, 2969 (-CH3, -CH2),
1
1616, 1400 (Ar-), 1244 (P=O), 1065 (P-O). 1H NMR (CDCl3) δ: 7.56- 1604, 1512, 1400 (Ar-), 1257 (P=O), 1028 (P-O). H NMR (CDCl3) δ:
7.46 (m, 3H), 7.39-7.37 (m, 3H), 6.26 (t, J = 17.6 Hz, 1H), 4.05-3.99 7.46-7.36 (m, 3H), 6.86 (d, J = 8.8 Hz, 2H), 6.05 (t, J = 17.6 Hz, 1H),
(m, 4H), 1.76-1.68 (m, 4H), 0.97 (d, J = 7.4 Hz, 6H). 13C NMR (CDCl3) 4.12-4.04 (m, 4H), 3.79 (s, 3H), 1.31 (t, J = 7.1 Hz, 6H). 13C NMR
δ: 148.8 (d, JP-C = 6.7 Hz), 134.8 (d, JP-C = 23.2 Hz), 130.3, 128.9, (CDCl3) δ: 161.2, 148.4 (d, JP-C = 6.9 Hz, CH), 129.3 (CH), 127.6 (d, JP-C
127.7, 113.6 (d, JP-C = 191.0 Hz), 67.4 (d, JP-C = 5.8 Hz), 23.8 (d, JP-C
=
= 23.7 Hz), 114.2 (CH), 110.6 (d, JP-C = 191.7 Hz, CH), 61.7 (d, JP-C =
6.5 Hz), 10.0. 31P NMR (CDCl3) δ: 19.6. MS (ESI) m/z: 269.2 [M + H]+ 5.3 Hz, CH2), 55.3 (CH3), 16.4 (d, JP-C = 6.5 Hz, CH3). 31P NMR (CDCl3)
(calcd for C14H22O3P+ 269.1).
δ: 20.4. MS (ESI) m/z: 271.3 [M + H]+ (calcd for C13H20O4P+ 271.1).
(E)-Diethyl 2-chlorostyrylphosphonate (3u)8a
(E)-dibutyl styrylphosphonate (3p)7b
6 | J. Name., 2013, 00, 1-9
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Light yellow viscous liquid. IR (KBr) ν(cm-1): 3132, 2969 (-CH3, -CH2), (CDCl3) δ: 149.4, 148.3 (d, JP-C = 5.0 Hz), 129.3 (d, JP-C = 23.7 Hz),
1595, 1401 (Ar-), 1254 (P=O), 1075 (P-O), 806 (C-Cl). 1H NMR (CDCl3) 123.9, 112.3, 110.4, 108.4, 106.2, 101.5, 67.3 (d, JP-C = 5.5 Hz), 23.8
δ: 7.86 (dd, J = 22.6 Hz, J = 17.5 Hz, 1H), 7.61-7.58 (m, 1H), 7.41-7.39 (d, JP-C = 6.5 Hz), 10.1. 31P NMR (CDCl3) δ: 20.1. HR MS (ESI) m/z:
(m, 1H), 7.31-7.28 (m, 2H), 6.30 (t, J = 17.7 Hz, 1H), 4.20-4.12 (m, 313.1202 [M + H]+ (calcd for C15H22O5P+ 313.1199).
4H), 1.37 (t, J = 7.0 Hz, 6H). 13C NMR (CDCl3) δ: 144.0 (d, JP-C = 7.8
(E)-Dibenzyl (2-(benzo[d][1,3]dioxol-5-yl)vinyl)phosphonate (3y)
Hz), 134.5, 133.2 (d, JP-C = 23.5 Hz), 131.0, 130.0, 127.4, 127.0, 117.2
(d, JP-C = 33.0 Hz), 62.1 (d, JP-C = 5.6 Hz), 16.4 (d, JP-C = 6.4 Hz). 31P
NMR (CDCl3) δ: 18.2. MS (ESI) m/z: 275.2 [M + H]+ (calcd for
Light yellow solid, m.p. 106-107 oC (from chloroform). IR (KBr) ν(cm-
1): 3126, 3033 (-CH2), 1601, 1491, 1448, 1400 (Ar-), 1254 (P=O),
1036 (P-O). 1H NMR (CDCl3) δ: 7.38-7.29 (m, 11H), 6.90-6.87 (m,
2H), 6.76 (d, J = 7.9 Hz, 1H), 6.01 (t, J = 17.6 Hz, 1H), 5.96 (s, 2H),
C12H17ClO3P+ 275.0).
