Synthesis and selective carbocupration reaction of fluorine-containing enynic esters, enynylphosphine oxides, and enynylphosphates

Article abstract of DOI:10.1016/j.tet.2008.06.084

Some new fluorine-containing enynic esters, enynylphosphine oxides, and enynylphosphates were synthesized stereoselectively in good yields by the dehydrohalogenation reaction of fluoroalkylated 3-iodoacrylates, 2-iodovinylphosphonates, and 2-iodovinylphos

Full text of DOI:10.1016/j.tet.2008.06.084

Tetrahedron 64 (2008) 8801–8806
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis and selective carbocupration reaction of fluorine-containing enynic
esters, enynylphosphine oxides, and enynylphosphates
*
Ying-Qiao Mei, Jin-Tao Liu
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 17 April 2008
Received in revised form 19 June 2008
Accepted 24 June 2008
Available online 26 June 2008
Some new fluorine-containing enynic esters, enynylphosphine oxides, and enynylphosphates were
synthesized stereoselectively in good yields by the dehydrohalogenation reaction of fluoroalkylated 3-
iodoacrylates, 2-iodovinylphosphonates, and 2-iodovinylphosphine oxides under basic conditions. These
fluorine-containing enynic compounds could undergo carbocupration reaction with organocopper re-
agents and the vinylcopper intermediates formed in situ could further react with some electrophiles such
as allyl bromide, phenylselenyl bromide, and iodine to give the corresponding polysubstituted fluorine-
containing dienoic esters, phosphates, and phosphine oxides with high regio- and stereoselectivity.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords:
Fluorine-containing enyne
Carbocupration
Fluorine-containing diene
1. Introduction
afforded a series of fluoroalkylated 3-iodoacrylates, 2-iodovinyl-
phosphonates, and 2-iodovinylphosphine oxides 1.4 Further
Recently, fluorine-containing compounds have drawn in-
creasing interest owing to their unique physical and biological
properties. Accordingly, considerable efforts have been devoted
to the development of methodologies for the efficient and se-
lective synthesis of fluorinated compounds.1 Among a great di-
versity of fluorine-containing molecules, fluorine-containing
enynes are well-known as a kind of important synthetic in-
termediates for the synthesis of fluorinated analogues of some
biologically active molecules.2 Therefore, significant efforts have
been made toward the synthesis of fluorine-containing enynes.3
However, to the best of our knowledge, fluorine-containing
enynic esters, enynylphosphine oxides, and enynylphosphates 2
(Fig. 1, R1¼COOEt, P(O)(OEt)2 or P(O)Ph2) have remained un-
exploited. Recently, we reported the regio- and stereoselective
addition of perfluoroalkyl iodides to allenes conjugated with
carbon–oxygen or phosphorus–oxygen double bonds, which
studies showed that these fluoroalkylated vinyl iodides could be
easily transformed to the corresponding enynes stereo-
selectively by treating with Et3N or DBU. In this paper we report
the synthesis of some fluorine-containing enynes 2 and their
carbocupration reaction5 with organocopper reagents.
2
2. Results and discussion
At room temperature, fluoroalkylated 2-iodovinylphosphine
oxides (1a–1c) and 2-iodovinylphosphonates (1d–1f) reacted
readily with triethylamine in THF. In this reaction, the elimination
of both hydrogen iodide and hydrogen fluoride occurred in one
step, giving the corresponding enynylphosphine oxides (2a–2c)
and enynylphosphates (2d–2f), respectively. After purification,
a careful analysis of the spectroscopic data of the product revealed
that only isomers in Z-configuration were formed. The 1H NMR
spectra showed a big coupling constant (J¼27–30 Hz) between the
vinylic proton and fluorine, which was in agreement with the
reported results.2a,6 When 3-iodoacrylate 1g was allowed to react
with triethylamine under similar conditions, the dehydrohaloge-
nation reaction did not occur. Raising the reaction temperature to
reflux afforded a complex mixture. Fortunately, the desired product
2g was obtained in good yield from the reaction of 1g and 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) at ꢀ78 ꢁC in Et2O. The
structure of 2a–g was further proved by X-ray crystallography of 2c
(Fig. 2).7 The results are summarized in Table 1.
I
R1
R1
CF2RF
RF
R1 = P(O)Ph2, P(O)(OEt)2, COOEt
F
1
2
Figure 1.
The carbocupration reaction of alkynes is an effective method
* Corresponding author. Tel.: þ86 21 54925188; fax: þ86 21 64166128.
E-mail address: jtliu@mail.sioc.ac.cn (J.-T. Liu).
for the synthesis of polysubstituted olefins.5 With these fluorine-
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.06.084

8802
Y.-Q. Mei, J.-T. Liu / Tetrahedron 64 (2008) 8801–8806
Figure 2. Crystal structure of 2c.
Table 1
NOE
Ha
Synthesis of fluorine-containing enynic esters, enynylphosphine oxides, and
enynylphosphates
Me Hb
Hb
I
J
Hc-F
= 38.4 Hz
F
R1
OEt
OEt
P
R1
CF2RF
RF
Et3N / THF, RT
ClF2C
Hc O
F
3g
1
2
Figure 3.
Entry
1
R1
RF
Product
Isolated yield (%)
1
2
3
4
5
6
7
1a
1b
1c
1d
1e
1f
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
COOEt
ClCF2
C3F7
C7F15
ClCF2
C3F7
2a
2b
2c
2d
2e
2f
86
78
86
91
78
89
90a
manner exclusively, and only one isomer was formed. The stereo-
selectivity of the reaction was consistent with previous studies.5
The regioselectivity can be rationalized in terms of the stabilization
effect of ester group, phosphine oxide group, or phosphate group
on the carbanion intermediate formed during the reaction.
The structure of 3 was determined by their NMR spectra and the
NOESY experiment of compound 3g (Fig. 3). The big coupling
constant of the vinylic proton Hc and fluorine indicates a trans
configuration. The NOESYexperiment of compound 3g showed that
there was a strong correlation between the vinylic proton Ha and
proton Hb in ethyl group, revealing that Ha and the ethyl group are
in the cis configuration. Additionally, no NOE is observed between
the vinylic proton Hc and Hb, indicating that 3g is in the s-trans
conformation.
