Convenient and efficient access to fluoroalkylated vinylphosphonates via highly regio- and stereoselective hydrometalation or carbometalation reactions of fluorine-containing alkynylphosphonates

Article abstract of DOI:10.1055/s-2008-1032143

The hydrostannation, carbocupration, and carbozincation reactions of fluorinated alkynylphosphonates were investigated. The hydrostannation reaction proceeded smoothly without an additive (e.g., BEt₃/O₂, AIBN) to give the corresponding vinylstannanes in a highly regio- and stereoselective manner. Various cuprates, prepared from organolithium, Grignard, and organozinc reagents, could participate nicely in the carbocupration reactions, the corresponding adducts were obtained in good to high yields. Dialkylzinc reagents reacted smoothly with the alkynylphosphonates even in the absence of copper salt to afford the corresponding adducts in good yields. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1032143

564
PAPER
Convenient and Efficient Access to Fluoroalkylated Vinylphosphonates via
Highly Regio- and Stereoselective Hydrometalation or Carbometalation
Reactions of Fluorine-Containing Alkynylphosphonates
S
ynthesis of Flu
s
oroalkyla
u
ted
V
inylpho
t
sphona
o
tes mu Konno,* Atsunori Morigaki, Kazuo Ninomiya, Tomotsugu Miyabe, Takashi Ishihara
Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
Fax +81(75)7247580; E-mail: konno@chem.kit.ac.jp
Received 28 September 2007; revised 9 November 2007
OEt
P OEt
O
Abstract: The hydrostannation, carbocupration, and carbozinca-
tion reactions of fluorinated alkynylphosphonates were investigat-
ed. The hydrostannation reaction proceeded smoothly without an
additive (e.g., BEt3/O2, AIBN) to give the corresponding vinylstan-
nanes in a highly regio- and stereoselective manner. Various cu-
prates, prepared from organolithium, Grignard, and organozinc
reagents, could participate nicely in the carbocupration reactions,
the corresponding adducts were obtained in good to high yields. Di-
alkylzinc reagents reacted smoothly with the alkynylphosphonates
even in the absence of copper salt to afford the corresponding ad-
ducts in good yields.
RF
R1
O
Met-X
RF
P
OEt
Met = Sn, Cu, Zn
X = H or C
R2
OEt
2
1
RF = CHF2, CF3, H(CF2)3
Scheme 1 Intended research program
O
O
P
1) BuLi (1.2 equiv),
40 min, THF, –78 °C
2) RFCO2Et (1.2 equiv),
–78 °C, 1 h
RF
OEt
Key words: fluoroalkenes, alkynylphosphonates, hydrostannation,
carbocupration, carbozincation, regioselective, stereoselective
OEt
4
O
3) NH4Cl (aq)
Me
P
OEt
+
74–84%
4/5 ≈ 70:30
OEt
Vinylphosphonates are recognized as extremely valuable
compounds because of their widespread applications.1
They are employed as synthetic intermediates in the prep-
aration of biologically and pharmacologically active mol-
ecules,2 as well as in other organic transformations,3 and
they are utilized in polymers,4 agricultural chemicals,5 or
flame retardants.6
O
P
HO OH
RF
3
OEt
OEt
5
Tf2O (2.4 equiv)
(i-Pr)2NEt (3.6 equiv)
O
RF
P
OEt
Fluorine-containing materials are also very important
molecules and have attracted great interest in recent years
in the medicinal, pharmaceutical, and agricultural fields,
among others, owing to the enhanced biological or physi-
ological activity exerted by fluorine(s).7 Consequently, it
is not surprising that much effort has recently been devot-
ed towards the development of new methodologies for the
synthesis of fluorinated vinylphosphonates 1 (Figure 1).8
CH2Cl2, 0 °C, 5 h
40–70%
OEt
2a: RF = CF3
2b: RF = CHF2
2c: RF = (CF2)2CF3
Scheme 2 Preparation of fluorinated alkynylphosphonates 2a–c
phonates 1 via highly regio- and stereoselective hydro-
metalation and carbometalation reactions of fluorine-
containing alkynylphosphonates 2 (Scheme 1).
However, to the best of our knowledge, methods for the
stereoselective preparation of such molecules are still
quite limited. We now report in detail a new synthetic
method for the preparation of fluoroalkylated vinylphos-
The starting phosphonates 2 were prepared with slight
modifications of the reported procedure (Scheme 2).9
Thus, treatment of diethyl methylphosphonate (3) with
butyllithium (1.2 equiv) at –78 °C for 40 minutes followed
by addition of ethyl perfluoroalkanoate (1.2 equiv) gave
the mixture of b-ketophosphonate 4 and its hydrate 5 in
74–84% yield in a ratio of ca. 70:30. This mixture was
subjected to trifluoromethansulfonic anhydride (2.4
equiv) and N,N-diisopropylethylamine (3.6 equiv) in
dichloromethane at 0 °C for five hours, the desired fluor-
inated alkynylphosphonates 2a–c were obtained in 40–
70% yield.
nRF
P
OR
OR
O
1
RF = F, CF3, CHF2, etc.
Figure 1
SYNTHESIS 2008, No. 4, pp 0564–0572
x
x
.
x
x
.2
0
0
8
Initial studies with the thus-obtained alkynylphospho-
nates 2 focused on the hydrostannation reaction (Table 1).
Advanced online publication: 31.01.2008
DOI: 10.1055/s-2008-1032143; Art ID: F17607SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Fluoroalkylated Vinylphosphonates
565
Table 1 Hydrostannation Reaction of Fluorine-Containing Alkynylphosphonates
additive
Bu3SnH (1.2 equiv)
RF
H
R
RF
R
H
RF
H
SnBu3
R
RF
H
R
RF
R
+
+
+
benzene, r.t., 2 h
Bu3Sn
Bu3Sn
SnBu3
2
(Z)-6
(E)-6
(Z)-7
(E)-7
Entry
RF
R
Additive
Yielda (%) of 6 + 7
Ratioa
6/7
Z/E
1b
2b
3b
4b
5b
6
CF3
4-ClC6H4
Et3B
99 (95)10
99 (90)10
310
100:0
100:0
100:0
35:65
21:79
0:100
0:100
0:100
6a: 100:0
CF3
4-MeOC6H4
4-ClC6H4
Et3B
6b: 98:2
CF3
–
–
–
–
–
–
6a: 100:0
CF3
4-EtO2CC6H4
4-O2NC6H4
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
6510
6c: 0:100, 7c: 0:100
6d: 0:100, 7d: 0:100
7e: 100:0
CF3
6510
CF3
99 (91)
72 (69)
66 (50)
7
CHF2
(CF2)2CF3
7f: 100:0
8
7g: 100:0
a Determined by 19F NMR. Values in parentheses are of isolated yields.
b Performed in toluene at 0 °C for 4 h.