(E)-Diethyl 2,6-dichlorostyrylphosphonate (3v)8a
5.07 (s, 2H), 5.05 (s, 2H). 13C NMR (CDCl3) δ: 149.6, 148.7 (d, JP-C
=
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3125, 3018 (-CH3, -CH2), 7.2 Hz, CH), 136.3 (d, JP-C = 6.6 Hz), 129.2 (d, JP-C = 24.4 Hz), 128.6
1615, 1578 (Ar-), 1250 (P=O), 1151 (P-O) , 764 (C-Cl). 1H NMR (CH), 128.4 (CH), 127.9 (CH), 124.0 (CH), 111.0 (d, JP-C = 192.8 Hz,
(CDCl3) δ: 7.53 (dd, J = 23.7 Hz, J = 17.9 Hz, 1H), 7.36 (d, J = 7.7 Hz, CH), 108.4 (CH), 106.2 (CH), 101.5 (CH2), 67.4 (d, JP-C = 5.2 Hz, CH2).
2H), 7.19 (t, J = 8.2 Hz, 1H), 6.42 (t, J = 18.2 Hz, 1H), 4.21-4.14 (m, 31P NMR (CDCl3) δ: 21.1. HR MS (ESI) m/z: 409.1196 [M + H]+ (calcd
4H), 1.38 (d, J = 7.0 Hz, 6H). 13C NMR (CDCl3) δ: 142.1 (d, JP-C = 7.6 for C23H22O5P+ 409.1199).
Hz), 134.5 (d, JP-C = 1.4 Hz), 129.8, 128.7, 127.9, 124.2 (d, JP-C = 182.5
Hz), 62.2 (d, JP-C = 5.4 Hz), 16.4 (d, JP-C = 6.4 Hz). 31P NMR (CDCl3) δ:
(E)-Dibenzyl 2-chlorostyrylphosphonate (3z)
17.0. MS (ESI) m/z: 309.2 [M + H]+ (calcd for C12H16Cl2O3P+ 309.0).
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3126 (-CH2), 1603, 1401
(Ar-), 1250 (P=O), 1049 (P-O). H NMR (CDCl3) δ: 7.87 (dd, J = 23.0
Hz, J = 17.5 Hz, 1H), 7.47 (dd, J = 7.5 Hz, J = 1.6 Hz, 1H), 7.39-7.24
(E)-diethyl (2-(benzo[d][1,3]dioxol-5-yl)vinyl)phosphonate (3w)21
1
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3138, 2969 (-CH3, -CH2), (m, 13H), 6.24 (t, J = 18.1 Hz, 1H), 5.11 (d, J = 2.8 Hz, 2H), 5.09 (d, J =
1
1603, 1590, 1401 (Ar-), 1254 (P=O), 1038 (P-O). H NMR (CDCl3) δ: 2.7 Hz, 2H). 13C NMR (CDCl3) δ: 144.4 (d, JP-C = 8.1 Hz, CH), 136.1 (d,
7.33 (dd, J = 22.4 Hz, J = 17.4 Hz, 1H), 6.94 (s, 1H), 6.90 (d, J = 8.0 Hz, JP-C = 6.5 Hz), 134.6, 133.0 (d, JP-C = 23.9 Hz), 131.0 (CH), 130.1 (CH),
1H), 6.73 (d, J = 8.0 Hz, 1H), 5.98 (t, J = 17.4 Hz, 1H), 5.93 (s, 2H), 128.6 (CH), 128.4 (CH), 128.0 (CH), 127.4 (d, JP-C = 1.0 Hz, CH), 127.0
4.09-4.01 (m, 4H), 1.28 (t, J = 7.1 Hz, 6H). 13C NMR (CDCl3) δ: 149.4, (CH), 116.9 (d, JP-C = 190.9 Hz, CH), 67.5 (d, JP-C = 5.6 Hz, CH2). 31P
148.4, 148.3 (d, JP-C = 3.8 Hz, CH), 129.3 (d, JP-C = 23.8 Hz), 123.9 NMR (CDCl3) δ: 19.2. HR MS (ESI) m/z: 399.0909 [M + H]+ (calcd for
(CH), 112.3 (CH), 110.4 (CH), 108.4 (CH), 106.2 (CH), 101.5 (CH2), C22H21ClO3P+ 399.0911).
61.7 (d, JP-C = 5.5 Hz, CH2), 16.3 (d, JP-C = 6.4 Hz, CH3). 31P NMR
(CDCl3) δ: 19.6. MS (ESI) m/z: 285.2 [M + H]+ (calcd for C13H18O5P+
(E)-dibutyl 3,4-dimethoxystyrylphosphonate (3zz)
285.0).