C7F15
C3F7
1g
2g
a
DBU was employed instead of Et3N at ꢀ78 ꢁC in Et2O.
containing enynes 2 in hand, we next investigated their carbo-
cupration reaction with some organocopper reagents. Using THF as
solvent, 2 reacted readily with organocopper reagents prepared
from CuCl and lithium reagent or Grignard reagent at ꢀ78 ꢁC. After
quenching with saturated ammonium chloride solution, the cor-
responding diene products 3 were obtained in moderate to good
yields. The results are summarized in Table 2. Again the reaction
showed high regio- and stereoselectivity. In all cases, the addition
According to the literature5 and above experimental results,
vinylcopper species were involved in the reaction and they were
very likely to react with other electrophiles added to the reaction
mixture to give olefin derivatives. Following previous experiments,
we examined the feasibility of the reaction of vinylcopper in-
termediates formed in situ with some electrophiles. As expected,
when electrophiles such as allyl bromide, phenylselenyl bromide,
and iodine were added to the above reaction system, the corre-
sponding coupling products 4a–h were obtained in satisfactory
yields. The results are summarized in Table 3.
The structure of 4 was also determined by their NMR spectra
and the NOESY experiment of 4a. As shown in Figure 4, the NOE
between Hd in the allyl group and He in the ethyl group was ob-
served, while no NOE was found between the vinylic proton Hf and
He in the ethyl group.
reaction took place at the b-position of enynes 2 in a cis-addition
Table 2
The carbocupration reaction of 2 with organocopper reagents
β
R2
1) R2Cu, THF, -78 °C, 3h
2) H3O+, 0 °C
R1
F
R1
RF
RF
F
2
3
Entry
R1
RF
R2a
Product
Isolated yield (%)
1
2
3
4
5
6
7
8
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
COOEt
ClCF2
ClCF2
ClCF2
ClCF2
ClCF2
ClCF2
ClCF2
C3F7
Et
3a
3b
3c
3d
3e
3f
3g
3h
3i
87
78
67
76
72
87
72
93
80
85
78
n-Bu
n-C12H25
4-ClC6H4
4-MeOC6H4
1-Naphthyl
Et
3. Conclusion
In summary, we have developed a convenient method for the
stereoselective synthesis of fluorine-containing enynic esters,
enynylphosphine oxides, and enynylphosphates from fluoroalky-
lated 3-iodoacrylates, 2-iodovinylphosphine oxides, and 2-iodovi-
nylphosphonates under mild conditions. The carbocupration
reaction of these fluoroalkylated enynes with copper reagents de-
rived from organolithium or Grignard reagents gave the corre-
sponding polysubstituted fluorine-containing dienoic esters,
n-Bub
n-C8H17
1-Naphthyl
n-Bub
9
10
11
C7F15
C7F15
C3F7
3j
3k
a
Copper reagents were prepared from Grignard reagent and CuCl, unless other-
wise noted.
b
Copper reagents were prepared from n-BuLi and CuCl.

Y.-Q. Mei, J.-T. Liu / Tetrahedron 64 (2008) 8801–8806
8803
1H NMR (CDCl3):
d
7.79–7.52 (4H, m), 7.51–7.38 (6H, m), 5.79 (1H,
Table 3
dd, J1¼27.6 Hz, J2¼3.3 Hz); 19F NMR (CDCl3):
d
ꢀ61.15 (2F, d,
The reaction of 2 with organocopper reagents and electrophiles
J¼15.2 Hz), ꢀ106.70 (1F, m); 31P NMR (CDCl3):
d
9.14; MS (EI) m/z
R2
E
R1
1) R2Cu, THF, -78 °C, 1h
F
(%): 355 (6.00), 261 (16.12), 230 (69.60), 195 (100.00). Anal. Calcd
for C17H11ClF3OP: C, 57.57; H, 3.13; Cl,10.00. Found: C, 57.18; H, 3.27;
Cl, 10.26.
RF
R1
2) Electrophile (EX), -78 °C, 2h
F
RF
2
4
4.2.2. (Z)-4,5,5,6,6,7,7,7-Octafluorohept-3-en-1-ynyl-
(diphenyl)phosphine oxide (2b)
Entry R1
RF
R2a
Electrophile (EX) Product Isolated yield (%)
1
2
3
4
5
6
7
8
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)(OEt)2 C3F7
P(O)(OEt)2 C3F7
P(O)(OEt)2 C3F7
ClCF2 Etb
ClCF2 Etb
4a
4b
4c
4d
4e
4f
77
75
75
89
82
85
78
75
Br
Br
Br
Yellow oil; IR (neat): 3060, 2982, 2927, 2198, 1673, 1591, 1485,
I2
1440, 1367, 1211, 1123, 1061, 1034, 999 cmꢀ1 1H NMR (CDCl3):
;
C7F15 n-Bu I2
n-Bu
n-Bu I2
n-Bu PhSeCl
d
7.88–7.81 (4H, m), 7.62–7.48 (6H, m), 5.94 (1H, dd, J1¼29.6 Hz,
J2¼2.7 Hz); 19F NMR (CDCl3):
d
ꢀ80.34 (3F, m), ꢀ106.14 (1F, m),
ꢀ119.02 (2F, m), ꢀ126.67 (2F, m); 31P NMR (CDCl3):
d 9.64; MS (ESI)
P(O)(OEt)2 C7F15 n-Bu
COOEt C3F7 n-Bu I2
4g
4h
m/z (%): 439. Anal. Calcd for C19H11F8OP: C, 52.07; H, 2.53. Found: C,
52.15; H, 2.68.
a
Copper reagents were prepared from n-BuLi and CuCl, unless otherwise noted.
Copper reagents were prepared from Grignard reagent and CuCl.
b
4.2.3. (Z)-4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Hexadecafluoroundec-
3-en-1-ynyl(diphenyl)phosphine oxide (2c)
NOE
White solid, mp: 67–68 ꢁC; IR (KBr): 3062, 2100, 1684, 1592,
1485, 1440, 1374, 1253, 1205, 1147, 1122, 1070, 989 cmꢀ1 1H NMR
;
Hd
He He
Hd
Me
(CDCl3):
d 7.88–7.81 (4H, m), 7.62–7.48 (6H, m), 5.95 (1H, dd,
F
JHf-F = 77.8 Hz
J1¼27.9 Hz, J2¼2.4 Hz); 19F NMR (CDCl3):
d
ꢀ80.75 (3F, m), ꢀ106.11
P(O)Ph2
(1F, m), ꢀ118.23 (2F, m), ꢀ121.95 (4F, m), ꢀ122.47 (4F, m), ꢀ126.11
ClF2C
Hf
(2F, m); 31P NMR (CDCl3):
d 9.22; MS (ESI) m/z (%): 639. Anal. Calcd
4a
for C23H11F16OP: C, 43.28; H, 1.74. Found: C, 43.13; H, 2.00.
Figure 4.
4.2.4. (Z)-Diethyl 4,5,5,5-tetrafluoropent-3-en-1-
ynylphosphonate (2d)
phosphates, and phosphine oxides with high regio- and
stereoselectivity.