PhI (1.5 equiv)
CuCN (20 mol%)
PdCl2(PPh3)2 (10 mol%)
We have already reported the hydrostannation reaction of
fluoroalkylated alkynes containing various aromatic sub-
stituents.10 Thus, as shown in Table 1, entries 1–3, the
alkynes bearing halogen or an electron-donating group on
the benzene ring underwent hydrostannation only in the
presence of a catalytic amount of triethylborane, giving
the corresponding vinylstannanes (Z)-6a–c in a highly
regio- and stereoselective manner. On the other hand, the
reaction of the alkynes bearing an electron-withdrawing
group on the benzene ring took place smoothly even in the
absence of triethylborane to give a mixture of (E)-6 and
(E)-7 isomers in a ratio of ca. 30:70 (Table 1, entries 4 and
5).
F3C
H
Bu3Sn
F3C
H
Ph
P(O)(OEt)2
toluene, 80 °C, 6 h
71%
P(O)(OEt)2
(Z)-7e
(E)-8d
Scheme 3 Stille coupling of a fluorine-containing vinylstannane
with iodobenzene
The reaction of 2a with butyllithium in the absence of
copper salts was investigated (Table 2, entry 1). Thus,
treatment of 2a with butyllithium (2.4 equiv) in tetrahy-
drofuran at –60 °C for two hours afforded a complex mix-
ture; none of the desired product was detected. On the
other hand, the addition of an equimolar amount of cop-
per(I) cyanide had a significant influence on the reaction.
Thus, the desired alkenylphosphonate (Z)-9a was ob-
tained exclusively (Table 2, entry 2); no other regio- and
stereoisomers were observed. Similarly, various organo-
lithium reagents were investigated. Methyllithium and
sec-butyllithium were found to be good reagents for this
carbocupration reaction, affording the corresponding ad-
ducts in high yields with high regio- and stereoselectivity
(Table 2, entries 3 and 4). The use of phenyllithium
caused a slight decrease of the chemical yield, while the
regio- and stereoselectivity still remained excellent
(Table 2, entry 5).
Very surprisingly, treatment of diethyl 3,3,3-trifluoro-
prop-1-ynylphosphonate (2a) with tributylstannane with-
out any additive in benzene at room temperature for two
hours gave the corresponding Z-adduct (Z)-7e, exclusive-
ly (Table 1, entry 6). As shown in entries 7 and 8, chang-
ing the fluoroalkyl group from trifluoromethyl to
difluoromethyl, or heptafluoropropyl did not influence the
reaction, (Z)-7f and (Z)-7g were obtained with excellent
regio- and stereoselectivity.
The obtained vinylstannane (Z)-7e was subjected to the
Stille coupling reaction (Scheme 3).11 Thus, treatment of
(Z)-7e with iodobenzene (1.5 equiv) in the presence of
copper(I) cyanide (20 mol%) and dichlorobis(triphe-
nylphosphine)palladium(II) (10 mol%) in toluene at 80 °C
for six hours gave the corresponding coupling product
(E)-8d in 71% yield.
We also studied the reaction using various Grignard re-
agents as shown in Table 2, entries 6–15. The employ-
ment of butylmagnesium bromide without a copper salt
resulted in complete consumption of the starting alkyne
but with the formation of a very low yield of the adduct,
though (E)-9a was obtained exclusively. As shown in en-
tries 7–10, alkyl Grignard reagents (e.g., BuMgBr,
We next examined the carbocupration reaction using var-
ious carbon nucleophiles, such as organolithium, Grig-
nard, and organozinc reagents,12 as summarized in
Table 2.
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566
T. Konno et al.
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Table 2 Carbocupration or Carbozincation Reaction of Trifluoromethylated Acetylenic Phosphonates
F3C
R
H
F3C
R
EWG
H
F3C
H
R
F3C
H
EWG
R
method A, B, or C
F3C
EWG
+
+
+
2a
EWG = P(O)(OEt)2
EWG
EWG
(E)-8
(Z)-8
(E)-9
(Z)-9
Entry
Organometallic reagent (R-Met)
Methoda
Product 9, 8
Yieldb (%) of 9 + 8
Isomer ratiob
9/8
E/Z
1
BuLi
Ac
A
A
A
A
Bc
B
a
a
b
c
d
a
a
b
e
c
d
f
0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
100:0
62:38
9a: 0:100
2
BuLi
99 (75)
86 (79)
72 (64)
54 (44)
13
9a: 0:100
9b: 0:100
9c: 0:100
9d: 0:100
9a: 100:0
9a: 5:95
3
MeLi
4
s-BuLi
5
PhLi
6
BuMgBr
BuMgBr
MeMgBr
CyMgBr
s-BuMgBr
PhMgBr
7
99 (91)
73 (69)
61 (53)
70 (51)
81 (61)
86 (69)
79 (78)
93 (82)
62 (53)
20d
8
B
9b: 0:100
9e: 1:99
9
B
10
11
12
13
14
15
16
17
B
9c: 2:98
B
9d: 13:87
9f: 21:79
9g: 9:91
4-F3CC6H4MgBr
4-MeOC6H4MgBr
3-MeOC6H4MgBr
2-MeOC6H4MgBr
Et2Zn
B
B
g
h
i
B
9h: 10:90
9i: 19:81
9j: 64:36
B
Ac
A
j
Et2Zn
j
79 (61)
9j: 0:100
8j: 0:100
18
19
Me2Zn
A
A
b
k
73 (62)
84 (69)
100:0
85:15
9b: 0:100
i-Pr2Zn
9k: 0:100
8k: 0:100
20
Ph2Zn
A
d
75 (67)
100:0
9d: 0:100
21
22
23f
24
25f
26
Et2Zn
C
C
C
C
C
C
j
77 (71)
13e
100:0
100:0
100:0
100:0
100:0
100:0
9j: 62:38
9b: 0:100
9b: 0:100
9k: 0:100
9k: 6:94
Me2Zn
Me2Zn
i-Pr2Zn
i-Pr2Zn
Ph2Zn
b
b
k
k
d
7g
22h
87 (45)
68 (39)
9d: 40:60
a Method A: 1. RLi or R2Zn, CuCN, THF, –60 °C, 2 h, 2. aq NH3–MeOH; Method B: 1. RMgBr, CuCN, THF, –60 °C, 2 h, 2. aq NH3–MeOH;
Method C: R2Zn, THF, –40 °C, 14 h, 2. aq NH4Cl.
