Stereoselective synthesis of fluoroalkenes via (Z)-2-fluoroalkenyliodonium salts

Article abstract of DOI:10.1016/j.tet.2006.05.085

Stereoselective synthesis of fluoroalkenes is described. (Z)-2-Fluoro-1-alkenyl(phenyl)iodonium tetrafluoroborates (1) were synthesized stereoselectively in good yields by Michael-type addition of HF to 1-alkynyl(phenyl)iodonium tetrafluoroborates (2) with a commercially available HF reagent, hydrofluoric acid or Et₃N-3HF. Pd-catalyzed cross-coupling reactions using 1 gave (Z)-2-fluoro-1-alkene derivatives in moderate yields. The treatment of 1 with KI in the presence of a catalytic amount of CuI gave (Z)-2-fluoro-1-iodo-1-alkenes (3). Pd-catalyzed cross-coupling reactions of 3 gave better results than that of 1, and a variety of (Z)-2-fluoro-1-alkene derivatives were synthesized in good yields.

Full text of DOI:10.1016/j.tet.2006.05.085

Tetrahedron 62 (2006) 8636–8645
Stereoselective synthesis of fluoroalkenes via
(Z)-2-fluoroalkenyliodonium salts
*
Masanori Yoshida, Ayumu Komata and Shoji Hara
*
Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
Received 6 April 2006; revised 15 May 2006; accepted 17 May 2006
Available online 13 July 2006
Abstract—Stereoselective synthesis of fluoroalkenes is described. (Z)-2-Fluoro-1-alkenyl(phenyl)iodonium tetrafluoroborates (1) were syn-
thesized stereoselectively in good yields by Michael-type addition of HF to 1-alkynyl(phenyl)iodonium tetrafluoroborates (2) with a commer-
cially available HF reagent, hydrofluoric acid or Et3N–3HF. Pd-catalyzed cross-coupling reactions using 1 gave (Z)-2-fluoro-1-alkene
derivatives in moderate yields. The treatment of 1 with KI in the presence of a catalytic amount of CuI gave (Z)-2-fluoro-1-iodo-1-alkenes
(3). Pd-catalyzed cross-coupling reactions of 3 gave better results than that of 1, and a variety of (Z)-2-fluoro-1-alkene derivatives were
synthesized in good yields.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
various (E)-2-fluoro-1-alkene derivatives by Pd-catalyzed
cross-coupling reactions using (E)-2-fluoro-1-alkenyl-
(p-tolyl)iodonium salts, which were prepared from terminal
alkynes and p-iodotoluene difluoride.6 Hence, we turned our
attention into the stereoselective synthesis of (Z)-2-fluoro-1-
alkene derivatives. Ochiai et al. reported that (Z)-2-fluoro-1-
alkenyl(phenyl)iodonium salts (1)7 were stereoselectively
prepared by Michael-type addition of a fluoride anion to
the corresponding 1-alkynyl(phenyl)iodonium salts (2)8
with CsF; however, the yields were only 15–20% due to
the low nucleophilicity of the fluoride anion. Although the
simplest reagent for an HF addition is hydrogen fluoride, it
requires special equipment, technique, and know-how to
use for organic synthesis due to the high toxicity and explo-
sive reactivity to organic compounds. In ordinary labora-
tories, amine–nHF9 and hydrofluoric acid are commonly
used as convenient HF reagents instead of hydrogen fluoride.
We found that the HF addition of 2 with these HF reagents
smoothly proceeded to afford 1 effectively.10 In this report,
we would like to present the details of the stereoselective
synthesis of 1 and their utilization to the synthesis of
(Z)-2-fluoro-1-alkene derivatives by Pd-catalyzed cross-
coupling reactions.
Fluorinated analogues of natural compounds have attracted
the interest of biological and medicinal chemists, because
the introduction of a fluorine atom into a natural product
can dramatically enhance the biological activity.1 However,
organofluorine compounds are scarce in nature; therefore,
they have to be synthesized by fluorination of organic com-
pounds or by using building-block methodology with readily
available fluorine-containing substrates.2 When a fluorine
atom is introduced into a carbon–carbon double bond of a
biologically active compound, the regio- and stereoselective
introduction of the fluorine atom is important because the
bioactivity is strongly dependent on the position and stereo-
chemistry of the fluorine atom.3 The most popular approach
to the stereoselective preparation of fluoroalkenes4 is the
Horner–Wadsworth–Emmons reaction using fluoroorgano-
phosphonates with carbonyl compounds; however, a mixture
of stereoisomers is generally formed.5 On the other hand,
Pd-catalyzed cross-coupling reaction using alkenyl halides
or metals is often employed as a powerful tool to obtain
further complex alkenes stereoselectively. Therefore, a
cross-coupling reaction using fluoroalkenyl halides or
metals would be a versatile method for the stereoselective
synthesis of fluoroalkenes. However, the cross-coupling
method has been adequately developed because the stereo-
selective synthesis of fluoroalkenyl halides or metals is dif-
ficult. Recently, we reported the stereoselective syntheses of
2. Results and discussions
2.1. Stereoselective synthesis of (Z)-2-fluoroalkenyl-
iodonium salts (1)
Keywords: Fluoroalkene; Alkenyliodonium salt; Stereoselective synthesis;
Pd catalyst; Cross-coupling.
* Corresponding authors. Tel./fax: +81 11 706 6557; e-mail addresses:
myoshida@eng.hokudai.ac.jp; shara@eng.hokudai.ac.jp
Initially, we employed 1-dodecynyl(phenyl)iodonium tetra-
fluoroborate (2a) as a simple starting material and attempted
an HF addition using Et3N–nHF (Table 1). Although
0040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.05.085

