Metal-Free Access to (E/Z)-α-Fluorovinyl Phosphorus Compounds from gem-Difluorostyrenes

Article abstract of DOI:10.1002/ejoc.201801602

A facile and efficient method for the synthesis of (E/Z)-α-fluorovinyl phosphorus compounds from gem-difluorostyrenes with diphenylphosphine oxide/dialkyl phosphate and DBU at room temperature was developed. A series of 1-fluorovinyl phosphine oxides/phosphonates were obtained with moderate to excellent yields in these reactions. Additionally, most isomers (E/Z type) of the target compounds could be easily separated and purified by column chromatography.

Full text of DOI:10.1002/ejoc.201801602

A Journal of
Accepted Article
Title: Metal-free access to (E/Z)-α-fluorovinyl phosphorus compounds
from gem-difluorostyrenes
Authors: Yingyuan Peng, Xiaofei Zhang, Xueyu Qi, Qian He, Bin
Zhang, Jian Hao, and Chunhao Yang
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801602
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801602
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10.1002/ejoc.201801602
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Metal-free access to (E/Z)-α-fluorovinyl phosphorus compounds
from gem-difluorostyrenes
Yingyuan Peng,[a] Xiaofei Zhang,[b] Xueyu Qi,[b] Qian He,[b] Bin Zhang,[a]Jian Hao,*[a] and Chunhao
Yang*[b]
Abstract: A facile and efficient method for the synthesis of (E/Z)-α-
fluorovinyl phosphorus compounds from gem-difluorostyrenes with
diphenylphosphine oxide/dialkyl phosphate and DBU at room
temperature was developed. A series of 1-fluorovinyl phosphine
oxides/phosphonates were obtained with moderate to excellent yields
in these reactions. Additionally, most isomers (E/Z type) of the target
compounds could be easily separated and purified by column
chromatography.
functional phosphorylated compounds, we tried to introduce
fluorine atoms to alkenyl phosphorus compounds which could
modify the electronic and stereoscopic properties of these
phosphorylated compounds for particular goals.[9] As far as we
know, the introduction of fluorine atom could effectively overcome
the unstable property of some phosphorus functional groups,
such as α,α-difluorophosphonates, α-fluorophosphonates and α-
fluorovinylphosphonates.[10] More importantly, some α-fluorovinyl
phosphorus compounds are very useful for the discovery of bio-
active or probe compounds to understand particular bio-chemical
processes.[11] For example, the analogs of lysophosphatidic acid
could be prepared directly from α-fluorovinyl phosphorus
compounds[12] and the α-fluoro-substituted phosphorus acids
could also be easily obtained from α-fluorovinyl phosphorus
compounds via hydrogenation reaction and so on.[13] Especially,
some α-fluorovinyl phosphorus compounds even display some
very interesting biological activities by themselves.[14]
Some methods for the preparation of α-fluorovinyl phosphorus
compounds have already been reported (Scheme 1). Burton’s
group employed Pd catalyst to synthesize predominately (E)-
isomer products from E/Z mixtures of 1-bromo-1-fluoroolefins and
diethyl phosphite (Scheme 1, a).[15] Beier and co-workers
synthesized α-fluorovinylphosphonates from α, α-difluoro-β-
arylphosphonates or α,α-difluoro-β-alkenylphosphonates under a
very harsh condition (Scheme 1, b).[16] Poisson and co-workers
reported Cu(I)-mediated access to (Z)-α-fluorovinylphosphonates
from unstable and pre-functional diazocarbonyl derivatives
(Scheme 1, c).[17] Recently, Couve-Bonnaire and Lakhdar
reported the first transition-metal-free stereospecific synthesis of
(E)-(1-fluoro-2-arylvinyl) phosphine boranes from the addition of
diarylphosphine-boranes to gem-bromofluoroalkenes with the
presence of Cs2CO3 (Scheme 1, d).[18] Although these methods
are useful to prepare α-fluorovinyl phosphorus compounds, they
were still limited by the scope of substrates, harsh conditions
and/or multiple synthetic steps. By considering the importance of
α-fluorovinyl phosphorus compounds and the existing
approaches, a new strategy was highly desirable. Driven by our
interests on the field of constructing fluorinated bio-activitive
compounds or fluorine-containing heterocycles,[19] here we
presented a novel, robust and practical method to synthesize (E)-
and (Z)-(1-fluoro-2-arylvinyl)phosphine oxides/phosphonates
from gem-difluorostyrenes under very mild conditions.
Introduction
In recent years, gem-difluorostyrenes have attracted more and
more attentions for their applications in organic chemistry as
building blocks for constructing specific compounds.[1] For
example, the unique gem-difluorostyrenes could be used as the
precursors of esters/carboxylic acids,[2] monofluoroalkenes[3] and
some other functional groups.[4] Besides, they can also be served
as precursors of fluorinated heterocycles via intramolecular
cyclization
reactions.[5]
Meanwhile,
organophosphorus
compounds are also an important class of functional molecules
which play a huge role in biological systems like protein activation,
energy metabolism and signal transductions.[6] Among these
organophosphorus compounds, alkenyl phosphorus compounds
are considered as an important motif in organic synthesis due to
their special electronic and stereoscopic properties. Previous
procedures for the synthesis of these compounds relied on the
transformation from alkenyl halides, but these reactions usually
required high temperature and the scope of substrates was
narrow.[7] Nowadays, the synthesis of these compounds highly
depend on transition-metal catalyzed reactions of P(O)-H
compounds to C-C triple bonds.[8] These methods are efficient for
the construction of C–P bonds but usually catalyzed by noble or
toxic transition-metal catalysts such as Rh,[8b] Ni[8c] and Pd[8d] etc.
For our interests, because the alkenyl phosphorus compounds
could be employed as potential intermediates for ligands in
transition-metal catalyzed reactions and substrates for some
[a]
[b]
Yingyuan Peng, Bin Zhang, Prof. Dr. Jian Hao
Department of Chemistry, Innovative Drug Research Center,
Shanghai University, Shangda Road 99, Shanghai 200436, China
E-mail: jhao@shu.edu.cn.
http://my.shu.edu.cn/Index.aspx?TID=4211
Xiaofei Zhang, Xueyu Qi, Qian He, Prof. Dr. Chunhao Yang
State Key Laboratory of Drug Research, Shanghai Institute of
Materia Medica, Chinese Academy of Science, 555 Zu Chong Zhi
Road, Shanghai 201203, China
Results and Discussion
Firstly we started our study by treating 4-phenyl-difluorostyrene
E-mail: chyang@simm.ac.cn.
http://sourcedb.simm.cas.cn/zw/zjrc/201111/t20111122_3399860.
html
Supporting information for this article is given via a link at the end
of the document.
[20]
1a prepared according to the literature
with easy-handling
diphenylphosphine oxide 2a in the presence of t-BuOK in MeCN
at room temperature for 4 h. To our delight, we obtained (E)-(2-
([1,1'-biphenyl]-4-yl)-1-fluorovinyl) diphenylphosphine oxide 3a
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10.1002/ejoc.201801602
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(E) with the yield of 39% and (Z)-(2-([1,1'-biphenyl]-4-yl)-1-
fluorovinyl)diphenylphosphine oxide 3a (Z) in 28% (Table 1, entry
1). And the structure of 3a (E) was quickly confirmed by NMR
spectroscopy and X-ray analysis (Figure 1).
reaction occured in these non-polar or low-polar solvents (entry 6,
11). In addition, reducing the amount of the DBU resulted the
decreased yield (77%) for 3a (entry 12). The best reaction time
was determined to be one hour (entry 13 vs entry 8). Afterwards,
the investigation of different temperatures indicated room
temperature was the best choice, and higher temperature did not
improve the reaction efficiency (entries 14-16). So, the optimized
reaction conditions were employing 1a (1 equiv.), 2a (2 equiv.)
and DBU (1.5 equiv.) in DMF at room temperature for 1 hour.
Table 1. Optimization for the synthesis of (E)- and (Z)-(1-fluoro-2-arylvinyl)
phosphine oxide.[a]
Temp
(oC)
Yield(%)b
(E/Z)
Entry
Base
Solvent
1
2
t-BuOK
DIPEA
Cs2CO3
KOH
DBU
MeCN
MeCN
MeCN
MeCN
MeCN
acetone
THF
r.t
r.t
66 (57:43)
0
3
r.t
71 (55:45)
67 (61:39)
87 (52:48)
0
4
r.t
5
r.t
Scheme 1. Synthesis of α-fluorovinyl phosphorus compounds.