b Determined by 19F NMR. Values in parentheses are of isolated yields.
c In the absence of CuCN.
d The starting alkyne was recovered in 44% yield.
e The product (Z)-10 was obtained in 37% yield.
f Hexane was used as solvent instead of THF.
g The starting material was recovered in only 24% yield.
h The product (E)-10 was obtained in 34% yield.
Synthesis 2008, No. 4, 564–572 © Thieme Stuttgart · New York

PAPER
Synthesis of Fluoroalkylated Vinylphosphonates
567
F3C
P(O)(OEt)2
H
F3C
H
MeMgBr, CyMgBr, and s-BuMgBr) gave the correspond-
ing trisubstituted adducts (Z)-9 in a highly regio- and ste-
reoselective manner in good to high yields. However,
switching the Grignard reagents from alkyl to aryl Grig-
nard reagents, such as phenyl-, 4-(trifluoromethyl)phenyl-,
4-, 3-, and 2-methoxyphenylmagnesium bromide, caused
a slight decrease of the stereoselectivity (ratio for 9 E/Z
20:80–10:90) (Table 2, entries 11–15). Additionally, we
examined the reaction with commercially available orga-
nozinc reagents as described in Table 2, entries 16–20.
Even in the absence of copper(I) cyanide, diethylzinc
could react with 2a to give the corresponding adducts,
(E)-9j and (Z)-9j in 20% yield, together with 44% of the
P(O)(OEt)2
O
O
(Z)-10
37% [R2Zn = Me2Zn]
(E)-10
34% [R2Zn = (i-Pr)2Zn]
Figure 2 Byproduct in the case of the carbozincation with di-
methylzinc or diisopropylzinc
with the Z or E configuration of R1 or R2 with respect to
phosphorus, respectively.
recovered alkyne (Table 2, entry 16).13 The addition of The vinylstannanes (Z)-7e–g were determined as the Z-
copper(I) cyanide brought about a significant improve- isomer based on the stereochemistry of (Z)-8d as well as
ment of the chemical yields. As shown in entries 17 and the chemical shifts of 19F NMR spectra.
19, diethylzinc or diisopropylzinc could participate nicely
in the carbocupration reaction, (Z)-9j,k and (Z)-8j,k were
obtained in good to high yields as an isomeric mixture.
In summary, we have investigated the hydrostannation,
carbocupration, and carbozincation reactions of fluorinat-
ed alkynylphosphonates in detail. The hydrostannation
Very interestingly, dimethylzinc and diphenylzinc were took place smoothly even in the absence of triethylborane,
found to be good reagents, the adducts (Z)-9b,d were af- giving the corresponding Z-adducts exclusively in good to
forded in a highly regio- and stereoselective manner high yields. The reaction with various copper reagents de-
(Table 2, entries 18 and 20); no other regio- and stereoiso- rived from organolithium, Grignard, and organozinc re-
mers were detected.
agents, also proceeded smoothly to give the
corresponding Z-adducts in a highly regio- and stereo-
selective manner. Additionally, organozinc reagents,
which are well known to be much less reactive, than orga-
nolithium and Grignard reagents, reacted smoothly with
fluorinated alkynylphosphonates even in the absence of a
copper salt at –40 °C, the corresponding adducts were ob-
tained in good to high yields.
Finally, we attempted the carbozincation reaction because
diethylzinc reacted with 2a even in the absence of a cop-
per salt to give the carbometalated adduct together with
the recovery of a large amount of the starting material
(Table 2, entry 16). After several attempts, we found that
2a reacted smoothly with 2.4 equivalents of diethylzinc in
tetrahydrofuran at –40 °C for 14 hours to give the corre-
sponding adduct 9j in 77% yield as a stereoisomeric mix-
ture (Table 2, entry 21). However, dimethylzinc and
diisopropylzinc were observed to be less reactive, the de-
sired products were obtained in poor yields (Table 2, en-
tries 22 and 24). After careful examination, it was found
that the low yields resulted from the formation of (Z)-10
or (E)-10 in the reaction in 37% or 34% yield, respective-
ly, with dimethylzinc or diisopropylzinc (Figure 2). As
IR spectra were taken on a JASCO FT/IR-4100 type A spectropho-
tometer; film on a NaCl plate. 1H and 13C NMR spectra were mea-
sured with a Bruker DRX-500 NMR spectrometer and a JEOL
JNM-AL 400 NMR spectrometer in CDCl3 soln with TMS as inter-
nal reference. A JEOL JNM-EX90A (84.21 MHz) FT-NMR spec-
trometer and a JEOL JNM-AL 400 NMR spectrometer were used
for determining the yield of the products with C6F6. 19F NMR
(376.05 MHz) spectra was measured with a JEOL JNM-AL 400
the tetrahydro-2-furyl moiety in these byproducts may NMR spectrometer in CDCl3 soln with CFCl3 as internal standard.
31P NMR (161.70 MHz) spectra was measured with a JEOL JNM-
come from the solvent, we performed the reaction of 2a
with dimethyl- or diisopropylzinc in hexane, instead of
tetrahydrofuran. As a result, the reaction with diisopropyl-
zinc took place smoothly, the desired adduct (Z)-9k was
afforded preferentially in high yield (Table 2, entry 25),
while dimethylzinc did not give a satisfactory result
(Table 2, entry 23). It is noteworthy that the use of diphe-
nylzinc caused a significant decrease of the stereoselectiv-
ity, (E)-9d and (Z)-9d were obtained in a stereorandom
manner in a good yield (Table 2, entry 26).
AL 400 NMR spectrometer in CDCl3 soln with Ph3P as external
standard. 13C and 31P NMR spectra were proton decoupled. HRMS
were taken on a Hitachi M-80B mass spectrometer by EI, CI, and
FAB methods.