Colorless oil; IR (neat): 3051, 2991, 2913, 2197, 1674, 1480, 1446,
1395, 1351, 1269, 1159, 1027, 982 cmꢀ1; 1H NMR (CDCl3):
d 5.77 (1H,
dd, J1¼27.9 Hz, J2¼3.9 Hz), 4.27–4.15 (4H, m), 1.42–1.36 (6H, m); 19
F
4. Experimental
NMR (CDCl3):
(CDCl3):
d
ꢀ61.27 (2F, d, J¼15.2 Hz), ꢀ106.99 (1F, m); 31P NMR
4.1. General experimental procedure
d
ꢀ8.46; MS (ESI) m/z (%): 291. Anal. Calcd for
C9H11ClF3O3P: C, 37.20; H, 3.82. Found: C, 37.07; H, 3.96.
Melting points were measured with a Temp-Melt apparatus and
uncorrected. 1H and 13C NMR spectra were recorded in CDCl3 on
4.2.5. (Z)-Diethyl 4,5,5,6,6,7,7,7-octafluorohept-3-en-1-
ynylphosphonate (2e)
Bruker AM-300 instruments with TMS as the internal standard. 19
F
NMR and 31P NMR spectra were recorded on the same spectrometer
using CFCl3 and 85% H3PO4 as external standards, respectively. IR
spectra were obtained with a Nicolet AV-360 spectrophotometer.
Massspectraand highresolutionmassspectra (HRMS) wereobtained
on a Finnigan GC–MS 4021 and a Finnigan MAT-8430 spectrometer,
respectively. Elemental analyses were performed by this institute.
Tetrahydrofuran (THF) and diethyl ether (Et2O) were freshly distilled
from sodium before use. Starting materials 1 were prepared in our
laboratory by previous reported procedures.4 All other chemicals
were commercially available and were used as received.
Yellow oil. IR (neat): 3056, 2991, 2914, 2201, 1675, 1481, 1447,
1396, 1369, 1267, 1234, 1126, 1030, 981 cmꢀ1 1H NMR (CDCl3):
;
d
5.92 (1H, dd, J1¼28.2 Hz, J2¼3.9 Hz), 4.28–4.14 (4H, m), 1.43–1.35
(6H, m); 19F NMR (CDCl3):
d
ꢀ81.01 (3F, m), ꢀ107.22 (1F, m),
ꢀ119.64 (2F, m), ꢀ127.29 (2F, m); 13C NMR (CDCl3):
d 156.41 (dt,
J1¼276.8 Hz, J2¼33.8 Hz), 95.18, 89.81 (dd, J1¼288.4 Hz, J2¼6.9 Hz),
85.70 (d, J¼52.1 Hz), 63.56, 15.69; 31P NMR (CDCl3):
d
ꢀ7.98; MS
(ESI) m/z (%): 375; HRMS calcd for C11H12F8O3P (MþH): 375.0391;
found: 375.0398.
4.2.6. (Z)-Diethyl 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
hexadecafluoroundec-3-en-1-ynylphosphonate (2f)
Yellow oil; IR (neat): 3059, 2991, 2913, 2188, 1673, 1481, 1447,
4.2. Typical procedure for the synthesis of 2
To a THF solution (10 mL) of fluoroalkylated 2-iodovinyl-
phosphonate or 2-iodovinylphosphine oxide 1 (1 mmol) was added
the THF solution (2 mL) of Et3N (3 mmol) at room temperature. The
mixture was stirred at room temperature for a few hours (moni-
tored by TLC). After the reaction, the mixture was poured into H2O
(20 mL) and extracted with Et2O (3ꢂ20 mL). The combined organic
layer was washed with saturated NaCl solution (20 mL), dried over
Na2SO4, and evaporated in vacuo. The crude product was subjected
to column chromatography using petroleum ether/ethyl acetate as
eluent to give 2.
1395,1356,1250,1210,1149,1028, 985 cmꢀ1; 1H NMR (CDCl3):
d 5.86
(1H, dd, J1¼28.2 Hz, J2¼3.9 Hz), 4.22 (4H, q, J¼7.5 Hz), 1.40 (6H, t,
J¼7.5 Hz); 19F NMR (CDCl3):
d
ꢀ80.77 (3F, m), ꢀ106.38 (1F, m),
ꢀ118.31 (2F, m), ꢀ121.83 (4F, m), ꢀ122.58 (4F, m), ꢀ126.16 (2F, m);
13C NMR (CDCl3):
d
156.89 (dt, J1¼251.8 Hz, J2¼28.1 Hz), 95.22, 90.06
(dd, J1¼222.3 Hz, J2¼2.3 Hz), 85.87 (d, J¼38.7 Hz), 63.77, 15.94; 31
P
NMR (CDCl3):
d
ꢀ7.62; MS (ESI) m/z (%): 575; HRMS calcd for
C15H12F16O3P (MþH): 575.0263; found: 575.0281.
4.3. Synthesis of (Z)-ethyl 5,6,6,7,7,8,8,8-octafluorooct-4-
en-2-ynoate (2g)
4.2.1. (Z)-5-Chloro-4,5,5-trifluoropent-3-en-1-ynyl-
(diphenyl)phosphine oxide (2a)
To an etheral solution (20 mL) of (E)-ethyl 5,5,6,6,7,7,8,8,8-
nonafluoro-3-iodooct-2-enoate 1g (1 mmol) was added the etheral
solution (2 mL) of DBU (2 mmol) at ꢀ78 ꢁC. After stirring at the
White solid, mp: 52–53 ꢁC; IR (KBr): 3060, 2990, 2920, 2188,
2162, 1674, 1591, 1485, 1440, 1350, 1255, 1211, 1157, 1123, 981 cmꢀ1
;

8804
Y.-Q. Mei, J.-T. Liu / Tetrahedron 64 (2008) 8801–8806
same temperature for 1 h, the reaction mixture was poured into the
cold NH4Cl solution (20 mL) and the resulted mixture was extracted
with Et2O (3ꢂ20 mL). The combined organic layer was washed with
saturated NaCl solution (20 mL), dried over Na2SO4, and evaporated
in vacuo. The crude product was subjected to column chromato-
graphy using petroleum ether/ethyl acetate (20:1) as eluent to
give 2g.
4.4.4. (1E,3Z)-5-Chloro-2-(4-chlorophenyl)-4,5,5-trifluoropenta-
1,3-dienyl(diphenyl)phosphine oxide (3d)
White solid, mp: 144–145 ꢁC; IR (KBr): 3059, 2991, 1683, 1592,
1557,1490,1438,1401,1361,1264,1232,1183,1142,1096,1033,1014,
945 cmꢀ1; 1H NMR (CDCl3):
d 7.78–7.72 (4H, m), 7.59–7.49 (7H, m),
7.35–7.26 (4H, m), 6.45 (1H, d, J¼20.7 Hz); 19F NMR (CDCl3):
d
d
ꢀ59.84 (2F, d, J¼17.4 Hz), ꢀ113.12 (1F, m); 31P NMR (CDCl3):
21.31; MS (ESI) m/z (%): 467. Anal. Calcd for C23H16Cl2F3OP: C,
4.3.1. (Z)-Ethyl 5,6,6,7,7,8,8,8-octafluorooct-4-en-2-ynoate (2g)
59.12; H, 3.45. Found: C, 59.13; H, 3.67.