M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
8637
Table 1. HF addition of 2a with Et3N–nHF or aq HF
Table 2. Synthesis of 1
R1
F
R1
C10H21
HF-reagent
20% aq HF
C10H21
I(Ph)BF4
solvent
CHCl3
60 °C
F
I(Ph)BF4
I(Ph)BF4
2a
1a, Z / E > 99 : 1
I(Ph)BF4
2
1, Z / E > 99 : 1
Entry HF reagent Solvent Temp (ꢀC) Time (h) Yield (%)
1
R1
Time (h) Yield (%)
1
2
3
4
5
6
7
8
9
10
Et3N–5HF
Et3N–3HF
Et3N–2HF
Et3N–3HF
Et3N–3HF
Et3N–3HF
46% aq HF CHCl3
30% aq HF CHCl3
20% aq HF CHCl3
10% aq HF CHCl3
CH2Cl2 rt
CH2Cl2 rt
CH2Cl2 rt
24
96
44
78
8
0.75
84
8
0a
b
c
d
e
f
Ph
t-Bu
8
43
84
74
80
72
76
71
12
12
6
6
6
32b
71
(cyclo-C6H11)-CH2
Cl-(CH2)9
t-Bu-CO-(CH2)8
i-PrO2C-(CH2)8
Neat
Neat
Neat
rt
40
60
60
60
60
60
72
67c
81
g
82
84
6
5
We found that the HF addition reaction was more effectively
carried out with diluted hydrofluoric acid (entries 8–10).11
Finally, the best result was obtained by using 20% hydro-
fluoric acid, and 1a was synthesized in 84% yield with excel-
lent stereoselectivity (Z/E>99:1) (entry 9).12
71c
a
Starting material 2a was recovered unchanged.
b
c
Tri-fluorinated compound, 1,2,2-trifluorododecane (4), was obtained in
26% yield.
Small amount of 4 was observed after the reaction.
Under the same reaction conditions, 1-alkynyl(phenyl)iodo-
nium salts 2, which have a n-alkyl or a sterically hindered
alkyl group, were converted into the corresponding (Z)-2-
fluoro-1-alkenyliodonium salts 1 in good yields (Table 2).
Unfortunately, 2-phenylethynyl(phenyl)iodonium tetrafluo-
roborate (2b) gave the desired product 1b in lower yield
because the starting material 2b was somewhat labile under
the reaction conditions, although 1b was isolated as a stable
white solid.
Et3N–5HF was inert to 2a in dichloromethane at room tem-
perature (entry 1), a more nucleophilic fluorinating reagent,
Et3N–3HF, reacted slowly with 2a to give (Z)-2-fluoro-1-
dodecenyl(phenyl)iodonium tetrafluoroborate (1a) in 71%
yield after 96 h (entry 2). The 1H NMR of the crude reaction
mixture indicated that the HF addition proceeded with excel-
lent stereoselectivity (Z/E>99:1). When 2a was treated with
a more nucleophilic reagent, Et3N–2HF, further Michael ad-
dition of fluoride anion to 1a occurred to produce 1,2,2-tri-
fluorododecane (4) in 26% yield, and the yield of 1a was
reduced to 32% (entry 3). When fluorination of 2a was car-
ried out with Et3N–3HF without dichloromethane, the reac-
tion time was reduced to 78 h (entry 4). The HF addition
reaction proceeded more effectively at 40 ꢀC (entry 5), but
the formation of a small amount of tri-fluorinated compound
4 was observed at 60 ꢀC (entry 6). Next, we attempted the
HF addition using hydrofluoric acid, which is commonly
used in a laboratory as a simple and cost effective HF re-
agent. Although commercially available 46% hydrofluoric
acid required 84 h at 60 ꢀC to consume 2a completely, the
desired product 1a was obtained in high yield (entry 7).
2.2. Stereoselective synthesis of (Z)-2-fluoro-1-alkene
derivatives by Pd-catalyzed cross-coupling reaction
using (Z)-2-fluoroalkenyliodonium salts (1)
First of all, we tried the methoxycarbonylation of 1a in
the presence of PdCl2 with CO in methanol.6b,13,14 The meth-
oxycarbonylation completed in 2 h at room temperature to
give the desired product, methyl (Z)-3-fluoro-2-tridecenoate
(5a) in 73% yield; however, methyl benzoate (6, 8%) and
(Z)-2-fluoro-1-iodo-1-dodecene (3a, 9%) were also formed
by the methoxycarbonylation of the phenyl group instead
of the fluoroalkenyl group on the starting material (Fig. 1).
C10H21
C10H21
+
+
Ph-COOMe
1a
2.0 ha
F
COOMe
5a, 73%
F
I
6, 8%
3a, 9%
Z / E > 99 : 1
C10H21
F
path a
C10H21
F
path a
+
Ph-I
Pd(0)
-
1a
Pd+BF4
-
I
Pd+BF4
path b
path b
Ph
-
Ph-Pd+BF4
+
3a
C10H21
C10H21
C10H21
+
+
+
6
0.5 ha
I(Ph)BF4
I(Ph)BF4
COOMe
I
I
7
8, 90%
E / Z > 99 : 1
9, 0%
0%
C10H21
F
C10H21
COOMe
C10H21
+
6
1.0 ha
F
F
10
11, 91%
E / Z = 98 : 2
12, <1%
<1%
Figure 1. Methoxycarbonylation of 1a, 7, and 10. aReagents and conditions: PdCl2 2 mol %, CO 1 atm, NaHCO3 1 equiv, MeOH, rt.