All chemicals were of reagent grade and, if necessary, were purified
in the usual manner prior to use. TLC was performed on aluminum
sheets coated with Merck silica gel 60 F254 plates, and column chro-
matography was carried out using Wacogel C-200 as adsorbent.
Diethyl (Z)-3,3,3-Trifluoro-1-(tributylstannyl)prop-1-enylphos-
phonate [(Z)-7e]; Typical Procedure for Hydrostannation
To a soln of diethyl 3,3,3-trifluoroprop-1-ynylphosphonate (2a, 60
mg, 0.25 mmol) in benzene (3 mL) was added Bu3SnH (87 mg, 0.3
mmol) at r.t. and the soln was stirred at r.t. for 2 h. The mixture was
quenched with aq NH4Cl and it was then extracted with EtOAc
(3 ×). The combined organic layers were dried (anhyd Na2SO4) and
concentrated in vacuo. The residue was chromatographed (silica
gel, hexane–EtOAc, 3:1) to afford (Z)-7e (0.119 g, 91%).
The structures of new compounds (E)-8d, (E)-9a–k, (Z)-
10, and (E)-10 were confirmed by 19F and 13C NMR spec-
troscopy (Table 3).14 Thus, the doublet (3J = 7.5 Hz) in 19F
NMR was assigned to the CF3CH= group, while the sin-
glets in 19F NMR are characteristic for CF3CR= (R ≠ H).
In the 13C NMR analysis, the small 3JC1-P (~10 Hz) or the
3
large JC2-P coupling constants (15–32 Hz) are consistent
Synthesis 2008, No. 4, 564–572 © Thieme Stuttgart · New York

568
T. Konno et al.
PAPER
Table 3 Determination of the Stereochemistry with the C–P Coupling Constants
3JC1-P
O
OCH2Me
R1
R2
P
OCH2Me
R3
3JC2-P
Compound
(E)-8d
(Z)-8j
R1
R2
R3
Ph
Et
H
3JC1-P (Hz)
–
3JC2-P (Hz)
31.4
–
Multiplicitya
H
CF3
H
db
db
s
CF3
CF3
CF3
CF3
CF3
CF3
Et
9.6
(Z)-9a
(Z)-9b
(Z)-9c
(Z)-9d
(Z)-9e
(E)-9j
Bu
Me
s-Bu
Ph
9.0
16.8
19.0
15.5
18.4
15.5
32.2
17.3
H
8.3
s
H
9.7
s
H
8.3
s
Cy
CF3
Et
H
9.8
dc
s
H
5.8
(Z)-9j
CF3
H
9.6
s
(Z)-10
(E)-10
CF3
H
H
9.1
6.6
15.0
30.6
s
s
O
CF3
O
a In 19F NMR.
b 3
J
coupling = 7.5 Hz.
F-H
c A long-range coupling, 4JF-P = 4.9 Hz.
IR (neat): 2958, 2924, 2873, 2856, 1465, 1392, 1378, 1319, 1278,
1246, 1146, 1026, 962, 911, 877, 841, 794, 748, 671 cm–1.
19F NMR (376 MHz, CDCl3): d = –112.26 (dd, J = 7.1, 56.0 Hz, 2
F).
1H NMR (500 MHz, CDCl3): d = 0.89 (t, J = 7.3 Hz, 9 H), 1.11–
1.13 (m, 6 H), 1.31–1.34 (m, 12 H), 1.48 (m, 6 H), 4.01–4.13 (m, 4
H), 7.23 (qd, J = 7.5, 34.2 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 11.78, 13.42, 16.16, 26.96, 28.52,
61.81 (d, J = 5.6 Hz), 122.25 (dq, J = 37.6, 268.4 Hz), 141.48 (q,
J = 34.7 Hz), 147.10 (qd, J = 5.5, 124.1 Hz).
31P NMR (162 MHz, CDCl3): d = 22.30–22.40 (m, 1 P).
HRMS (FAB): m/z [M + Na]+ calcd for C19H39F2NaO3PSn:
527.1527; found: 527.1539.
Diethyl (Z)-3,3,4,4,5,5,5-Heptafluoro-1-(tributylstannyl)pent-1-
enylphosphonate [(Z)-7g]
IR (neat): 2959, 2925, 2873, 1604, 1456, 1353, 1231, 1178, 1118,
19F NMR (376 MHz, CDCl3): d = –63.69 (d, J = 7.5 Hz, 3 F).
31P NMR (162 MHz, CDCl3): d = 22.01 (s, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C19H39F3O3PSn: 521.1454;
1052, 964, 907, 786 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.88 (t, J = 7.4 Hz, 9 H), 1.08–
1.11 (m, 6 H), 1.25–1.35 (m, 13 H), 1.44–1.50 (m, 5 H), 4.04–4.13
(m, 4 H), 7.27 (td, J = 13.8, 34.5 Hz, 1 H).
found: 521.1426.
13C NMR (125 MHz, CDCl3): d = 12.17, 13.54, 16.30 (d, J = 6.4
Hz), 27.13, 28.64, 62.04 (d, J = 5.9 Hz), 108.46–119.14 (m, 2 C),
139.34 (t, J = 21.9 Hz), 150.07 (td, J = 6.8, 121.5 Hz), 151.56.
19F NMR (376 MHz, CDCl3): d = –127.44 (s, 2 F), –112.69 (s, 2 F),
–80.78 (t, J = 9.8 Hz, 3 F), 151.56.
31P NMR (162 MHz, CDCl3): d = 21.79 (t, J = 4.4 Hz, 1 P).
HRMS (FAB): m/z [M – H]+ calcd for C21H38F7O3PSn: 621.1390;
Diethyl (Z)-3,3-Difluoro-1-(tributylstannyl)prop-1-enylphos-
phonate [(Z)-7f]
IR (neat): 2958, 2959, 2872, 2855, 1704, 1464, 1363, 1244, 1131,
1081, 1030, 962, 882, 795, 740 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.87 (t, J = 7.3 Hz, 9 H), 1.06–
1.10 (m, 6 H), 1.27–1.34 (m, 12 H), 1.44–1.50 (m, 6 H), 4.03–4.07
(m, 4 H), 6.04 (ddt, J = 2.2, 5.5, 55.5 Hz, 1 H), 7.21 (dtd, J = 5.5,
8.8, 33.5 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 11.86, 13.53, 16.32 (d, J = 6.4
Hz), 27.10, 28.65, 61.76 (d, J = 6.1 Hz), 113.86 (dt, J = 41.4, 237.7
Hz), 144.12 (td, J = 10.9, 128.0 Hz), 147.65 (t, J = 25.7 Hz).
found: 621.1422.