Yellow oil; IR (neat): 3095, 2991, 2233, 1724, 1370, 1237, 1127,
1072 cmꢀ1; 1H NMR (CDCl3):
d
5.78 (1H, d, J¼28.5 Hz), 4.22 (2H, q,
4.4.5. (1E,3Z)-5-Chloro-4,5,5-trifluoro-2-(4-methoxyphenyl)penta-
1,3-dienyl(diphenyl)phosphine oxide (3e)
J¼7.2 Hz), 1.27 (3H, t, J¼7.2 Hz); 19F NMR (CDCl3):
d
ꢀ80.86 (3F, t,
J¼9.3 Hz), ꢀ107.15 (1F, m), ꢀ119.52 (2F, m), ꢀ127.22 (2F, m); 13C
White solid, mp: 120–121 ꢁC; IR (KBr): 3056, 2986, 2841, 1684,
NMR (CDCl3):
d
156.13 (dt, J1¼282.7 Hz, J2¼28.1 Hz), 152.60, 95.11,
1606, 1559, 1513, 1437, 1361, 1294, 1253, 1179, 1142, 1039, 940 cmꢀ1
;
90.08 (d, J¼6.8 Hz), 73.11, 62.64, 13.83; MS (EI) m/z (%): 265
(100.00), 238 (28.77), 219 (13.43), 119 (49.45); HRMS calcd for
C8HF8O (MꢀEtO): 264.9900; found: 264.9900.
1H NMR (CDCl3):
d 7.80–7.73 (4H, m), 7.54–7.42 (6H, m), 7.35–7.31
(3H, m), 6.90 (2H, d, J¼8.4 Hz), 6.45 (1H, d, J¼20.3 Hz), 3.83 (3H, s);
19F NMR (CDCl3):
NMR (CDCl3):
d
ꢀ59.73 (2F, d, J¼14.1 Hz), ꢀ114.22 (1F, m); 31P
d
21.35; MS (ESI) m/z (%): 463. Anal. Calcd for
C24H19ClF3O2P: C, 62.28; H, 4.14. Found: C, 62.05; H, 4.39.
4.4. Typical procedure for the reaction of 2 with
organocopper reagents derived from Grignard reagents
4.4.6. (1E,3Z)-5-Chloro-4,5,5-trifluoro-2-(naphthalen-1-yl)penta-
1,3-dienyl(diphenyl)phosphine oxide (3f)
Under nitrogen atmosphere, CuCl (2 mmol) was added to the
solution of ethylmagnesium bromide in THF (10 mL) prepared from
magnesium turning (2 mmol) and ethyl bromide (2 mmol) at
ꢀ40 ꢁC. After stirring for 30 min at that temperature, the reaction
mixture was cooled to ꢀ78 ꢁC and the solution of 2 (0.5 mmol) in
THF (2 mL) was added. After stirring for 3 h at ꢀ78 ꢁC, the mixture
was allowed to warm to ꢀ10 ꢁC and quenched with saturated
NH4Cl solution. The resulted mixture was extracted with Et2O
(3ꢂ20 mL). The combined organic layer was washed with saturated
NaCl solution (20 mL), dried over Na2SO4, and evaporated in vacuo.
The residue was purified by silica gel column chromatography us-
ing petroleum ether/ethyl acetate as eluent to give 3.
White solid, mp: 124–125 ꢁC; IR (KBr): 3061, 2986, 1671, 1570,
1508, 1437, 1359, 1259, 1188, 1146, 1122, 1067, 1048, 993 cmꢀ1 1H
;
NMR (CDCl3):
d
8.15 (1H, d, J¼33.0 Hz), 7.89–7.75 (7H, m), 7.56–7.35
(10H, m), 6.44 (1H, d, J¼23.7 Hz); 19F NMR (CDCl3):
ꢀ59.75 (2F, d,
d
J¼16.1 Hz), ꢀ115.56 (1F, m); 31P NMR (CDCl3):
d 21.48; MS (ESI) m/z
(%): 483. Anal. Calcd for C27H19ClF3OP: C, 67.16; H, 3.97. Found: C,
67.20; H, 3.93.
4.4.7. Diethyl (1Z,3Z)-5-chloro-2-ethyl-4,5,5-trifluoropenta-1,3-
dienylphosphonate (3g)
Colorless oil; IR (neat): 3078, 2983, 2942, 1750, 1683, 1591, 1460,
1393, 1369, 1245, 1150, 1052, 965 cmꢀ1; 1H NMR (CDCl3):
d 7.27 (1H,
d, J¼38.4 Hz), 5.67 (1H, d, J¼14.1 Hz), 4.09 (4H, q, J¼7.5 Hz), 2.54
4.4.1. (1Z,3Z)-5-Chloro-2-ethyl-4,5,5-trifluoropenta-1,3-
dienyl(diphenyl)phosphine oxide (3a)
(2H, q, J¼7.5 Hz), 1.33 (6H, t, J¼7.5 Hz), 1.14 (3H, t, J¼7.5 Hz); 19F
NMR (CDCl3):
(CDCl3):
d
ꢀ59.45 (2F, d, J¼15.8 Hz), ꢀ119.68 (1F, m); 13C NMR
Yellow oil; IR (neat): 3062, 2977, 2940, 2881, 1749, 1681, 1583,
d
153.42, 149.20 (dt, J1¼203.5 Hz, J2¼23.3 Hz), 119.37 (dd,
1485, 1465, 1438, 1365, 1266, 1195, 1147, 1050, 990 cmꢀ1
;
1H NMR
J1¼151.9 Hz, J2¼3.1 Hz), 106.17, 61.85, 30.41, 16.29, 12.52; 31P NMR
(CDCl3):
d
7.74–7.67 (4H, m), 7.58–7.44 (7H, m), 6.15 (1H, d,
(CDCl3): d 18.09; MS (ESI) m/z (%): 321; HRMS calcd for
J¼22.2 Hz), 2.61 (2H, q, J¼7.2 Hz), 1.16 (3H, t, J¼7.2 Hz); 19F NMR
C11H18ClO3F3OP (MþH): 321.0628; found: 321.0643.