6
DBU
r.t
7
DBU
r.t
81 (52:48)
93 (54:46)
89 (54:46)
91 (53:47)
0
8
DBU
DBU
DMF
r.t
r.t
9
DMSO
NMP
10
11
12c
13d
14
15
16
DBU
r.t
DBU
toluene
DMF
r.t
DBU
r.t
77 (53:47)
76 (51:49)
82 (50:50)
77 (53:47)
81 (50:50)
DBU
DMF
r.t
DBU
DMF
60
80
100
Figure 1. X-ray crystal structure of 3a (E) [21]
DBU
DMF
DBU
DMF
[a] Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), base (0.3 mmol) in
solvent (2.0 mL) at room temperature for 1 h. [b] Isolated yields. [c] DBU
(1 equiv.) was used. [d] Reaction time: 45 minutes.
Based on this exciting result, we optimized the reaction conditions
(Table 1). In the beginning, the bases were extensively screened.
The yield of the desired product was dramatically improved from
66% to 87% when DBU (1,8-diazabicyclo[5,4,0]undec-7-ene) was
employed in the reaction (Table 1, entry 5). Further optimization
showed that the choice of solvent also significantly affected the
yield (Table 1, entries 5–11). When polar N,N-dimethylformamide
(DMF) was used, the overall yield of compounds 3a (E) and (Z)
was best (Table 1, entry 8, 93%). And similar yield was obtained
in NMP(Table 1, entry 10). However, the target compound was
not observed when toluene or acetone was used because no
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10.1002/ejoc.201801602
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4-sulfonylstyrene and 4-cyanostyrene were employed as
substrates, only the (E)-isomers were obtained with low yields (3i-
3k). The low yields of 3i-3k were caused by the degradation of
those styrenes with strong electron-withdrawing groups in the
basic media. And the intermediate anions of 3i-3k may be
stabilized by the strong electron-withdrawing groups (-NO2,
CH3SO2-, -CN) so as to form the favored low-energy (E)-isomers.
Some multi-substituted difluorostyrenes gave good results (3o,
3q, 3r and 3s). The heterocyclic substrate like 2-benzothiophene
difluorine olefin afforded good yield of the product (3n), and
interestingly, the 2-benzofuran difluorine olefin only gave the (E)-
isomer product in 49% yield (3m). For substrates 1l, 1o, 1r and
1s, only the mixtures of (E)- and (Z)- isomers were obtained due
to their difficult separation. To extend the scope of phosphorus
compounds, alkylphosphine oxide like dibutylphosphine oxide
was employed to give a relatively lower yield (3p). To our delight,
the dimethyl phosphite reacted with gem-difluorostyrenes well to
afford good yields (3t, 3u).
In order to explain the mechanism of this reaction, 2 equiv. of free
radical trapper TEMPO (2,2,6,6-Tetramethyl-1-piperidyloxy) or
PBN (α-phenyl-N-tert-butylnitrone) was added to the reaction of
4-phenyl-difluorostyrene 1a and the diphenylphosphine oxide 2a
which was performed under the optimized conditions. The yield of
product 3a only decreased slightly (< 5%) under these two
circumstances. According to the reported literature,[22] 2a could be
converted to phosphinite anion A by a base, so the possible
addition/elimination mechanism was proposed. The phosphinite
anion attacked gem-difluorinated carbon to form the carbon anion
B, then the elimination of fluoride occurred to provide 3a. This
mechanism also explained why most compounds have no
selectivity for E/Z isomers (Figure 2).
[a] Reaction conditions: 1a (0.5 mmol), 2a (1 mmol), DBU (0.75 mmol) in
DMF (5.0 mL) at room temperature for 1 h . [b] Isolated yields. [c] Reaction
conditions: 4.0 equiv. of Cs2CO3 as base, 4.0 equiv. of POH(OCH3)2 was
used, and reaction time extend to 4 hour.
Scheme 2. Exploration of Substrate Scope a, b
Figure 2. Proposed reaction mechanism.
With the optimized conditions in hand, the substrates’ scope was
investigated (Scheme 2). This reaction is readily applicable to
most substrates, including both electron-rich and electron-
deficient difluorostyrenes with moderate to excellent yields. Thus,
difluorostyrenes attached with either alkyl or methoxy groups on
benzene ring reacted with 2a to give the desired products with
good yields (3b-3f). Halogen groups such as Cl and Br were well
tolerated under the reaction conditions (3g, 3o, 3r). The reaction
was not significantly affected by the steric effect, and the ortho-
substituted difluorostyrenes also effectively reacted with
diphenylphosphine oxide to provide the corresponding products
with good yields (3c and 3s). However, the substrates with strong
electron-withdrawing groups on benzene ring provided relatively
lower yields. When the substituent was an ester group, the
desired product was only in 61% yield (3h). While 4-nitrostyrene,
Conclusions
In conclusion, we disclosed a convenient and mild metal-free
approach to (E/Z)-α-fluorovinyl phosphorus compounds from
easily obtained gem-difluorostyrenes and diarylphosphine
oxides/dialkyl phosphite. This method may provide a practical and
concise route for the synthesis of these phosphorus compounds
in material chemistry and drug discovery for the future.
Experimental Section
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10.1002/ejoc.201801602
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o
General Information: All reagents were purchased from commercial
suppliers and used without further purification. The progress of all of the
reactions was monitored by thin layer chromatography with standard TLC
silica gel plates, and the developed plates were visualized under UV light.
All of the compounds were purified by column chromatography.
Chromatography was performed on silica gel (100–200 mesh). Nuclear
magnetic resonance spectra (1H, 13C NMR, 19F NMR and 31P NMR) were
recorded on Varian Mercury-300/400 and Varian Mercury-400/500
spectrometers and CDCl3 was used as the solvent. NMR peaks were
calibrated by reference to standard peaks of chloroform at 7.260 ppm for
1H and 77.160 ppm for 13C. For peak descriptions, the following
abbreviations have been used: s (singlet), d (doublet), t (triplet), dd
(doublet of doublets), td (triplet of doublets), dt (doublet of triplets), pt
(pseudo-triplet), ddd (double of doublets of doublets). High resolution
3a (Z): White solid (92 mg, 43%). M.P. 129-130 C. 1H NMR (500 MHz,
Chloroform-d) δ 7.82 (dd, J= 12.7, 8.0 Hz, 4H), 7.66 (d, J= 8.2 Hz, 2H), 7.5
–7.52 (m, 4H), 7.46 (ddd, J= 9.1, 7.4, 2.3 Hz, 6H), 7.42 (t, J= 7.6 Hz, 2H),
7.38–7.26 (m, 2H). 13C NMR (125 MHz, Chloroform-d) δ 153.68 (dd, J=
272.0, 121.3 Hz), 141.49, 140.49, 132.46 (d, J= 2.7 Hz), 131.78 (d, J= 1.8
Hz), 131.70 (d, J= 1.7 Hz), 130.90, 130.68, 130.02, 128.78, 128.67, 128.57,
128.16 (dd, J= 20.8, 18.3 Hz), 127.51, 127.02, 126.76. 19F NMR (471 MHz,
Chloroform-d) δ -108.07 (dd, J= 85.6, 31.6 Hz). 31P NMR (202 MHz,
Chloroform-d) δ 20.71 (d, J= 85.8 Hz). HRMS (ESI): calcd. for C26H20FOP
[M+H]+ 399.1309, found 399.1315.
(E/Z)-(1-fluoro-2-(4-methoxyphenyl)vinyl)diphenylphosphine oxide:
o
3b (E): White solid (88 mg, 50%). M.P. 113-114 C. 1H NMR (500 MHz,
mass spectra (HRMS) were performed on
a Finnigan MAT 95
Chloroform-d) δ 7.85 (d, J= 7.8 Hz, 2H), 7.83 (d, J= 7.8 Hz, 2H), 7.65–7.59
(m, 4H), 7.53 (td, J= 7.5, 3.1 Hz, 4H), 6.94 (dd, J= 44.2, 6.8 Hz, 1H), 6.92
(d, J= 8.8 Hz, 2H), 3.85 (s, 3H). 13C NMR (125 MHz, Chloroform-d) δ
160.37 (d, J= 3.1 Hz), 152.24 (dd, J= 288.3, 134.5 Hz), 132.56 (d, J= 2.8
Hz), 131.82, 131.74, 131.59 (d, J= 7.5 Hz), 130.69, 129.83, 128.74, 128.64,
124.26 (d, J= 10.6 Hz), 122.20 (d, J= 21.9 Hz), 114.16, 55.31. 19F NMR
(471 MHz, Chloroform-d) δ -124.92 (dd, J= 73.9, 45.0 Hz). 31P NMR (202
MHz, Chloroform-d) δ 19.40 (d, J= 73.4 Hz). HRMS (ESI): calcd. for
C21H18FO2P [M+H]+ 353.1101, found 353.1110.
spectrometer. Melting points were measured by Büchi 510 melting point
apparatus without further corrected.