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Diethyl (E)-3,3,3-Trifluoro-1-phenylprop-1-en-1-ylphospho-
nate [(E)-8d]; Typical Procedure for the Stille Coupling Reac-
tion
Diethyl (Z)-2-(Trifluoromethyl)hex-1-enylphosphonate [(Z)-9a]
IR (neat): 2962, 2933, 2874, 1729, 1649, 1456, 1378, 1259, 1227,
1175, 1133, 1054, 1028, 967, 794 cm–1.
To soln of PdCl2(PPh3)2 (18 mg, 0.025 mmol, 10 mol%) in toluene
(3 mL) was added (Z)-7e (0.130 g, 0.25 mmol), CuCN (45 mg,
0.050 mmol, 20 mol%), and PhI (0.042 mL, 0.375 mmol) and the
mixture was heated to 80 °C and stirred at this temperature for 6 h.
The mixture was quenched with aq NH4Cl and then it was extracted
with Et2O (3 ×). The combined organic layers were dried (anhyd
Na2SO4) and concentrated in vacuo. The residue was chromato-
graphed (silica gel, hexane–EtOAc, 1: 1) to afford (E)-8d (54 mg,
71%).
1H NMR (500 MHz, CDCl3): d = 0.92 (t, J = 7.4 Hz, 3 H), 1.33 (t,
J = 7.1 Hz, 6 H), 1.36 (q, J = 7.4 Hz, 2 H), 1.46–1.51 (m, 2 H), 2.31
(t, J = 7.4 Hz, 2 H), 4.12 (dq, J = 7.1, 7.1 Hz, 4 H), 5.94 (d, J = 9.4
Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.72, 16.20 (d, J = 5.7 Hz),
22.02, 29.32, 33.07 (qd, J = 1.6, 16.5 Hz), 62.28 (d, J = 5.8 Hz),
122.14 (dq, J = 9.0, 276.1 Hz), 122.62 (qd, J = 3.3, 189.4 Hz),
148.03 (d, J = 31.4 Hz).
19F NMR (376 MHz, CDCl3): d = –63.95 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 10.34–10.51 (m, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C11H21F3O3P: 289.1181;
found: 289.1183.
IR (neat): 2985, 1738, 1648, 1494, 1445, 1393, 1356, 1281, 1254,
1193, 1140, 1052, 1024, 976, 771 (m), 728, 699, 594 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.27 (t, J = 7.1 Hz, 6 H), 4.09–
4.13 (m, 4 H), 6.75 (dq, J = 7.7, 24.0 Hz, 1 H), 7.24–7.26 (m, 2 H),
7.36–7.39 (m, 3 H).
13C NMR (125 MHz, CDCl3): d = 16.19 (d, J = 6.6 Hz), 63.17 (d,
J = 5.8 Hz), 121.62 (dq, J = 31.4, 273.6 Hz), 128.11 (q, J = 1.7 Hz),
128.71 (d, J = 2.5 Hz), 130.23 (dq, J = 11.5, 33.9 Hz), 130.74 (d,
J = 11.6 Hz), 132.15 (d, J = 5.8 Hz), 143.40 (qd, J = 7.5, 127.8 Hz).
Diethyl (Z)-3,3,3-Trifluoro-2-methylprop-1-enylphosphonate
[(Z)-9b]
IR (neat): 2986, 2934, 2910, 1648, 1480, 1448, 1371, 1258, 1180,
1103, 1029, 968, 845, 795, 762, 609, 569 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.33 (t, J = 7.0 Hz, 6 H), 2.05 (m,
3 H), 4.12 (dq, J = 7.0, 7.0 Hz, 4 H), 5.98 (qd, J = 1.2, 9.7 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.22 (d, J = 6.6 Hz), 20.43 (qd,
J = 2.5, 19.0 Hz), 62.3 (d, J = 5.7 Hz), 121.89 (dq, J = 8.3, 274.5
Hz), 123.73 (dq, J = 3.3, 189.3 Hz), 143.7 (q, J = 33.1 Hz).
19F NMR (376 MHz, CDCl3): d = –58.62 (d, J = 7.5 Hz, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.88–12.11 (m, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C13H17F3O3P: 309.0868;
found: 309.0875.
19F NMR (376 MHz, CDCl3): d = –65.58–65.57 (m, 3 F).
31P NMR (162 MHz, CDCl3): d = 9.58–9.69 (m, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C8H15F3O3P: 247.0712;
Diethyl (Z)-2-(Trifluoromethyl)hex-1-enylphosphonate [(Z)-
9a]; Typical Procedure, Method A, for Carbocupration Using
Various Organolithium or Organozinc Reagents
To a soln of CuCN (53 mg, 0.6 mmol) in THF (1 mL) was added 1.6
M BuLi in hexane (0.38 mL, 0.6 mmol) at –60 °C and the soln was
stirred for 10 min. To this soln was added dropwise 2a (58 mg, 0.25
mmol) in THF (1 mL). The mixture was stirred at –60 °C for 2 h and
then quenched with aq NH3–MeOH (1:5, 6 mL) and extracted with
Et2O (3 ×). The combined organic layers were dried (anhyd
Na2SO4) and concentrated in vacuo. The residue was chromato-
graphed (silica gel, hexane–EtOAc, 1:1) to afford (Z)-9a (54 mg,
75%).
found: 247.0701.
Diethyl (Z)-3-Methyl-2-(trifluoromethyl)pent-1-enylphospho-
nate [(Z)-9c]
IR (neat): 2964, 2910, 1638, 1456, 1389, 1332, 1261, 1221, 1026,
865, 797, 432 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.89 (t, J = 7.4 Hz, 3 H), 1.13 (d,
J = 6.8 Hz, 3 H), 1.33 (t, J = 7.1 Hz, 6 H), 1.39–1.46 (m, 1 H), 1.54–
1.62 (m, 1 H), 2.46 (dq, J = 2.3, 6.8 Hz, 1 H), 4.12 (dq, J = 7.1, 7.1
Hz, 4 H), 5.93 (d, J = 9.3 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 11.42, 16.23 (d, J = 6.5 Hz),
19.94, 28.86, 37.76 (d, J = 15.5 Hz), 62.24–62.32 (m), 121.61 (qd,
J = 6.9, 190.5 Hz), 122.45 (dq, J = 9.7, 276.8 Hz), 153.0 (q,
J = 30.1 Hz).