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3147, 2962 (-CH3, -CH2),
1514, 1400 (Ar-), 1269 (P=O), 1159 (P-O). 1H NMR (CDCl3) δ: 7.37
Tetraethyl (2-(benzo[d][1,3]dioxol-5-yl)ethene-1,1-
(dd, J = 22.4 Hz, J = 17.4 Hz, 1H), 7.02 (dd, J = 8.2 Hz, J = 1.5 Hz, 1H),
diyl)bis(phosphonate) (3w′)
6.98 (d, J = 1.5 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 6.04 (t, J = 17.4 Hz,
1H), 4.03-3.96 (m, 4H), 3.85 (s, 6H), 1.66-1.59 (m, 4H), 1.41-1.32 (m,
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3122, 2987 (-CH3, -CH2),
4H), 0.87 (t, J = 7.4 Hz, 6H). 13C NMR (CDCl3) δ: 150.9, 149.1, 148.5
1603, 1405 (Ar-), 1254 (P=O), 1106 (P-O). 1H NMR (CDCl3) δ: 8.18
(d, JP-C = 6.9 Hz, CH), 127.8 (d, JP-C = 23.5 Hz), 122.0 (CH), 111.0 (d, JP-
(dd, J = 29.4 Hz, J = 47.7 Hz, 1H), 7.55 (d, J = 1.3 Hz, 1H), 7.30 (d, J =
C = 191.9 Hz, CH), 110.9 (CH), 109.3 (CH), 65.5 (CH3), 65.4 (CH3), 55.9
8.2 Hz, 1H), 6.83 (d, J = 8.2 Hz, 1H), 6.83 (s, 2H), 4.22-4.14 (m, 4H),
(d, JP-C = 8.9 Hz, CH2), 32.5 (d, JP-C = 6.5 Hz, CH2), 18.7 (CH2), 13.6
4.13-4.05 (m, 4H), 1.37 (t, J = 7.0 Hz, 6H), 1.24 (t, J = 7.0 Hz, 6H). 13
C
=
(CH3). 31P NMR (CDCl3) δ: 19.8. HR MS (ESI) m/z: 357.1823 [M + H]+
NMR (CDCl3) δ: 161.1 (d, JP-C = 2.2 Hz), 150.1, 147.6, 128.3 (dd, JP-C
(calcd for C18H30O5P+ 357.1825).
22.6 Hz, JP-C = 8.8 Hz), 127.8, 110.6, 107.9, 101.6, 62.6 (d, JP-C = 5.2
Hz), 62.4 (d, JP-C = 5.8 Hz), 16.3 (d, JP-C = 6.6 Hz), 16.1 (d, JP-C = 6.6
Hz). 31P NMR (CDCl3) δ: 18.3 (d, JP-P = 49.5 Hz), 12.8 (d, JP-P = 49.5
Acknowledgements
+
Hz). HR MS (ESI) m/z: 421.1178 [M + H]+ (calcd for C17H27O8P2
We gratefully acknowledge the National Natural Science
Foundation of China (No. 21302042 and 21172055),
Department of Henan Province Natural Science and
Technology Foundation (No. 142102210410), Natural Science
Foundation in Henan Province Department of Education (No.
14B150053 and 17A150005), the Program for Innovative
Research Team from Zhengzhou (No. 131PCXTD605).
421.1176).
(E)-Dipropyl (2-(benzo[d][1,3]dioxol-5-yl)vinyl)phosphonate (3x)
Light yellow viscous liquid. IR (KBr) ν(cm-1): 3140, 2967 (-CH3, -CH2),
1607, 1582, 1406 (Ar-), 1247 (P=O), 1036 (P-O). H NMR (CDCl3) δ:
7.40 (dd, J = 22.4 Hz, J = 17.4 Hz, 1H), 7.01 (d, J = 1.3 Hz, 1H), 6.97
(d, J = 8.0 Hz, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.09-6.00 (m, 3H), 4.03-
3.97 (m, 4H), 1.76-1.67 (m, 4H), 0.96 (t, J = 7.4 Hz, 6H). 13C NMR
1
Notes and references
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Graphic Abstract
Silver-catalyzed synthesis of 2-arylvinylphosphonates by cross-coupling
of β-nitrostyrenes with H-phosphites
Jin-Wei Yuan,* Liang-Ru Yang, Pu Mao, and Ling-Bo Qu*
School of Chemistry & Chemical Engineering, Henan University of Technology; Academician
Workstation for Natural Medicinal Chemistry of Henan Province, Zhengzhou 450001, PR China
An efficient protocol for stereoselective synthesis of vinylphosphonates has been developed via
AgNO3-catalyzed cross-coupling of β-nitrostyrenes with dialkyl H-phosphites under mild
conditions.