General Procedure for the Synthesis of Various Substituted 2-(2,2-
difluorovinyl) benzene (1a-1u): A 250 mL, three-necked round-bottom
flask was equipped with a stir bar. The vessel was then fitted with a
condenser topped by a T-tube with slow flow of N2, and then sealed with
septa. The vessel was flamed dried and then allowed to cool to room
temperature. Under the inert nitrogen atmosphere, acetonitrile (75 mL)
was added to the vessel, and the temperature was increased to 70 oC.
Then, triphenylphosphine (6 mmol), potassium iodide (4 mmol), and
aldehyde (2 mmol) were added and let it stir for 30 min. Methyl 2,2-difluoro-
2-(fluorosulfonyl) acetate (MDFA) (3.5 mmol) was then added slowly over
a period of 10 min. The resulting mixture was stirred for three hours, a
nitrogen atmosphere was maintained until the end of the reaction. Then
the reaction was quenched with water and extracted with ethyl acetate.
The ethyl acetate was then removed by rotary evaporation to produce a
black, semi-solid slurry. Additional impurities were removed via column
chromatography using a mixture of petroleum ether and ethyl acetate to
obtain pure product.[20]
1
3b (Z): colourless oil (76 mg, 43%). H NMR (500 MHz, Chloroform-d) δ
7.83 (d, J= 8.0 Hz, 2H), 7.81 (d, J= 8.0 Hz, 2H), 7.62–7.54 (m, 4H), 7.52–
7.45 (m, 4H), 7.26 (dd, J= 32.3, 21.2 Hz, 1H), 6.81 (d, J= 8.8 Hz, 2H), 3.79
(s, 3H). 13C NMR (125 MHz, Chloroform-d) δ 160.11, 152.01 (dd, J= 268.1,
123.1 Hz), 132.35 (d, J= 2.9 Hz), 131.82 (d, J= 2.5 Hz), 131.75, 131.66,
131.14, 130.27, 128.61, 128.51, 128.41 (d, J= 2.4 Hz), 122.43 (d, J= 11.3
Hz), 113.61, 55.22. 19F NMR (471 MHz, Chloroform-d) δ -111.23 (dd, J=
86.6, 32.3 Hz). 31P NMR (202 MHz, Chloroform-d) δ 20.78 (d, J= 87.1 Hz).
HRMS (ESI): calcd. for C21H18FO2P [M+H]+ 353.1101, found 353.1103.
(E/Z)-(1-fluoro-2-(2-methoxyphenyl)vinyl)diphenylphosphine oxide:
General Procedure for the Synthesis of (E/Z)-(1-fluoro-2-arylvinyl)
phosphine oxide. (Example of 3a)
3c (E): White solid (55 mg, 31%). M.P. 68 oC. 1H NMR (500 MHz,
Chloroform-d) δ 7.88 (d, J= 7.8 Hz, 1H), 7.84 (d, J= 7.9 Hz, 2H), 7.82 (d,
J= 7.9 Hz, 2H), 7.58 (ddt, J= 7.3, 5.5, 1.4 Hz, 2H), 7.53–7.49 (m, 4H), 7.49–
7.40 (m, 1H), 7.33–7.28 (m, 1H), 6.94 (t, J= 7.6 Hz, 1H), 6.89 (d, J= 8.3
Hz, 1H), 3.83 (s, 3H). 13C NMR (125 MHz, Chloroform-d) δ 157.04, 153.75
(dd, J= 290.5, 134.2 Hz), 132.52 (d, J= 2.7 Hz), 131.88, 131.79, 130.72 (d,
J= 9.7 Hz), 129.88, 128.71, 128.61, 120.49, 120.31 (d, J= 10.6 Hz), 116.38
(d, J= 23.0 Hz), 110.74, 55.49. 19F NMR (471 MHz, Chloroform-d) δ -
122.60 (dd, J = 75.4, 45.7 Hz). 31P NMR (202 MHz, Chloroform-d) δ 19.41
(d, J= 74.4 Hz). HRMS (ESI): calcd. for C21H18FO2P [M+H]+ 353.1101,
found 353.1105.
A 50 mL sealed tube equipped with a magnetic stirrer was charged with 4-
phenyl-difluorostyrene 1a (0.5 mmol), diphenylphosphine oxide 2a (1
mmol) in DMF (5.0 mL), and then DBU (0.75 mmol) was added, the
reaction mixture was stirred for 1h at room temperature. Then the mixture
was diluted with water. Subsequently the mixture was extracted with
EtOAc (5 mL × 3). The combined extract was successively washed with
brine, dried over anhydrous Na2SO4 and evaporated to dryness. The crude
product was purified by silica gel chromatography eluted with PE/EtOAc =
2:1 to give the product 3a.
3c (Z): colourless oil (72mg, 41%). 1H NMR (500 MHz, Chloroform-d) δ
7.78 (dd, J= 12.6, 7.9 Hz, 4H), 7.61–7.56 (m, 1H), 7.53–7.46 (m, 2H), 7.41
(td, J= 7.7, 3.2 Hz, 5H), 7.18 (t, J= 8.5 Hz, 1H), 6.79 (t, J= 7.5 Hz, 1H),
6.71 (d, J= 8.3 Hz, 1H), 3.73 (s, 3H). 13C NMR (125 MHz, Chloroform-d) δ
156.80, 153.68 (dd, J= 272.2, 123.6 Hz), 132.20 (d, J= 2.6 Hz), 132.01,
131.66, 131.58, 131.21, 130.42, 130.34, 128.48, 128.38, 123.87 (dd, J=
20.8, 18.6 Hz), 120.04, 119.14 (d, J= 10.8 Hz), 109.88, 55.25. 19F NMR
(471 MHz, Chloroform-d) δ -109.23 (dd, J= 85.6, 30.2 Hz). 31P NMR (202
MHz, Chloroform-d) δ 20.06 (d, J= 85.6 Hz). HRMS (ESI): calcd. for
C21H18FO2P [M+H]+ 353.1101, found 353.1103.
(E/Z)-(2-([1,1'-biphenyl]-4-yl)-1-fluorovinyl) diphenylphosphine oxide:
1
3a (E): White solid (107 mg, 50%), M.P. 163 oC. H NMR (500 MHz,
Chloroform-d) δ 7.84 (dd, J= 12.6, 7.8 Hz, 4H), 7.72 (d, J= 8.4 Hz, 2H),
7.64–7.58 (m, 6H), 7.55–7.50 (m, 4H), 7.47–7.42 (m, 2H), 7.38–7.34 (m,
1H), 7.03 (dd, J= 43.7, 6.7 Hz, 1H). 13C NMR (125 MHz, Chloroform-d) δ
154.15 (dd, J= 292.0, 131.6 Hz), 142.10, 140.23, 132.69 (d, J= 2.6 Hz),
131.82 (d, J= 10.5 Hz), 130.42 (d, J= 7.5 Hz), 129.60, 128.88, 128.81,
128.71, 127.76, 127.37, 127.06, 122.12 (d, J= 21.5 Hz). 19F NMR (471
MHz, Chloroform-d) δ -120.95 (dd, J= 72.4, 43.8 Hz). 31P NMR (202 MHz,
Chloroform-d) δ 19.29 (d, J= 72.6 Hz). HRMS (ESI): calcd. for C26H20FOP
[M+H]+ 399.1309, found 399.1306.