19F NMR (376 MHz, CDCl3): d = –63.74 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.3–11.5 (m, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C11H21F3O3P: 289.1181;
Diethyl (Z)-3,3,3-Trifluoro-2-phenylprop-1-enylphosphonate
[(Z)-9d]; Typical Procedure, Method B, for Carbocupration
Using Various Grignard Reagents
To a soln of CuCN (53 mg, 0.6 mmol) in THF (1 mL) was added a
THF soln of PhMgBr (0.6 mmol, prepared readily from Mg and Ph-
Br) at –60 °C and the whole was stirred for 10 min, then allowed to
warm to –20 °C. After stirring the mixture for 30 min, it was again
cooled to –60 °C, and to this soln was added dropwise 2a (58 mg,
0.25 mmol) in THF (1 mL). The mixture was stirred at –60 °C for 2
h, and was then quenched with aq NH3–MeOH (1:5, 6 mL). The
soln was extracted with Et2O (3 ×). The combined organic layers
were dried (anhyd Na2SO4) and concentrated in vacuo. The residue
was chromatographed (silica gel, hexane–EtOAc, 1:1) to afford (Z)-
9d (47 mg, 61%).
found: 289.1175.
Diethyl (Z)-3,3,3-Trifluoro-2-phenylprop-1-enylphosphonate
[(Z)-9d]
IR (neat): 2985, 1621, 1496, 1362, 1261, 1195, 1177, 1135, 1052,
1026, 972, 831, 795, 763, 698 cm–1.
Diethyl (Z)-2-(Trifluoromethyl)but-1-enylphosphonate [(Z)-
9j]; Typical Procedure, Method C, for Carbozincation
To a soln of 2a (58 mg, 0.25 mmol) in THF (1 mL) added 1.0 M
Et2Zn in hexane (0.6 mL) at –40 °C. The mixture was stirred at –40
°C for 14 h, and then quenched with aq NH4Cl. The soln was ex-
tracted with EtOAc (3 ×). The combined organic layers were dried
(anhyd Na2SO4) and concentrated in vacuo. The residue was chro-
matographed (silica gel, hexane–EtOAc, 1:1) to afford (Z)-9j (46
mg, 71%).
1H NMR (500 MHz, CDCl3): d = 1.37 (t, J = 7.1 Hz, 6 H), 4.20 (dq,
J = 7.1, 7.1 Hz, 4 H), 6.27 (d, J = 8.9 Hz, 1 H), 7.40–7.44 (m, 5 H).
13C NMR (125 MHz, CDCl3): d = 16.28 (d, J = 6.5 Hz), 62.50 (d,
J = 6.1 Hz), 121.83 (dq, J = 8.3, 276.7 Hz), 126.46 (qd, J = 2.9,
188.0 Hz), 127.56, 128.63, 129.86, 134.86 (d, J = 18.4 Hz), 146.57
(d, J = 32.8 Hz).
19F NMR (376 MHz, CDCl3): d = –60.36 (s, J = 2.0 Hz, 3 F).
31P NMR (162 MHz, CDCl3): d = 9.69–9.72 (m, 1 P).
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T. Konno et al.
PAPER
HRMS (FAB): m/z [M + H]+ calcd for C13H17F3O3P: 309.0868;
found: 309.0880.
124.37 (qd, J = 2.5, 189.3 Hz), 126.87, 127.06, 129.02, 130.60,
146.01 (dq, J = 1.7, 33.0 Hz).
19F NMR (376 MHz, CDCl3): d = –60.31 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 10.08–10.38 (m, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C14H19F3O4P: 339.0974;
found: 339.0963.
Diethyl (E)-3,3,3-Trifluoro-2-phenylprop-1-enylphosphonate
[(E)-9d]
IR (neat): 2985, 2933, 1735, 1496, 1478, 1445, 1369, 1259, 1180,
1134, 1099, 1026, 976, 795, 772, 751, 702, 673, 606 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.12 (t, J = 7.1 Hz, 6 H), 3.71–
Diethyl (Z)-3,3,3-Trifluoro-2-(3-methoxyphenyl)prop-1-
enylphosphonate [(Z)-9h]
3.94 (m, 4 H), 6.52–6.55 (m, 1 H), 7.42 (br s, 5 H).
13C NMR (125 MHz, CDCl3): d = 16.06 (d, J = 6.6 Hz), 62.18 (d,
J = 6.2 Hz), 122.12 (dq, J = 30.0, 275.8 Hz), 123.36 (qd, J = 4.6,
191.6 Hz), 128.14, 129.13 (d, J = 1.3 Hz), 129.65, 131.27 (d, J = 7.0
Hz), 146.26 (q, J = 31.2 Hz).
19F NMR (376 MHz, CDCl3): d = –68.20 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.29–11.46 (m, 1 P).
IR (neat): 2985, 1600, 1578, 1489, 1434, 1360, 1290, 1135, 1059,
1025, 977, 852, 793, 704, 474 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.37 (t, J = 6.8 Hz, 6 H), 3.82 (s,
3 H), 4.20 (dq, J = 6.8, 6.8 Hz, 4 H), 6.27 (d, J = 8.8 Hz, 1 H), 6.92–
6.99 (m, 3 H), 7.29–7.31 (m, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.18 (d, J = 5.8 Hz), 55.26,
62.51 (d, J = 6.5 Hz), 113.26, 115.27, 119.83, 121.25, 121.71 (dq,
J = 8.3, 276.1 Hz), 126.48 (qd, J = 3.3, 187.6 Hz), 129.66, 136.02
(dd, J = 1.7, 20.0 Hz), 146.33 (dq, J = 1.6, 33.0 Hz), 159.48.
HRMS (FAB): m/z [M + H]+ calcd for C13H17F3O3P: 309.0868;
found: 309.0864.