(CDCl3):
(CDCl3):
d
ꢀ59.27 (2F, d, J¼15.8 Hz), ꢀ119.76 (1F, m); 31P NMR
d
21.91; MS (ESI) m/z (%): 385. Anal. Calcd for C19H17ClF3OP:
4.4.8. Diethyl (1Z,3Z)-4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
hexadecafluoro-2-octylundeca-1,3-dienylphosphonate (3i)
Colorless oil; IR (neat): 3078, 2933, 2860, 1683, 1590, 1490, 1368,
C, 59.31; H, 4.45. Found: C, 59.38; H, 4.53.
4.4.2. (Z)-2-((Z)-3-Chloro-2,3,3-trifluoroprop-1-enyl)hex-1-
enyl(diphenyl)phosphine oxide (3b)
1320, 1242, 1151, 1105, 1028, 966 cmꢀ1; 1H NMR (CDCl3):
d 7.31 (1H,
dd, J1¼39.3 Hz, J2¼1.2 Hz), 5.69 (1H, d, J¼14.4 Hz), 4.09 (4H, q,
White solid, mp: 87–88 ꢁC; IR (KBr): 3059, 2962, 2933, 1677,
J¼6.9 Hz), 2.49 (2H, t, J¼7.8 Hz), 1.50–1.43 (2H, m), 1.35–1.27 (16H,
1583, 1487, 1459, 1437, 1373, 1265, 1185, 1146, 1120, 1052, 957 cmꢀ1
;
m), 0.88 (3H, t, J¼7.2 Hz); 19F NMR (CDCl3):
d
ꢀ80.80 (3F, t,
1H NMR (CDCl3):
d
7.73–7.66 (4H, m), 7.55–7.44 (7H, m), 6.13 (1H, d,
J¼10.2 Hz), ꢀ117.15 (2F, m), ꢀ119.48 (1F, m), ꢀ121.93 (4F, m),
J¼22.5 Hz), 2.56 (2H, t, J¼7.2 Hz), 1.51–1.49 (2H, m), 1.41–1.36 (2H,
ꢀ122.75 (4F, m), ꢀ126.15 (2F, m); 13C NMR (CDCl3):
d 151.94, 146.3
m), 0.92 (3H, t, J¼6.9 Hz); 19F NMR (CDCl3):
d
ꢀ59.25 (2F, d,
(dt, J1¼205.3 Hz, J2¼22.5 Hz), 120.79 (dd, J1¼137.7 Hz, J2¼2.7 Hz),
J¼17.2 Hz), ꢀ119.72 (1F, m); 31P NMR (CDCl3):
d
21.69; MS (ESI) m/z
110.90, 61.88, 37.78, 31.78, 29.24, 29.11, 28.28, 22.61, 16.25, 16.18,
(%): 413. Anal. Calcd for C21H21ClF3OP: C, 61.10; H, 5.13. Found: C,
61.06; H, 5.12.
14.00; 31P NMR (CDCl3):
d 17.58; MS (ESI) m/z (%): 689; HRMS calcd
for C23H30F16O3P (MþH): 689.1672; found: 689.1650.
4.4.3. (Z)-2-((Z)-3-Chloro-2,3,3-trifluoroprop-1-enyl)tetradec-1-
enyl(diphenyl)phosphine oxide (3c)
4.4.9. Diethyl (1E,3Z)-4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
hexadecafluoro-2-(naphthalen-1-yl)undeca-1,3-
dienylphosphonate (3j)
White solid, mp: 58–59 ꢁC; IR (KBr): 3057, 2997, 2932, 2854,
1680, 1589, 1469, 1438, 1377, 1344, 1265, 1175, 1138, 1118, 1060,
Yellow oil; IR (neat): 3050, 2988, 1918, 1716, 1509, 1364, 1244,
962 cmꢀ1; 1H NMR (CDCl3):
d
7.73–7.66 (4H, m), 7.56–7.44 (7H, m),
1220, 1151,1105, 1052, 1024, 970 cmꢀ1; 1H NMR (CDCl3):
d 7.88–7.86
6.12 (1H, d, J¼22.5 Hz), 2.55 (2H, t, J¼6.9 Hz), 1.52–1.49 (20H, m),
(2H, m), 7.74–7.34 (2H, m), 7.52–7.43 (3H, m), 7.35–7.31 (1H, m),
0.88 (3H, t, J¼6.9 Hz); 19F NMR (CDCl3):
d
ꢀ59.24 (2F, d, J¼16.4 Hz),
5.96 (1H, d, J¼17.7 Hz), 4.22 (4H, q, J¼6.3 Hz), 1.38 (6H, t, J¼6.3 Hz);
ꢀ119.71 (1F, m); 31P NMR (CDCl3):
d
21.77; MS (ESI) m/z (%): 525.
19F NMR (CDCl3):
d
ꢀ80.76 (3F, t, J¼10.2 Hz), ꢀ115.11 (1F, m),
Anal. Calcd for C29H37ClF3OP: C, 66.34; H, 7.10. Found: C, 66.56; H,
6.80.
ꢀ117.49 (2F, m), ꢀ121.93 (4F, m), ꢀ122.73 (4F, m), ꢀ126.12 (2F, m);
13C NMR (CDCl3):
d
149.03, 147.4 (dt, J1¼207.3 Hz, J2¼24.0 Hz),

Y.-Q. Mei, J.-T. Liu / Tetrahedron 64 (2008) 8801–8806
8805
138.22, 138.00, 133.37, 130.38, 129.11, 128.52, 126.59, 125.41 (dd,
J1¼124.4 Hz, J2¼3.5 Hz), 126.24, 125.18, 124.48, 111.47, 62.28, 16.38;
31P NMR (CDCl3):
16.26; MS (ESI) m/z (%): 703; HRMS calcd for
25H20F16O3P (MþH): 703.0889; found: 703.0868.
4.6.1. (4Z,6Z)-8-Chloro-5-ethyl-7,8,8-trifluoroocta-1,4,6-trien-4-
yl(diphenyl)phosphine oxide (4a)
d
White solid, mp: 87–88 ꢁC; IR (KBr): 3078, 2977, 2941, 1680,
1636, 1574, 1483, 1470, 1434, 1358, 1314, 1269, 1176, 1140, 1116,
C
1043 cmꢀ1; 1H NMR (CDCl3)
d 7.69–7.64 (4H, m), 7.52–7.44 (6H, m),
4.5. Typical procedure for the reaction of 2 with
organocopper reagents derived from n-BuLi
7.34 (1H, d, J¼77.8 Hz), 5.44–5.34 (1H, m), 4.89 (1H, d, J¼10.2 Hz),
4.78 (1H, d, J¼17.1 Hz), 2.99 (2H, dd, J1¼16.8 Hz, J2¼5.7 Hz), 2.57
(2H, q, J¼7.4 Hz), 1.11 (3H, t, J¼7.4 Hz); 19F NMR (CDCl3)
d
ꢀ59.19
To a solution of CuCl (0.32 mmol) in THF (5 mL) was added
0.2 mL (0.32 mmol) of n-BuLi (1.6 M hexane solution) at ꢀ78 ꢁC
under an atmosphere of nitrogen. The mixture was stirred for
30 min and 2 (0.24 mmol) was added. After stirring at ꢀ78 ꢁC for
3 h, the reaction mixture was allowed to warm to ꢀ10 ꢁC and
quenched with saturated NH4Cl solution (10 mL), extracted with
Et2O (3ꢂ20 mL). The combined organic layer was washed with
saturated NaCl solution (20 mL), dried over anhydrous Na2SO4, and
concentrated in vacuo. The residue was purified by silica gel column
chromatography using petroleum ether/ethyl acetate as eluent to
give 3.