(E/Z)-(1-fluoro-2-(3-methoxyphenyl)vinyl)diphenylphosphine oxide:
o
3d (E): White solid (86 mg, 49%). M.P. 128-129 C. 1H NMR (500 MHz,
Chloroform-d) δ 7.85 (dd, J= 12.6, 7.9 Hz, 4H), 7.62 (dd, J= 7.5, 1.5 Hz,
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10.1002/ejoc.201801602
European Journal of Organic Chemistry
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2H), 7.54 (td, J= 7.6, 3.1 Hz, 4H), 7.31 (d, J= 7.8 Hz, 1H), 7.24 (d, J= 7.3
Hz, 2H), 7.04–6.91 (m, 2H), 3.83 (s, 3H). 13C NMR (125 MHz, Chloroform-
d) δ 159.67, 154.22 (dd, J= 292.4, 131.3 Hz), 132.66, 132.59 (d, J= 10.5
Hz), 131.85, 131.76, 130.41, 129.70, 129.55, 128.79, 128.69, 122.58 (d,
J= 7.0 Hz), 122.41 (d, J= 21.4 Hz), 115.52, 114.89 (d, J= 7.9 Hz), 55.27.
(d, J= 11.1 Hz), 125.77, 33.49, 23.33. 19F NMR (471 MHz, Chloroform-d)
δ -109.72 (dd, J= 86.5, 31.8 Hz). 31P NMR (202 MHz, Chloroform-d) δ
20.60 (d, J= 86.0 Hz). HRMS (ESI): calcd. for C23H22FOP [M+H]+ 365.1465,
found 365.1471.
19F NMR (471 MHz, Chloroform-d) δ -120.51 (dd, J= 72.5, 43.6 Hz). 31
P
(E/Z)-(2-(4-chlorophenyl)-1-fluorovinyl)diphenylphosphine oxide:
NMR (202 MHz, Chloroform-d) δ 19.21 (d, J= 73.4 Hz). HRMS (ESI): calcd.
for C21H18FO2P [M+H]+ 353.1101, found 353.1106.
3g (E): White solid (82 mg, 46%). M.P. 122 oC. 1H NMR (500 MHz,
Chloroform-d) δ 7.82 (dd, J= 12.3, 7.7 Hz, 4H), 7.64–7.59 (m, 2H), 7.58 (d,
J= 8.6 Hz, 2H), 7.55–7.49 (m, 4H), 7.37–7.33 (m, 2H), 6.96 (dd, J= 43.2,
6.7 Hz, 1H). 13C NMR (125 MHz, Chloroform-d) δ 154.54 (dd, J= 293.0,
130.8 Hz), 135.28 (d, J= 3.3 Hz), 132.79 (d, J= 2.6 Hz), 131.77 (d, J= 10.5
Hz), 131.15 (d, J= 7.6 Hz), 130.74 (d, J= 11.5 Hz), 130.14, 129.88 (d, J=
10.5 Hz), 129.27, 129.01, 128.85, 128.74, 121.38, 121.21. 19F NMR (471
MHz, Chloroform-d) δ -120.40 (dd, J= 71.7, 43.2 Hz). 31P NMR (202 MHz,
3d (Z): White solid (76 mg, 43%). M.P. 90 oC. 1H NMR (500 MHz,
Chloroform-d) δ 7.82 (dd, J= 12.7, 7.9 Hz, 4H), 7.59–7.54 (m, 2H), 7.48
(td, J= 7.6, 3.2 Hz, 4H), 7.41–7.38 (m, 1H), 7.28 (dd, J= 42.0, 6.8 Hz, 1H),
7.17 (t, J= 7.9 Hz, 1H), 7.08 (d, J= 7.7 Hz, 1H), 6.80 (dd, J= 8.2, 2.3 Hz,
1H), 3.79 (s, 3H). 13C NMR (125 MHz, Chloroform-d) δ 159.19, 153.95 (dd,
J= 272.5, 120.8 Hz), 132.39 (d, J= 2.7 Hz), 131.68, 131.60, 131.31 (d, J=
11.5 Hz), 130.92, 130.05, 129.05, 128.61, 128.51, 128.36 (d, J= 2.8 Hz),
128.20, 122.77 (d, J= 2.2 Hz), 115.62, 114.72, 55.29. 19F NMR (471 MHz,
Chloroform-d) δ -85.53 (dd, J= 86.2, 31.4 Hz). 31P NMR (202 MHz,
Chloroform-d) δ 20.90 (d, J= 86.9 Hz). HRMS (ESI): calcd. for C21H18FO2P
[M+H]+ 353.1101, found 353.1107.
Chloroform-d)
δ 19.24 (d, J= 70.5 Hz). HRMS (ESI): calcd. for
C20H15ClFOP [M+H]+ 357.0606, found 357.0608.
3g (Z): colourless oil (75 mg, 42%). 1H NMR (300 MHz, Chloroform-d) δ
7.78 (dd, J= 12.6, 8.0 Hz, 4H), 7.61–7.42 (m, 8H), 7.33–7.11 (m, 3H). 13
C
NMR (125 MHz, Chloroform-d) δ 154.21 (dd, J= 274.0, 120.1 Hz), 134.85,
132.56 (d, J= 2.7 Hz), 131.72, 131.64, 131.48 (d, J= 2.5 Hz), 130.68,
129.80, 128.71, 128.61, 128.29, 127.28 (dd, J= 21.4, 18.0 Hz). 19F NMR
(471 MHz, Chloroform-d) δ -107.06 (dd, J= 84.1, 30.9 Hz). 31P NMR (202
MHz, Chloroform-d) δ 20.60 (d, J= 84.3 Hz). HRMS (ESI): calcd. for
C20H15ClFOP [M+H]+ 357.0606, found357.0614.
(E/Z)-(1-fluoro-2-(p-tolyl)vinyl)diphenylphosphine oxide:
3e (E): White solid (52 mg, 31%). M.P. 78-80 oC. 1H NMR (500 MHz,
Chloroform-d) δ 7.86 (d, J= 7.9 Hz, 2H), 7.83 (d, J= 7.9 Hz, 2H), 7.62 (td,
J= 8.6, 8.0, 2.1 Hz, 2H), 7.58–7.51 (m, 6H), 7.21 (d, J= 8.0 Hz, 2H), 6.97
(dd, J= 44.0, 6.8 Hz, 1H), 2.39 (s, 3H). 13C NMR (125 MHz, Chloroform-d)
δ 153.25 (dd, J= 290.1, 133.3 Hz), 139.68 (d, J= 2.5 Hz), 132.61 (d, J= 2.9
Hz), 131.79 (d, J= 10.5 Hz), 130.54, 129.68, 129.46, 128.71 (d, J= 12.7
Hz), 122.53 (d, J= 21.6 Hz), 21.44. 19F NMR (471 MHz, Chloroform-d) δ -
122.45 (dd, J= 73.2, 44.1 Hz). 31P NMR (202 MHz, Chloroform-d) δ 19.40
(d, J= 71.0 Hz). HRMS (ESI): calcd. for C21H18FOP [M+H]+ 337.1152,
found 337.1160.
Methyl (E/Z)-4-(2-(diphenylphosphoryl)-2-fluorovinyl)benzoate:
3h (E): White solid (91 mg 47%). M.P. 150 oC. 1H NMR (500 MHz,
Chloroform-d) δ 8.05 (d, J= 8.5 Hz, 2H), 7.84 (dd, J= 12.7, 7.9 Hz, 4H),
7.71 (d, J= 8.4 Hz, 2H), 7.63 (dd, J= 7.5, 1.6 Hz, 2H), 7.54 (td, J= 7.6, 3.2
Hz, 4H), 7.05 (dd, J= 43.0, 6.7 Hz, 1H), 3.94 (s, 3H). 13C NMR (125 MHz,
Chloroform-d) δ 168.37, 157.86 (dd, J= 295.3, 128.3 Hz), 134.75 (d, J= 2.6
Hz), 133.69 (d, J= 10.4 Hz), 132.38, 131.94, 131.83, 131.67 (d, J= 7.6 Hz),
131.08, 130.73 (d, J= 12.7 Hz), 123.22 (d, J= 21.3 Hz), 54.16. 19F NMR
(471 MHz, Chloroform-d) δ -117.46 (dd, J= 71.0, 43.0 Hz). 31P NMR (202
MHz, Chloroform-d) δ 19.04 (d, J= 70.0 Hz). HRMS (ESI): calcd. for
C22H18FO3P [M+H]+ 381.1050, found 380.1051.