Diethyl (Z)-2-Cyclohexyl-3,3,3-trifluoroprop-1-enylphospho-
nate [(Z)-9e]
19F NMR (376 MHz, CDCl3): d = –60.43 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 9.62 (q, J = 2.9 Hz, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C14H19F3O4P: 339.0974;
IR (neat): 2932, 2857, 1641, 1451, 1391, 1348, 1313, 1256, 1167,
1131, 1026, 965, 845, 796 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.13–1.25 (m, 2 H), 1.33 (t,
J = 7.0 Hz, 8 H), 1.67–1.74 (m, 2 H), 1.81–1.88 (m, 4 H), 2.30 (t,
J = 11.4 Hz, 1 H), 4.12 (dq, J = 7.4, 7.4 Hz, 4 H), 5.93 (d, J = 8.6
Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.18 (d, J = 6.5 Hz), 25.62,
26.23, 32.56, 40.67 (qd, J = 1.1, 15.5 Hz), 62.2 (d, J = 6.1 Hz),
121.23 (qd, J = 3.4, 190.4 Hz), 122.43 (dq, J = 9.8, 276.9 Hz),
153.02 (q, J = 29.8 Hz).
19F NMR (376 MHz, CDCl3): d = –63.39 (d, J = 4.9 Hz, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.63 (q, J = 3.1 Hz, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C13H23F3O3P: 315.1338;
found: 339.0963.
Diethyl (Z)-3,3,3-Trifluoro-2-(2-methoxyphenyl)prop-1-
enylphosphonate [(Z)-9i]
IR (neat): 2985, 2842, 1631, 1600, 1582, 1492, 1464, 1438, 1353,
1260, 1173, 1024, 970, 784, 756, 606 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.36 (t, J = 7.2 Hz, 6 H), 3.81 (s,
3 H), 4.15–4.22 (m, 4 H), 6.17 (d, J = 10.4 Hz, 1 H), 6.90–6.97 (m,
2 H), 7.15–7.18 (m, 1 H), 7.34–7.39 m, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.21 (d, J = 6.6 Hz), 55.56,
62.45 (d, J = 6.6 Hz), 110.99, 120.48, 121.39 (dq, J = 8.3, 276.1
Hz), 124.80 (qd, J = 1.7, 18.2 Hz), 127.73 (qd, J = 3.3, 183.4 Hz),
129.99, 131.00, 145.20 (dq, J = 1.7, 34.7 Hz), 156.90.
found: 315.1308.
19F NMR (376 MHz, CDCl3): d = –60.95 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 9.23–9.27 (m, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C14H19F3O4P: 339.0974;
Diethyl (Z)-3,3,3-Trifluoro-2-[4-(trifluoromethyl)phenyl]prop-
1-enylphosphonate [(Z)-9f]
IR (neat): 2987, 1620, 1362, 1328, 1261, 1178, 1132, 1069, 1053,
1022, 973, 847, 827, 672, 615, 465 cm–1.
found: 339.0973.
1H NMR (500 MHz, CDCl3): d = 1.38 (t, J = 7.2 Hz, 6 H), 4.17–
4.25 (m, 4 H), 6.31 (d, J = 8.4 Hz, 1 H), 7.5–7.7 (m, 4 H).
13C NMR (125 MHz, CDCl3): d = 16.23 (d, J = 5.7 Hz), 62.75 (d,
J = 6.6 Hz), 121.51 (dq, J = 8.2, 276.1 Hz), 123.60 (q, J = 271.9
Hz), 125.65 (q, J = 4.1 Hz), 128.08, 128.55 (qd, J = 2.4, 187.6 Hz),
131.83 (q, J = 33.0 Hz), 138.30 (qd, J = 1.6, 19.0 Hz), 145.06 (dq,
J = 1.7, 33.9 Hz).
Diethyl (Z)-2-(Trifluoromethyl)but-1-enylphosphonate [(Z)-9j]
IR (neat): 2984, 2942, 1446, 1391, 1373, 1326, 1259, 1224, 1178,
1134, 1027, 970, 856, 795 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.13 (t, J = 7.3 Hz, 3 H), 1.33 (t,
J = 7.1 Hz, 6 H), 2.35–2.39 (m, 2 H), 4.13 (dq, J = 7.1, 7.1 Hz, 4 H),
5.93 (d, J = 9.1 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 11.15, 16.19 (d, J = 6.5 Hz),
26.09 (qd, J = 1.7, 17.3 Hz), 62.25 (d, J = 6.1 Hz), 121.68 (qd,
J = 3.4, 190.4 Hz), 122.17 (dq, J = 9.6, 276.7 Hz), 149.18 (q,
J = 31.1 Hz).
19F NMR (376 MHz, CDCl3): d = –60.42 (s, 3 F), –63.47 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 8.83 (q, J = 2.1 Hz, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C14H16F6O3P: 377.0742;
found: 377.0755.
19F NMR (376 MHz, CDCl3): d = –64.29 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 10.71 (q, J = 2.9 Hz, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C9H17F3O3P: 261.0868;
Diethyl (Z)-3,3,3-Trifluoro-2-(4-methoxyphenyl)prop-1-
enylphosphonate [(Z)-9g]
IR (neat): 2985, 2938, 2909, 2843, 1606, 1514, 1464, 1444, 1361,
found: 261.0859.
1177, 1134, 1027, 970, 828, 790, 737, 588, 492 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.35 (t, J = 7.2 Hz, 6 H), 3.81 (s,
3 H), 4.17 (dq, J = 7.2, 7.2 Hz, 4 H), 6.20 (d, J = 8.8 Hz, 1 H), 6.88–
6.93 (m, 2 H), 7.34–7.36 (m, 2 H).
Diethyl (E)-2-(Trifluoromethyl)but-1-enylphosphonate [(E)-9j]
IR (neat): 2985, 2945, 1650, 1446, 1393, 1351, 1322, 1250, 1181,
1132, 1025, 970, 859, 797 (s), 762 (m), 642 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.16–1.20 (m, 3 H), 1.34 (t,
J = 7.6 Hz, 6 H), 2.68 (dq, J = 2.4, 7.2 Hz, 2 H), 4.12 (m, 4 H), 6.13
(dd, J = 1.6, 12.8 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.22 (d, J = 6.6 Hz), 55.21,
62.42 (d, J = 23.2 Hz), 114.01, 121.93 (dq, J = 8.2, 276.1 Hz),
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13C NMR (125 MHz, CDCl3): d = 13.50 (d, J = 2.4 Hz), 16.27, 21.6
(d, J = 5.8 Hz), 62.16 (d, J = 5.7 Hz), 119.92 (qd, J = 5.8, 189.4
Hz), 123.02 (dq, J = 32.2, 276.1 Hz), 150.81 (dq, J = 9.9, 28.9 Hz).