(2F, d, J¼15.2 Hz), ꢀ122.15 (1F, m); 13C NMR (CDCl3):
d 150.18, 147.11
(dt, J1¼201.9 Hz, J2¼24.1 Hz), 132.73 (d, J¼118.0 Hz), 131.87, 131.84,
131.74, 128.51, 128.39, 116.79, 108.07, 34.47, 25.88, 12.90; 31P NMR
(CDCl3):
d 31.47; MS (ESI) m/z (%): 425. Anal. Calcd for
C22H21ClF3OP: C, 62.20; H, 4.98. Found: C, 62.02; H, 4.93.
4.6.2. (1E,3Z)-5-Chloro-2-ethyl-4,5,5-trifluoro-1-iodopenta-1,3-
dienyl(diphenyl)phosphine oxide (4b)
Colorless oil; IR (neat): 3062, 2983, 2938, 1725, 1672, 1592, 1485,
1439, 1265, 1176, 1130, 1061 cmꢀ1; 1H NMR (CDCl3)
d 7.82–7.65 (5H,
m), 7.57–7.45 (6H, m), 2.82 (2H, q, J¼7.8 Hz), 1.12 (3H, t, J¼7.8 Hz);
19F NMR (CDCl3):
(CDCl3):
d
ꢀ59.25 (2F, m), ꢀ119.26 (1F, m); 13C NMR
4.5.1. Diethyl (1Z,3Z)-2-butyl-4,5,5,6,6,7,7,7-octafluorohepta-1,3-
dienylphosphonate (3h)
d
156.94, 146.81 (dt, J1¼203.85 Hz, J2¼23.2 Hz), 132.40,
132.30, 131.47 (d, J¼82.5 Hz), 128.48, 128.35, 106.40, 37.64, 11.63;
31P NMR (CDCl3):
32.42; MS (ESI) m/z (%): 511; HRMS calcd for
19H17ClF3IOP (MþH): 510.9697; found: 510.9715.
Yellow oil; IR (neat): 3065, 2938, 2878, 1683, 1590, 1373, 1350,
d
1235, 1188, 1122, 1054, 1029, 962 cmꢀ1; 1H NMR (CDCl3):
d
7.33 (1H,
C
dd, J1¼39.0 Hz, J2¼1.8 Hz), 5.70 (1H, d, J¼14.4 Hz), 4.14–4.04 (4H,
m), 2.51 (2H, t, J¼8.1 Hz), 1.50–1.40 (4H, m), 1.35 (6H, t, J¼7.2 Hz),
4.7. Typical procedure for the reaction of 2 with
organocopper reagents derived from n-BuLi and electrophiles
0.93 (3H, t, J¼7.2 Hz); 19F NMR (CDCl3):
d
ꢀ80.95 (3F, t, J¼9.3 Hz),
ꢀ118.37 (2F, m), ꢀ119.97 (1F, m), ꢀ127.31 (2F, m); 13C NMR (CDCl3):
d
151.85, 146.41 (dt, J1¼275.4 Hz, J2¼27.7 Hz), 120.74 (dd,
To a solution of CuCl (0.32 mmol) in THF (5 mL) was added
0.2 mL (0.32 mmol) of n-BuLi (1.6 M hexane solution) at ꢀ78 ꢁC
under an atmosphere of nitrogen. After stirring for 30 min, 2
(0.27 mmol) was added. The mixture was stirred at ꢀ78 ꢁC for 1 h.
Then allyl bromide, phenylselenyl bromide or iodine (1 mmol) was
added dropwise or in portion. After stirring for 2 h, the mixture was
allowed to warm to room temperature and quenched with satu-
rated NH4Cl solution (10 mL). The resulted mixture was extracted
with Et2O (3ꢂ20 mL). The combined organic layer was washed with
saturated NaCl solution (20 mL) (in the case of iodine, the solution
of Na2S2O3 was added until the color disappeared), dried over an-
hydrous Na2SO4, and concentrated in vacuo. The residue was pu-
rified by silica gel column chromatography using petroleum ether/
ethyl acetate as eluent to give 4.
J1¼182.6 Hz, J2¼4.1 Hz), 110.65, 61.80, 37.41, 30.35, 22.15, 16.13,
13.57; 31P NMR (CDCl3):
d
15.20; MS (EI) m/z (%): 390 (81.69), 375
(6.19), 43 (100.00); HRMS calcd for C15H21F8O3P: 432.1101; found:
432.1107.
4.5.2. (2Z,4Z)-Ethyl 3-butyl-5,6,6,7,7,8,8,8-octafluoroocta-2,4-
dienoate (3k)
Yellow oil; IR (neat): 3094, 2966, 2939, 2879, 1717, 1683, 1614,
1469, 1383, 1355, 1235, 1157, 1122, 1037, 963 cmꢀ1; 1H NMR (CDCl3):
d
7.54 (1H, d, J¼39.9 Hz), 5.86 (1H, s), 4.19 (2H, q, J¼7.2 Hz), 2.47
(2H, t, J¼7.8 Hz), 1.50–1.32 (4H, m), 1.30 (3H, t, J¼7.2 Hz), 0.93 (3H, t,
J¼7.2 Hz); 19F NMR (CDCl3):
ꢀ81.44 (3F, t, J¼10.8 Hz), ꢀ118.81 (2F,
d
m), ꢀ119.87 (1F, m), ꢀ127.79 (2F, m); 13C NMR (CDCl3):
d 165.40,
148.31, 122.34, 110.05, 60.45, 36.22, 30.58, 22.65, 14.10, 13.72; MS
(EI) m/z (%): 368 (4.48), 339 (8.04), 326 (94.86), 171 (100.00); HRMS
calcd for C14H16F8O2: 368.1023; found: 368.1022.