3e (Z): colourless oil (59 mg, 35%). 1H NMR (500 MHz, Chloroform-d) δ
7.83 (d, J= 8.0 Hz, 2H), 7.80 (d, J= 8.0 Hz, 2H), 7.57 (td, J= 7.3, 1.5 Hz,
2H), 7.49 (td, J= 7.7, 3.9 Hz, 6H), 7.29 (dd, J= 31.8, 21.3 Hz, 1H), 7.08 (d,
J= 8.0 Hz, 2H), 2.31 (s, 3H). 13C NMR (125 MHz, Chloroform-d) δ 152.93
(dd, J= 270.3, 122.3 Hz), 138.89, 132.33 (d, J= 2.7 Hz), 131.71 (d, J= 10.4
Hz), 131.09, 130.22, 130.11, 128.80, 128.60, 128.50, 127.05 (d, J= 11.4
Hz), 21.30. 19F NMR (471 MHz, Chloroform-d) δ -109.68 (dd, J= 86.0, 31.8
Hz). 31P NMR (202 MHz, Chloroform-d) δ 20.54 (d, J= 95.1 Hz). HRMS
(ESI): calcd. for C21H18FOP [M+H]+ 337.1152, found 337.1154.
3h (Z): colourless oil (25 mg, 13%). 1H NMR (500 MHz, Chloroform-d) δ
7.93 (d, J= 8.4 Hz, 2H), 7.85–7.78 (m, 4H), 7.65 (d, J= 8.3 Hz, 2H), 7.58
(td, J= 7.3, 1.5 Hz, 2H), 7.50 (td, J= 7.6, 3.2 Hz, 4H), 7.31 (dd, J= 30.6,
20.7 Hz, 1H), 3.91 (s, 3H). 13C NMR (125 MHz, Chloroform-d) δ 166.63,
154.90 (dd, J= 270.0, 120.0 Hz), 134.66 (d, J= 10.9 Hz), 132.63 (d, J= 2.9
Hz), 131.72, 131.64, 130.51, 130.10, 130.01, 129.64, 129.25, 128.74,
128.63, 127.37 (d, J= 17.8 Hz), 127.20 (d, J= 17.7 Hz), 52.15. 19F NMR
(471 MHz, Chloroform-d) δ -104.66 (dd, J= 83.4, 30.5 Hz).31P NMR (202
MHz, Chloroform-d) δ 20.56 (d, J= 93.8 Hz). HRMS (ESI): calcd. for
C22H18FO3P [M+H]+ 381.1050, found 380.1057.
(E/Z)-(1-fluoro-2-(4-isopropylphenyl)vinyl)diphenylphosphine oxide:
3f (E): colourless oil (68 mg, 37%). 1H NMR (500 MHz, Chloroform-d) δ
7.82 (dd, J= 12.6, 8.0 Hz, 4H), 7.62–7.56 (m, 4H), 7.51 (td, J= 7.6, 3.1 Hz,
4H), 7.24 (d, J= 8.3 Hz, 2H), 6.96 (dd, J= 44.1, 6.8 Hz, 1H), 2.95–2.88 (m,
1H), 1.25 (d, J= 6.9 Hz, 6H). 13C NMR (125 MHz, Chloroform-d) δ 153.06
(dd, J= 293.9, 132.2 Hz), 150.16, 132.20 (d, J= 3.0 Hz), 131.37 (d, J= 10.5
Hz), 130.10, 129.63 (d, J= 7.3 Hz), 129.23, 128.62 (d, J= 11.0 Hz), 128.29
(d, J= 12.7 Hz), 126.43, 122.08 (d, J= 21.5 Hz), 33.64, 23.36. 19F NMR
(471 MHz, Chloroform-d) δ -122.37 (dd, J= 73.2, 44.1 Hz). 31P NMR (202
MHz, Chloroform-d) δ 19.43 (d, J= 73.8 Hz). HRMS (ESI): calcd. for
C23H22FOP [M+H]+ 365.1465, found 365.1464.
(E)-4-(2-(diphenylphosphoryl)-2-fluorovinyl)benzonitrile:
3i (E): colourless oil (69 mg, 40%).1H NMR (500 MHz, Chloroform-d) δ
7.83 (dd, J= 12.6, 7.9 Hz, 4H), 7.73 (d, J= 8.0 Hz, 2H), 7.65 (dd, J= 17.9,
8.0 Hz, 4H), 7.58–7.50 (m, 4H), 7.04 (dd, J= 42.3, 6.6 Hz, 1H). 13C NMR
(125 MHz, Chloroform-d) δ 157.09 (dd, J= 300.0, 122.4 Hz), 135.66 (d, J=
10.3 Hz), 133.00 (d, J= 2.5 Hz), 132.45, 131.75 (d, J= 10.5 Hz), 130.24 (d,
J= 7.7 Hz), 129.71, 128.90 (d, J= 12.8 Hz), 120.47 (d, J= 21.2 Hz), 118.39,
112.58. 19F NMR (471 MHz, Chloroform-d) δ -115.72 (dd, J= 69.4, 42.3
Hz). 31P NMR (202 MHz, Chloroform-d) δ 18.95 (d, J= 69.0 Hz). HRMS
(ESI): calcd. for C21H15NFOP [M+H]+ 348.0948, found 348.0952.
1
3f (Z): colourless oil (89 mg, 49%). H NMR (500 MHz, Chloroform-d) δ
7.79 (dd, J= 12.6, 7.8 Hz, 4H), 7.55–7.48 (m, 4H), 7.45 (td, J= 7.6, 3.2 Hz,
4H), 7.27 (dd, J= 31.7, 20.9 Hz, 1H), 7.09 (d, J= 8.2 Hz, 2H), 2.83 (p, J=
6.9 Hz, 1H), 1.19 (d, J= 6.9 Hz, 6H). 13C NMR (125 MHz, Chloroform-d) δ
152.57 (dd, J= 270.1, 122.5 Hz), 149.27, 131.92 (d, J= 2.7 Hz), 131.29 (d,
J= 10.3 Hz), 130.59, 129.80 (d, J= 2.4 Hz), 129.72, 128.17, 128.07, 127.02
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10.1002/ejoc.201801602
European Journal of Organic Chemistry
FULL PAPER
(E)-(1-fluoro-2-(4-nitrophenyl)vinyl)diphenylphosphine oxide:
155.54 (dd, J= 279.3, 142.8 Hz), 139.04, 137.66, 132.77 (d, J= 2.7 Hz),
131.81 (d, J= 10.5 Hz), 130.34, 129.53 (d, J= 14.1 Hz), 128.81 (d, J= 12.7
Hz), 125.97 (d, J= 10.5 Hz), 124.87 (d, J= 15.6 Hz), 122.68, 121.57, 113.98
(d, J= 22.3 Hz). 19F NMR (471 MHz, Chloroform-d) δ -118.32 (dd, J= 70.5,
42.5 Hz).31P NMR (202 MHz, Chloroform-d) δ 19.49 (d, J= 70.0 Hz).
HRMS (ESI): calcd. for C22H16FOPS [M+H]+ 379.0716, found 379.0718.
3j (E): White solid (35 mg, 19%). M.P. 224 oC. 1H NMR (500 MHz,
Chloroform-d) δ 8.26 (d, J= 8.8 Hz, 2H), 7.89–7.79 (m, 6H), 7.69–7.63 (m,
2H), 7.57 (td, J= 7.6, 3.1 Hz, 4H), 7.11 (dd, J= 42.1, 6.6 Hz, 1H). 13C NMR
(125 MHz, Chloroform-d) δ 157.55 (dd, J= 299.9, 125.8 Hz), 147.66,
137.51 (d, J= 10.3 Hz), 133.03 (d, J= 3.0 Hz), 131.82, 131.73, 130.51 (d,
J= 7.8 Hz), 129.67, 128.97, 128.87, 128.80, 123.96, 120.01 (d, J= 21.1
Hz). 19F NMR (471 MHz, Chloroform-d) δ -115.08 (dd, J= 68.8, 42.2 Hz).
31P NMR (202 MHz, Chloroform-d) δ 18.90 (d, J= 69.0 Hz). HRMS (ESI):
calcd. for C20H15FNO3P [M+H]+ 368.0846, found 368.0849.