19F NMR (376 MHz, CDCl3): d = –69.04 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 12.80 (q, J = 1.5 Hz, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C9H17F3O3P: 261.0868;
1H NMR (500 MHz, CDCl3): d = 1.34 (t, J = 7.2 Hz, 6 H), 1.88–
2.05 (m, 3 H), 2.30–2.36 (m, 1 H), 3.85 (td, J = 4.8, 8.0 Hz, 1 H),
4.01 (dt, J = 7.2, 7.2 Hz, 1 H), 4.07–4.16 (m, 4 H), 5.23 (dt, J = 0.8,
7.2 Hz, 1 H), 6.22 (td, J = 1.2, 10.4 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.25 (dd, J = 4.1, 6.6 Hz), 26.20,
32.38, 62.27 (dd, J = 5.7, 14.9 Hz), 69.18, 75.38 (d, J = 6.6 Hz),
121.54 (qd, J = 5.4, 189.3 Hz), 122.26 (dq, J = 30.6, 276.9 Hz),
149.44 (dq, J = 9.9, 27.3 Hz).
found: 261.0876.
19F NMR (376 MHz, CDCl3): d = –64.77 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.67 (q, J = 1.5 Hz, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C11H19F3O4P: 303.0974;
found: 303.0961.
Diethyl (Z)-1-Ethyl-3,3,3-trifluoroprop-1-enylphosphonate
[(Z)-8j]
IR (neat) 2983, 2938, 1648, 1446, 1393, 1368, 1283, 1240, 1138,
1104, 1023, 968, 795, 760, 677 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.15 (t, J = 7.3 Hz, 3 H), 1.34 (t,
J = 7.1 Hz, 6 H), 2.43–2.47 (m, 2 H), 4.11–4.20 (m, 4 H), 6.1 (dq,
J = 8.84, 43.62 Hz, 1 H).
References
13C NMR (125 MHz, CDCl3): d = 12.82 (d, J = 5.4 Hz), 16.18 (d,
J = 6.4 Hz), 28.90 (d, J = 8.7 Hz), 62.49 (d, J = 6.3 Hz), 121.41 (dq,
J = 9.6, 271.4 Hz), 128.17 (dq, J = 5.7, 37.2 Hz), 145.07 (dq,
J = 5.0, 170.9 Hz).
19F NMR (376 MHz, CDCl3): d = –58. 01 (d, J = 7.5 Hz, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.34–11.53 (m, 1 P).
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I.; Srebnik, M. Tetrahedron Lett. 2001, 42, 8059.
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(n) Quntar, A. A. A.; Rosenthal, D.; Srebnik, M.
HRMS (FAB): m/z [M + H]+ calcd for C9H17F3O3P: 261.0868;
found: 261.0874.
Diethyl (Z)-2-(Trifluoromethyl)-3-methylbut-1-enylphospho-
nate [(Z)-9k]
IR (neat): 2980, 2939, 1638, 1469, 1391, 1327, 1258, 1223, 1189,
1167, 1135, 1100, 1028, 966, 839, 795, 483 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.13 (d, J = 6.8 Hz, 6 H), 1.32 (t,
J = 7.1 Hz, 6 H), 2.69 (dq, J = 6.8, 6.8 Hz, 1 H), 4.11 (dq, J = 7.1,
7.1 Hz, 4 H), 5.95 (d, J = 6.8 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.19 (d, J = 6.5 Hz), 21.85,
30.91 (d, J = 15.8 Hz), 62.25 (d, J = 6.2 Hz), 120.85 (qd, J = 3.4,
190.5 Hz), 122.46 (dq, J = 9.9, 277.3 Hz), 153.86 (q, J = 29.8 Hz).
19F NMR (376 MHz, CDCl3): d = –63.11 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.41–11.45 (m, 1 P).
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1998, 54, 3807.
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HRMS (FAB): m/z [M + H]+ calcd for C10H19F3O3P: 275.1025;
found: 275.1030.
Diethyl (Z)-3,3,3-Trifluoro-2-(tetrahydrofuran-2-yl)prop-1-
enylphosphonate [(Z)-10]
IR (neat): 2986, 2910, 1649, 1444, 1391, 1333, 1259, 1208, 1168,
1139, 1053, 1025, 969, 795 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.34 (dt, J = 1.2, 7.2 Hz, 6 H),
1.75–1.80 (m, 1 H), 1.91–1.97 (m, 2 H), 2.27–2.32 (m, 1 H), 3.88
(dt, J = 6.8, 8.0 Hz, 1 H), 3.97 (td, J = 7.2, 7.6 Hz, 1 H), 4.10–4.17
(m, 4 H), 4.59 (t, J = 7.2 Hz, 1 H), 6.41 (dd, J = 1.6, 10.4 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 16.19 (dd, J = 3.3, 6.5 Hz), 25.58,
31.95 (d, J = 1.7 Hz), 62.30 (dd, J = 6.1, 9.0 Hz), 68.75, 76.29 (qd,
J = 3.3, 15.0 Hz), 120.60 (qd, J = 3.3, 189.4 Hz), 121.71 (dq,
J = 9.1, 276.1 Hz), 148.31 (q, J = 31.4 Hz).
19F NMR (376 MHz, CDCl3): d = –61.49 (s, 3 F).
31P NMR (162 MHz, CDCl3): d = 11.07 (q, J = 2.9 Hz, 1 P).
HRMS (FAB): m/z [M + H]+ calcd for C12H19F3O4P: 303.0974;
found: 303.0979.
Diethyl (E)-3,3,3-Trifluoro-2-(tetrahydrofuran-2-yl)prop-1-
enylphosphonate [(E)-10]
IR (neat): 2985, 2887, 1638, 1446, 1393, 1370, 1252, 1165, 1051,
1025, 970, 858, 838, 794, 746, 482 cm–1.
Synthesis 2008, No. 4, 564–572 © Thieme Stuttgart · New York

572
T. Konno et al.
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