4.7.1. (1E,3Z)-2-Butyl-4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
hexadecafluoro-1-iodoundeca-1,3-dienyl(diphenyl)phosphine
oxide (4c)
4.6. Typical procedure for the reaction of 2 with
organocopper reagents derived from Grignard reagents
and electrophiles
White solid, mp: 75–76 ꢁC; IR (KBr): 3066, 2971, 2939, 1666,
1519, 1439, 1371, 1206, 1151, 1118, 1000 cmꢀ1 1H NMR (CDCl3):
;
d
7.81–7.67 (5H, m), 7.59–7.42 (6H, m), 2.83 (2H, t, J¼7.2 Hz), 1.52–
1.41 (4H, m), 0.95 (3H, t, J¼7.2 Hz); 19F NMR (CDCl3):
ꢀ80.86 (3F, t,
d
Under nitrogen atmosphere, CuCl (2 mmol) was added to the
solution of ethylmagnesium bromide in THF (10 mL) prepared from
magnesium turning (2 mmol) and ethyl bromide (2 mmol) at
ꢀ40 ꢁC. After stirring for 30 min at that temperature, the reaction
mixture was cooled to ꢀ78 ꢁC and a solution of 2 (0.5 mmol) in THF
(2 mL) was added. The resulted mixture was stirred at ꢀ78 ꢁC for
1 h, then allyl bromide or iodine (2 mmol) was added slowly to the
mixture. After stirring for 2 h, the mixture was allowed to warm to
room temperature and quenched with saturated NH4Cl solution
(20 mL). The resulted mixture was extracted with Et2O (3ꢂ20 mL).
The combined organic layer was washed with saturated NaCl so-
lution (20 mL) (in the case of iodine, the solution of Na2S2O3 was
added until the color disappeared), dried over anhydrous Na2SO4,
and concentrated in vacuo. The residue was purified by silica gel
column chromatography using petroleum ether/ethyl acetate as
eluent to give 4.
J¼8.7 Hz), ꢀ117.25 (2F, m), ꢀ119.42 (1F, m), ꢀ121.99 (4F, m),
ꢀ122.76 (4F, m), ꢀ126.18 (2F, m); 31P NMR (CDCl3):
d 31.98; MS (ESI)
m/z (%): 823. Anal. Calcd for C27H20F16OP: C, 39.44; H, 2.45. Found:
C, 39.73; H, 2.40.
4.7.2. Diethyl (4Z,6Z)-5-butyl-7,8,8,9,9,10,10,10-octafluorodeca-
1,4,6-trien-4-ylphosphonate (4d)
Yellow oil; IR (neat): 3083, 2984, 2936, 2877, 1679, 1639, 1575,
1447, 1393, 1349, 1233, 1188, 1158, 1121, 1027, 954 cmꢀ1 1H NMR
;
(CDCl3)
d
7.35 (1H, dd, J1¼39.3 Hz, J2¼2.1 Hz), 5.86–5.77 (1H, m),
5.13–5.07 (2H, m), 4.14–3.99 (4H, m), 3.18 (2H, dd, J1¼17.4 Hz,
J2¼5.7 Hz), 2.49 (2H, t, J¼7.8 Hz), 1.38–1.33 (4H, m), 1.30 (6H, t,
J¼7.2 Hz), 0.92 (3H, t, J¼6.9 Hz); 19F NMR (CDCl3):
ꢀ81.01 (3F, m),
d
ꢀ118.17 (2F, m), ꢀ123.44 (1F, m), ꢀ127.36 (2F, m); 13C NMR (CDCl3):
d
147.12, 144.24 (dt, J1¼204.1 Hz, J2¼22.3 Hz), 134.56, 130.74 (d,
J¼132.4 Hz), 116.24, 113.09, 61.94, 34.09, 31.80, 30.60, 22.83, 16.15,

8806
Y.-Q. Mei, J.-T. Liu / Tetrahedron 64 (2008) 8801–8806
13.69; 31P NMR (CDCl3):
for C18H26F8O3P (MþH): 473.1486; found: 473.1484.
d
18.46; MS (ESI) m/z (%): 473; HRMS calcd
4.7.6. (2E,4Z)-Ethyl 3-butyl-5,6,6,7,7,8,8,8-octafluoro-
2-iodoocta-2,4-dienoate (4h)
Yellow oil; IR (neat): 3090, 2966, 2938, 2879, 1727, 1468, 1350,
4.7.3. Diethyl (1E,3Z)-2-butyl-4,5,5,6,6,7,7,7-octafluoro-1-
iodohepta-1,3-dienylphosphonate (4e)
1233, 1123, 1031, 950 cmꢀ1 1H NMR (CDCl3):
; d 6.56 (1H, d,
J¼35.7 Hz), 4.26 (2H, q, J¼7.2 Hz), 2.64 (2H, t, J¼7.8 Hz), 1.42–1.35
Yellow oil; IR (neat): 3080, 2966, 2936, 2877, 1676, 1532, 1469,
(4H, m), 1.30 (3H, t, J¼6.9 Hz), 0.93 (3H, t, J¼7.2 Hz); 19F NMR
1393, 1365, 1233, 1160, 1122, 1025, 961 cmꢀ1; 1H NMR (CDCl3)
d
7.47
(CDCl3):
d
ꢀ81.23 (3F, m); ꢀ118.99 (2F, m), ꢀ121.77 (1F, m), ꢀ127.76
(1H, dd, J1¼37.5 Hz, J2¼2.4 Hz), 4.20–4.05 (4H, m), 2.79 (2H, t,
(2F, m); 13C NMR (CDCl3):
d
164.91, 145.48, 144.37 (dt, J1¼194.3 Hz,
J¼7.5 Hz), 1.49–1.43 (4H, m), 1.36 (6H, t, J¼7.2 Hz), 0.96 (3H, t,
J2¼20.6 Hz), 110.13, 96.27, 62.72, 40.55, 29.31, 22.50, 14.07, 13.67;
MS (EI) m/z (%): 494 (12.22), 449 (11.36), 424 (49.68), 297 (100.00);
HRMS calcd for C14H15F8IO2: 493.9989; found: 493.9995.
J¼6.9 Hz); 19F NMR (CDCl3):
d
ꢀ80.84 (3F, t, J¼9.9 Hz), ꢀ118.31 (2F,
m), ꢀ119.91 (1F, m), ꢀ127.19 (2F, m); 13C NMR (CDCl3):
d 154.57,
144.09 (dt, J1¼275.2 Hz, J2¼26.6 Hz), 110.60, 97.57 (d, J¼186.2 Hz),
63.15, 42.80, 29.32, 22.53, 15.99, 13.69; 31P NMR (CDCl3):
d 9.28; MS
Acknowledgements
(ESI) m/z (%): 559; HRMS calcd for C15H21F8IO3P (MþH): 559.0140;
found: 559.0130.
We thank the National Natural Science Foundation of China for
financial support (No. 20572124).