3n (Z): colourless oil (106 mg, 56%). 1H NMR (500 MHz, Chloroform-d) δ
8.32 (s, 1H), 7.81–7.75 (m, 5H), 7.70 (d, J= 8.0 Hz, 1H), 7.50 (td, J= 7.7,
1.4 Hz, 2H), 7.46–7.44 (m, 1H), 7.40 (qd, J= 8.1, 2.1 Hz, 5H), 7.36–7.31
(m, 1H). 13C NMR (125 MHz, Chloroform-d) δ 155.48 (dd, J= 275.7, 121.6
Hz), 139.58, 138.16, 132.39 (d, J= 2.7 Hz), 131.49 (d, J= 10.3 Hz), 130.48,
130.12, 129.61, 128.55 (d, J= 12.7 Hz), 124.36 (d, J= 10.5 Hz), 124.08 (d,
J= 9.6 Hz), 122.77, 121.15, 119.52 (dd, J= 22.3, 18.9 Hz). 19F NMR (471
MHz, Chloroform-d) δ -107.90 (dd, J= 83.7, 28.8 Hz).31P NMR (202 MHz,
Chloroform-d) δ 20.93 (d, J= 92.3 Hz). HRMS (ESI): calcd. for C22H16FOPS
[M+H]+ 379.0716, found 379.0726.
(E)-(1-fluoro-2-(4-(methylsulfonyl)phenyl)vinyl)diphenylphosphine
oxide:
3k (E): colourless oil (54 mg, 27%). 1H NMR (500 MHz, Chloroform-d) δ
7.96 (d, J= 8.0 Hz, 2H), 7.84 (t, J= 9.2 Hz, 6H), 7.64 (t, J= 7.4 Hz, 2H),
7.58 – 7.51 (m, 4H), 7.08 (dd, J= 42.2, 6.5 Hz, 1H), 3.06 (s, 3H).13C NMR
(125 MHz, Chloroform-d) δ 157.17 (dd, J= 298.7, 126.5 Hz), 140.60,
136.56 (d, J= 10.2 Hz), 133.01 (d, J= 2.6 Hz), 131.76 (d, J= 10.5 Hz),
130.51 (d, J= 7.5 Hz), 129.69, 128.91 (d, J= 12.8 Hz), 127.80, 120.35 (d,
J= 21.2 Hz), 44.44.19F NMR (471 MHz, Chloroform-d) δ -115.70 (dd, J=
69.5, 42.2 Hz). 31P NMR (202 MHz, Chloroform-d) δ 19.04 (d, J= 69.2 Hz).
HRMS (ESI): calcd. for C21H18FOPS [M+H]+ 401.0771, found 401.0778.
(E/Z)-(2-(2-bromo-4-methoxyphenyl)-1-
fluorovinyl)diphenylphosphine oxide:
1
Mixture of 3o (E) and 3o (Z): colourless oil (168mg, 78%). H NMR (500
MHz, Chloroform-d) δ 7.86 (dd, J= 12.6, 7.6 Hz, 4H), 7.78 (dd, J= 12.6, 7.4
Hz, 4H), 7.62 (t, J= 7.5 Hz, 2H), 7.57–7.50 (m, 4H), 7.50–7.46 (m, 3H),
7.45–7.32 (m, 6H), 7.30 (dd, J= 6.5, 4.1 Hz, 2H), 7.22 (dd, J= 17.1, 7.9 Hz,
1H), 6.77 (dd, J= 8.9, 3.0 Hz, 1H), 6.57 (dd, J= 8.8, 3.0 Hz, 1H), 3.76 (d,
J= 9.8 Hz, 6H). 13C NMR (125 MHz, Chloroform-d) δ 158.42 (d, J= 76.0
Hz), 157.40 (d, J= 15.5 Hz), 156.42 (d, J= 5.3 Hz), 155.12, 154.13 (d, J=
11.2 Hz), 133.55, 132.81 (d, J= 2.6 Hz), 132.58, 132.39 (d, J= 2.7 Hz),
131.87 (d, J= 10.4 Hz), 131.67 (d, J= 10.6 Hz), 131.39 (d, J= 10.2 Hz),
129.80 (dd, J= 109.3, 48.0 Hz), 128.68 (dd, J= 33.5, 12.7 Hz), 127.05 (dd,
J= 22.0, 18.1 Hz), 121.08 (d, J= 22.9 Hz), 117.38, 117.21, 116.88, 116.26
(d, J= 12.1 Hz), 115.04, 114.20 (d, J= 2.9 Hz), 55.54. 19F NMR (471 MHz,
Chloroform-d) δ -106.98 (dd, J= 84.0, 27.3 Hz), -120.06 (dd, J= 73.5, 42.1
Hz). 31P NMR (202 MHz, Chloroform-d) δ 20.15 (ddd, J= 131.5, 69.5, 40.4
Hz). HRMS (ESI): calcd. for C21H17BrFO2P [M+H]+ 431.0206, found
431.0212.
(E/Z)-(1-fluoro-2-(naphthalen-2-yl)vinyl)diphenylphosphine oxide:
1
Mixture of 3l (E) and 3l (Z): colourless oil (164 mg, 88%). H NMR (600
MHz, Chloroform-d) δ 8.14 (d, J= 8.3 Hz, 1H), 7.96 (d, J= 7.2 Hz, 1H), 7.88
(dd, J= 12.3, 7.7 Hz, 7H), 7.76 (dd, J= 11.4, 6.1 Hz, 2H), 7.73–7.66 (m,
4H), 7.66–7.59 (m, 3H), 7.54 (tt, J= 7.5, 3.8 Hz, 6H), 7.48 (dt, J= 14.8, 8.0
Hz, 3H), 7.40 (t, J= 7.5 Hz, 2H), 7.32–7.27 (m, 3H), 7.25 (s, 1H). 13C NMR
(150 MHz, Chloroform-d) δ 133.05, 132.49, 132.19, 131.53, 131.27 (d, J=
10.5 Hz), 130.82 (d, J= 10.0 Hz), 130.65, 129.87 (d, J= 33.6 Hz), 129.24,
129.04, 128.78, 128.30, 128.21, 128.13, 127.89 (d, J= 18.9 Hz), 127.78,
127.69, 126.67 (d, J= 10.0 Hz), 126.28, 125.78, 125.56, 125.32, 124.76 (d,
J= 8.3 Hz), 124.48, 123.78, 123.24, 118.70 (d, J= 21.8 Hz). 19F NMR (471
MHz, Chloroform-d) δ -107.30 (dd, J= 83.4, 27.0 Hz), -121.04 (dd, J= 73.5,
41.3 Hz)31P NMR (202 MHz, Chloroform-d) δ 20.01–19.01 (m). HRMS
(ESI): calcd. for C24H18FOP [M+H]+ 373.1152, found 373.1151.
(E/Z)-(2-([1,1'-biphenyl]-4-yl)-1-fluorovinyl)dibutylphosphine oxide:
3p (E): colourless oil (18 mg, 10%). 1H NMR (500 MHz, Chloroform-d) δ
7.70 (d, J= 8.4 Hz, 2H), 7.62 (dd, J= 9.5, 8.3 Hz, 4H), 7.49–7.42 (m, 2H),
7.40–7.34 (m, 1H), 6.78 (dd, J= 42.3, 8.5 Hz, 1H), 4.21–4.09 (m, 4H),
1.76–1.68 (m, 4H), 1.49–1.40 (m, 4H), 0.95 (t, J= 7.4 Hz, 6H). 13C NMR
(125 MHz, Chloroform-d) δ 142.17, 140.19, 130.51 (d, J= 7.7 Hz), 130.18
(d, J= 14.8 Hz), 128.89, 127.80, 127.38, 127.06, 122.80 (d, J= 29.9 Hz),
66.88, 32.35 (d, J= 6.4 Hz), 18.66, 13.56. 19F NMR (471 MHz, Chloroform-
d) δ -126.24 (dd, J= 97.0, 42.3 Hz). 31P NMR (202 MHz, Chloroform-d) δ
6.08 (d, J= 104.5 Hz). HRMS (ESI): calcd. for C22H28FOP [M+H]+ 358.4401,
found 358.4406.
(E)-(2-(benzofuran-2-yl)-1-fluorovinyl)diphenylphosphine oxide (3m):
1
3m (E): White solid (89 mg, 49%). M.P. 110 oC. H NMR (500 MHz,
Chloroform-d) δ 7.83 (dd, J= 12.4, 7.6 Hz, 4H), 7.65–7.60 (m, 2H), 7.60–
7.57 (m, 1H), 7.56–7.51 (m, 4H), 7.48 (dd, J= 8.3, 0.8 Hz, 1H), 7.33 (ddd,
J= 8.4, 7.3, 1.3 Hz, 1H), 7.24 (td, J= 7.6, 0.9 Hz, 1H), 7.11 (s, 1H), 7.09
(dd, J= 40.4, 6.3 Hz, 1H). 13C NMR (125 MHz, Chloroform-d) δ 154.97 (dd,
J= 296.9, 129.3 Hz), 154.89 (d, J= 2.0 Hz), 148.51 (d, J= 12.5 Hz), 132.89
(d, J= 2.7 Hz), 131.81 (d, J= 10.6 Hz), 129.93, 129.05, 128.86 (d, J= 12.8
Hz), 128.22, 125.87, 123.30, 121.57, 112.53 (d, J= 23.2 Hz), 111.45,
110.35 (d, J= 9.9 Hz). 19F NMR (471 MHz, Chloroform-d) δ -115.18 (dd, J
= 66.2, 40.5 Hz). 31P NMR (202 MHz, Chloroform-d) δ 19.43 (d, J= 67.6
Hz). HRMS (ESI): calcd. for C22H16FO2P [M+H]+ 363.0945, found
363.0954.
3p (Z): colourless oil (23 mg, 13%). 1H NMR (500 MHz, Chloroform-d) δ
7.59 (dd, J= 4.9, 1.9 Hz, 6H), 7.47–7.40 (m, 2H), 7.38–7.32 (m, 1H), 7.12
(t, J= 29.4 Hz, 1H), 4.12–3.97 (m, 4H), 1.57 (p, J= 6.7 Hz, 4H), 1.32 (h, J=
7.4 Hz, 4H), 0.87 (t, J= 7.4 Hz, 6H). 13C NMR (125 MHz, Chloroform-d) δ
150.93 (dd, J= 267.5, 229.4 Hz), 141.57, 140.42, 130.08, 129.32 (d, J=
10.7 Hz), 128.83, 127.59, 126.94 (d, J= 19.0 Hz), 125.42 (dd, J= 27.5, 20.9
Hz), 66.97 (d, J= 6.1 Hz), 32.19 (d, J= 6.6 Hz), 18.58, 13.51. 19F NMR (471
MHz, Chloroform-d) δ -115.33 (dd, J= 109.3, 29.3 Hz). 31P NMR (202 MHz,
Chloroform-d) δ 5.52–2.85 (m). HRMS (ESI): calcd. for C22H28FOP [M+H]+
358.4401, found 358.4402.
(E/Z)-(2-(benzo[b]thiophen-2-yl)-1-fluorovinyl)diphenylphosphine
oxide:
3n (E): colourless oil (64 mg, 34%). 1H NMR (500 MHz, Chloroform-d) δ
8.07 (s, 1H), 7.95 (d, J= 8.1 Hz, 1H), 7.90 – 7.82 (m, 5H), 7.62 (td, J= 7.3,
1.5 Hz, 2H), 7.56–7.51 (m, 4H), 7.46 (ddd, J= 8.2, 7.1, 1.2 Hz, 1H), 7.43–
7.38 (m, 1H), 7.34–7.26 (m, 1H). 13C NMR (125 MHz, Chloroform-d) δ
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10.1002/ejoc.201801602
European Journal of Organic Chemistry
FULL PAPER
(E/Z)-(2-(1,3-dihydroisobenzofuran-5-yl)-1
fluorovinyl)diphenylphosphine oxide:
126.34 (dd, J= 21.9, 17.8 Hz), 125.39, 125.35, 120.61 (d, J= 10.5 Hz),
119.93 (d, J= 23.6 Hz), 113.83, 111.91, 111.63, 55.65, 55.52, 55.48, 19.58,
19.46. 19F NMR (471 MHz, Chloroform-d) δ -108.19 (dd, J= 87.8, 32.3 Hz),
-124.86 (dd, J= 78.0, 44.0 Hz). 31P NMR (202 MHz, Chloroform-d) δ 24.26–
18.24 (m). HRMS (ESI): calcd. for C29H25ClFO3P [M+H]+ 507.1287, found
507.1301.
3q (E): White solid (79 mg, 43%). M.P. 168-170 C. 1H NMR (500 MHz,
Chloroform-d) δ 7.81 (dd, J= 12.4, 7.7 Hz, 4H), 7.59 (tq, J= 6.9, 1.4 Hz,
2H), 7.54–7.47 (m, 4H), 7.24 (d, J= 1.5 Hz, 1H), 7.08 (dd, J= 8.1, 1.3 Hz,
1H), 6.89 (dd, J= 43.5, 6.8 Hz, 1H), 6.81 (d, J= 8.1 Hz, 1H), 5.97 (s, 2H).
13C NMR (125 MHz, Chloroform-d) δ 152.05 (dd, J= 289.2, 133.7 Hz),
148.09 (d, J= 2.8 Hz), 147.52, 132.20 (d, J= 2.6 Hz), 131.33 (d, J= 10.4
Hz), 130.08, 129.21, 128.29 (d, J= 12.7 Hz), 124.89 (dd, J= 58.6, 8.3 Hz),
121.86 (d, J= 21.9 Hz), 109.19 (d, J= 9.7 Hz), 108.07, 100.97. 19F NMR
(471 MHz, Chloroform-d) δ -123.99 (dd, J= 72.8, 43.5 Hz). 31P NMR (202
MHz, Chloroform-d) δ 19.35 (d, J= 72.3 Hz). HRMS (ESI): calcd. for
C21H16FO3P [M+H]+ 367.0894, found 367.0894.
o
Dimethyl (E/Z)-(2-([1,1'-biphenyl]-4-yl)-1-fluorovinyl)phosphonate:
3t (E): White solid (63 mg, 41%). M.P. 62 oC. 1H NMR (600 MHz,
Chloroform-d) δ 7.72 (d, J= 8.3 Hz, 2H), 7.64 (dd, J= 13.6, 7.8 Hz, 4H),
7.48 (t, J= 7.7 Hz, 2H), 7.40 (t, J= 7.4 Hz, 1H), 6.82 (dd, J= 42.3, 8.6 Hz,
1H), 3.89 (d, J= 11.3 Hz, 6H). 13C NMR (150 MHz, Chloroform-d) δ 148.76
(dd, J= 285.6, 237.8 Hz), 142.40, 140.13, 130.61 (d, J= 7.7 Hz), 129.95 (d,
J= 14.3 Hz), 128.93, 127.87, 127.43, 127.09, 123.64 (d, J= 30.2 Hz), 53.49
(d, J= 5.3 Hz).19F NMR (471 MHz, Chloroform-d) δ -116.45 (dd, J= 109.1,
29.5 Hz). 31P NMR (202 MHz, Chloroform-d) δ 6.60 (dddd, J= 109.1, 41.2,
22.6, 11.3 Hz). HRMS (ESI): calcd. for C16H16FO3P [M+H]+ 307.0894,
found 307.0899.
3q (Z): colourless oil (82 mg, 45%). 1H NMR (500 MHz, Chloroform-d) δ
7.82–7.76 (m, 4H), 7.56–7.51 (m, 2H), 7.48–7.43 (m, 4H), 7.27 (d, J= 1.8
Hz, 1H), 7.18 (dd, J= 31.9, 21.1 Hz, 1H), 7.01 (dd, J= 8.1, 1.7 Hz, 1H),
6.67 (d, J= 8.1 Hz, 1H), 5.89 (s, 2H). 13C NMR (125 MHz, Chloroform-d) δ
152.15 (dd, J= 269.3, 122.5 Hz), 147.79, 147.00, 131.97 (d, J= 2.7 Hz),
131.29 (d, J= 1.8 Hz), 131.21 (d, J= 1.8 Hz), 130.53, 129.66, 128.19 (d, J=
4.8 Hz), 128.10, 128.01 (d, J= 3.3 Hz), 127.85, 124.58 (d, J= 2.1 Hz),
123.44 (d, J= 11.5 Hz), 109.89, 107.50, 100.78. 19F NMR (471 MHz,
Chloroform-d) δ -110.47 (dd, J= 86.2, 31.9 Hz). 31P NMR (202 MHz,
Chloroform-d) δ 20.63 (d, J= 86.2 Hz). HRMS (ESI): calcd. for C21H16FO3P
[M+H]+ 367.0894, found 367.0895.