4.7.4. Diethyl (1E,3Z)-2-butyl-4,5,5,6,6,7,7,7-octafluoro-1-
(phenylselanyl)hepta-1,3-dienylphosphonate (4f)
References and notes
Yellow oil; IR (neat): 3075, 2964, 2935, 2876, 1674, 1579, 1531,
1478, 1440, 1364, 1233, 1188, 1159, 1122, 1052, 1024, 963 cmꢀ1
;
1. (a) Uneyama, K. Organofluorine Chemistry; Blackwell: Oxford, 2006; (b) Fluorine-
containing Synthons; Soloshonok, V. A., Ed.; American Chemical Society: Wash-
ington, DC, 2005; (c) Chambers, R. D. Fluorine in Organic Chemistry; Blackwell:
Oxford, 2004; (d) Hiyama, T. Organofluorine Compounds: Chemistry and Appli-
cations; Springer: Berlin, 2000; (e) Chambers, R. D. Organofluorine Chemistry:
Fluorinated Alkenes and Reactive Intermediates; Springer: Berlin, 1997; (f) Orga-
nofluorine Chemistry: Techniques and Synthons; Chambers, R. D., Ed.; Springer:
Berlin, 1997.
2. (a) Saito, S.; Kawasaki, T.; Tsuboya, N.; Yamamoto, Y. J. Org. Chem. 2001, 66, 796–
802; (b) Koetting, C.; Sander, W.; Senzlober, M. Chem.dEur. J. 1998, 11, 2360–
2365; (c) Xu, Z.-Q.; Zemlicka, J. Tetrahedron 1997, 53, 5389–5396; (d) Eddarir, S.;
Francesch, C.; Mestdagh, H.; Rolando, C. Bull. Soc. Chim. Fr. 1997, 8–9, 741–756.
3. (a) Yoshida, M.; Komata, A.; Hara, S. Tetrahedron 2006, 62, 8636–8645; (b) Pit-
terna, T.; Boeger, M.; Maienfisch, P. Chimia 2004, 3, 108–116; (c) Yoshida, M.;
Hara, S. Org. Lett. 2003, 4, 573–574; (d) Yoshida, M.; Yoshikawa, S.; Fukuhara, T.;
Yoneda, N.; Hara, S. Tetrahedron 2001, 57, 7143–7148; (e) Yamanaka, H.; Odani,
Y.; Ishihara, T.; Gupton, J. T. Tetrahedron Lett. 1998, 39, 6943–6946; (f) Shen, Y.; Ni,
J.; Li, P. J. Fluorine Chem. 1998, 91, 59–61; (g) Eddarir, S.; Mestdagh, H.; Rolando, C.
Tetrahedron Lett. 1991, 32, 69–72; (h) Tellier, F.; Sauvetre, R.; Normant, J.-F. Tet-
rahedron Lett. 1986, 27, 3147–3148.
1H NMR (CDCl3)
d
7.44 (1H, dd, J1¼38.1 Hz, J2¼2.1 Hz), 7.36–7.33
(2H, m), 7.18–7.15 (3H, m), 3.99–3.79 (4H, m), 2.83 (2H, t,
J¼7.2 Hz), 1.25–1.19 (4H, m), 1.11 (6H, t, J¼6.9 Hz), 0.78 (3H, t,
J¼6.9 Hz); 19F NMR (CDCl3):
d
ꢀ80.86 (3F, t, J¼9.6 Hz), ꢀ118.18
(2F, m), ꢀ120.03 (1F, m), ꢀ127.13 (2F, m); 13C NMR (CDCl3):
d
156.40, 144.84 (dt, J1¼267.2 Hz, J2¼27.2 Hz), 131.83, 131.1, 129.95
(d, J¼104.0 Hz), 129.18, 127.08, 112.53, 62.64, 37.53, 30.80, 22.64,
16.10, 13.58; 31P NMR (CDCl3):
13.47; MS (ESI) m/z (%): 588;
21H25F8O3PSe (MþNa): 611.0471; found:
d
HRMS calcd for
611.0467.
C
4.7.5. Diethyl (4Z,6Z)-5-butyl-7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-
hexadecafluorotetradeca-1,4,6-trien-4-ylphosphonate (4g)
Yellow oil; IR (neat): 3080, 2962, 2930, 2871, 1700, 1678, 1629,
1464, 1362, 1245, 1211, 1151, 994 cmꢀ1; 1H NMR (CDCl3)
d 7.43 (1H,
4. Mei, Y.-Q.; Liu, J.-T.; Liu, Z.-J. Synthesis 2007, 5, 739–743.
5. (a) Mori, S. Organometallics 2004, 23, 1081–1088; (b) Nakamura, E.; Mori, S.
Angew. Chem., Int. Ed. 2000, 39, 3750–3771; (c) Woodward, S. Chem. Soc. Rev.
2000, 29, 393–401; (d) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135–631;
(e) Normant, J. F.; Alexakis, A. Synthesis 1981, 841–870; (f) Corey, E. J.; Katze-
nellenbogen, J. A. J. Am. Chem. Soc. 1969, 91, 1851–1852.
6. (a) Benayoud, F.; Chen, L.; Moniz, G. A.; Zapata, A. J.; Hammond, G. B. Tetrahedron
1998, 54, 15541–15554; (b) Peter, J. D.; Yranzo, G. I.; de Paz, J. L. G.; Elguero, J.
J. Fluorine Chem. 1993, 63, 271–280.
7. The crystal structure of 2c has been deposited as supplementary publication No.
CCDC-691263 at the Cambridge Crystallographic Data Centre. Copies of the data
can be obtained free of charge on application to: CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: þ44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk.
dd, J1¼41.1 Hz, J2¼2.4 Hz), 5.86–5.73 (1H, m), 5.14–5.07 (2H, m),
4.14–3.99 (4H, m), 3.18 (2H, dd, J1¼17.7 Hz, J2¼5.7 Hz), 2.48 (2H, t,
J¼9.3 Hz), 1.43–1.35 (4H, m), 1.31 (6H, t, J¼6.9 Hz), 0.92 (3H, t,
J¼7.5 Hz); 19F NMR (CDCl3)
d
ꢀ80.91 (3F, t, J¼10.7 Hz), 117.00 (2F,
m), ꢀ121.99 (4F, m), ꢀ123.03 (4F, m), ꢀ123.16 (1F, m), ꢀ126.23 (2F,
m); 13C NMR (CDCl3)
134.60, 130.86 (d, J¼129.6 Hz), 116.20, 113.19, 61.87, 34.11, 31.78,
30.62, 22.82,16.12,13.63; 31P NMR (CDCl3)
18.39; MS (ESI) m/z (%):
d
147.14, 144.42 (dt, J1¼202.4 Hz, J2¼24.1 Hz),
d
673; HRMS calcd for C22H26F16IO3P (MþH): 673.1359; found:
673.1368.