3t (Z): colourless oil (55 mg, 36%). 1H NMR (600 MHz, Chloroform-d) δ
7.62 (d, J= 7.1 Hz, 6H), 7.46 (t, J= 7.7 Hz, 2H), 7.38 (t, J= 7.4 Hz, 1H),
7.19 (t, J= 29.7 Hz, 1H), 3.77 (d, J= 11.4 Hz, 6H). 13C NMR (150 MHz,
Chloroform-d) δ 149.99 (dd, J= 267.0, 230.5 Hz), 141.69, 140.27, 130.03,
128.87, 127.69, 126.99 (d, J= 16.0 Hz), 126.31 (dd, J= 27.8, 20.5 Hz),
53.53 (d, J= 5.8 Hz). 19F NMR (471 MHz, Chloroform-d) δ -126.91 (dd, J=
97.7, 42.2 Hz). 31P NMR (202 MHz, Chloroform-d) δ 8.89 (ddq, J= 97.7,
21.8, 11.1 Hz). HRMS (ESI): calcd. for C16H16FO3P [M+H]+ 307.0894,
found 307.0896.
(E/Z)-(2-(2-bromo-4,5-dimethoxyphenyl)-1-
fluorovinyl)diphenylphosphine oxide:
Mixture of 3r (E) and 3r (Z): colourless oil (205 mg, 89%). 1H NMR (500
MHz, Chloroform-d) δ 7.86 (dd, J= 12.6, 7.6 Hz, 4H), 7.78 (dd, J= 12.6, 7.4
Hz, 4H), 7.62 (t, J= 7.5 Hz, 2H), 7.56–7.50 (m, 4H), 7.50–7.46 (m, 3H),
7.42 (td, J= 7.6, 3.0 Hz, 5H), 7.34 (d, J= 6.5 Hz, 1H), 7.30 (dd, J= 6.5, 4.1
Hz, 2H), 7.24 (d, J= 8.8 Hz, 1H), 7.21 (d, J= 7.0 Hz, 1H), 6.77 (dd, J= 8.9,
3.0 Hz, 1H), 6.57 (dd, J= 8.8, 3.0 Hz, 1H), 3.76 (d, J= 9.8 Hz, 6H). 13C NMR
(125 MHz, Chloroform-d) δ 155.73, 155.43, 154.78, 154.38, 153.54,
153.10, 152.59, 152.06, 149.85, 149.43, 147.73, 147.11, 132.30 (d, J= 2.6
Hz), 131.95 (d, J= 2.7 Hz), 131.48, 131.40, 130.99, 130.91, 130.08, 129.79,
129.21, 128.93, 128.40, 128.30, 128.17, 128.07, 126.91, 126.75 (d, J= 4.9
Hz), 126.59, 122.97 (d, J= 11.1 Hz), 122.33 (d, J= 11.9 Hz), 120.39 (dd,
J= 23.3, 2.1 Hz), 115.58, 114.98, 114.93, 114.41, 114.35 (d, J= 3.9 Hz),
112.56 (d, J= 13.4 Hz), 55.69 (d, J= 2.2 Hz), 55.60. 19F NMR (471 MHz,
Chloroform-d) δ -106.98 (dd, J= 84.0, 27.3 Hz), -120.06 (dd, J= 73.5, 42.1
Hz). 31P NMR (202 MHz, Chloroform-d) δ 21.00 (d, J= 85.0 Hz), 19.80 (d,
J= 72.8 Hz). HRMS (ESI): calcd. for C22H19BrFO3P [M+H]+ 461.0312,
found 461.0306.
Dimethyl (E/Z)-(1-fluoro-2-(4-methoxyphenyl)vinyl)phosphonate:
o
3u (E): White solid (42 mg, 32%). M.P. 164-165 C. 1H NMR (500 MHz,
Chloroform-d) δ 7.60 (d, J= 8.7 Hz, 2H), 6.94 (d, J= 8.8 Hz, 2H), 6.72 (dd,
J = 42.7, 8.6 Hz, 1H), 3.88 (s, 3H), 3.86 (d, J= 2.4 Hz, 6H). 13C NMR (125
MHz, Chloroform-d) δ 160.60, 147.04 (dd, J= 281.9, 239.7 Hz), 131.76,
123.77 (d, J= 30.6 Hz), 114.21, 55.32, 53.32 (d, J= 5.3 Hz). 19F NMR (471
MHz, Chloroform-d) δ -130.93 (dd, J= 97.4, 42.8 Hz). 31P NMR (202 MHz,
Chloroform-d) δ 9.55 (ddq, J= 97.5, 22.0, 11.1 Hz). HRMS (ESI): calcd. for
C11H14FO4P [M+H]+ 261.0687, found 261.0686.
3u (Z): colourless oil (34 mg, 26%). 1H NMR (500 MHz, Chloroform-d) δ
7.50 (d, J= 8.7 Hz, 2H), 7.16 (dd, J= 86.6, 56.2 Hz, 1H), 6.91 (d, J= 8.7 Hz,
2H), 3.86–3.71 (m, 9H). 13C NMR (125 MHz, Chloroform-d) δ 160.22,
148.64 (dd, J= 263.6, 231.2 Hz), 131.08, 126.55 (dd, J= 28.1, 20.7 Hz),
122.25 (dd, J= 10.9, 1.6 Hz), 113.76, 55.26, 53.36 (d, J= 5.8 Hz). 19F NMR
(471 MHz, Chloroform-d) δ -119.37 (dd, J= 109.0, 30.1 Hz).31P NMR (202
MHz, Chloroform-d) δ 7.13 (dddd, J= 109.0, 41.4, 22.8, 11.4 Hz). HRMS
(ESI): calcd. for C11H14FO4P [M+H]+ 261.0687, found 261.0687.
(E/Z)-(2-(4'-chloro-4,5-dimethoxy-2'-methyl-[1,1'-biphenyl]-2-yl)-1-
fluorovinyl)diphenylphosphine oxide:
Mixture of 3s (E) and 3s (Z): colourless oil (243 mg, 96%). 1H NMR (500
MHz, Chloroform-d) δ 7.83–7.74 (m, 5H), 7.69 (dt, J= 13.0, 7.2 Hz, 4H),
7.56 (q, J= 9.5, 8.6 Hz, 3H), 7.51–7.41 (m, 4H), 7.25 (s, 1H), 7.19 (d, J=
8.1 Hz, 2H), 7.12 (d, J= 13.2 Hz, 2H), 7.05 (d, J= 8.1 Hz, 2H), 6.96 (d, J=
8.0 Hz, 1H), 6.83 (dd, J= 32.3, 21.2 Hz, 1H), 6.64 (s, 1H), 6.56 (s, 1H),
6.15 (dd, J= 44.0, 7.5 Hz, 1H), 3.93–3.90 (m, 3H), 3.87 (s, 3H), 3.86–3.84
(m, 3H), 3.83–3.79 (m, 3H), 2.06 (s, 3H), 1.97 (s, 3H). 13C NMR (125 MHz,
Chloroform-d) δ 154.72, 153.65, 152.68, 152.42, 151.50, 151.36, 150.54,
149.17, 148.94, 147.76, 147.26, 138.12 (d, J= 13.6 Hz), 137.68 (d, J= 15.1
Hz), 133.32 (d, J= 3.6 Hz), 132.93 (d, J= 5.7 Hz), 132.16 (d, J= 2.4 Hz),
132.05, 131.22 (d, J= 10.7 Hz), 131.06 (d, J= 8.3 Hz), 130.86, 130.66 (d,
J= 8.2 Hz), 129.66 (d, J= 23.2 Hz), 129.52, 128.31, 128.25, 128.20, 128.15,
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Grant Number 21502208 to Q. H.,
21672139 to J.H.) and SKLDR/SIMM (SIMM1601ZZ-03 to C.Y.).
Keywords: addition • gem-difluorostyrene • elimination • α-
fluorovinyl • phosphine oxide/phosphonate
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CCDC-1874700
(for
3a)
contains
the
supplementary
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European Journal of Organic Chemistry
FULL PAPER
FULL PAPER
Key Topic* α-fluorovinyl phosphorus
compounds
Yingyuan Peng, Xiaofei Zhang, Xueyu
Qi, Qian He, Bin Zhang, Jian Hao,* and
Chunhao Yang*
Page No. – Page No.
A
facile and efficient method to synthesize (E/Z)-α-fluorovinyl phosphorus
compounds from gem-difluorostyrenes and diphenylphosphine oxide/dialkyl
phosphate under the presence of DBU at room temperature was developed. This
method may provide a practical and concise route for the synthesis of these
phosphorus compounds in material chemistry and drug discovery in the future.
Title: Metal-free access to (E/Z)-α-
fluorovinyl phosphorus compounds
from gem-difluorostyrenes
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