8638
M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
Table 3. Synthesis of 3 from 1a
When a nonfluorinated starting material, (E)-1-dodecenyl-
(phenyl)iodonium tetrafluoroborate (7), was subjected to the
reaction conditions, the methoxycarbonylation proceeded
much faster than that of 1a to give methyl (E)-2-tridecenoate
(8, 90%) without the formation of (E)-1-iodo-1-dodecene (9)
and 6.14 Interestingly, the methoxycarbonylation of (E)-2-
fluoro-1-dodecenyl(phenyl)iodonium tetrafluoroborate (10),
which has an alkyl group on the cis-position to the iodonio
group, proceeded faster than that of 1a to give methyl (E)-
3-fluoro-2-tridecenoate (11, 91%) with only a trace amount
of (E)-2-fluoro-1-iodo-1-dodecene (12) and 6.6b Generally,
the Pd-catalyzed methoxycarbonylation of an (E)-alkenyl-
iodide proceeds faster than that of the (Z)-isomer.15 Hence,
we found that the cis-bonded vinylic fluorine atom to the
iodonio group disturbed ‘path a’, which gave (Z)-fluoro-
alkenylpalladium intermediate, and it caused to produce
the phenylpalladium intermediate by ‘path b’; however,
the effect of the fluorine atom is unclear now.14,16,17
R1
R1
F
CuI, KI
DMF
F
I(Ph)BF4
I
1
3, Z / E > 99 : 1
Entry
3
R1
Time (h)
Yield (%)
1b
2
a
a
a
b
d
e
f
C10H21
C10H21
C10H21
Ph
(cyclo-C6H11)-CH2
Cl-(CH2)9
12
36
24
3
36
36
36
36
87
89
0
87
88
92
91
91
3c
4
5
6
7
8
t-Bu-CO-(CH2)8
i-PrO2C-(CH2)8
g
a
Unless otherwise mentioned, reactions were carried out with 0.5 mmol of
1, 5 mol % of CuI, and 0.5 mmol of KI in DMF (0.125 M) at rt.
CuI (0.5 mmol) was used.
b
c
KI (0.75 mmol) was used in the absence of CuI.
Similarly, Heck reaction,6c,d,16 Sonogashira reaction,4k,6f,17
and Stille reaction6d,18 of 1a gave the desired (Z)-2-fluoro-
1-alkene derivatives 13a–15a in moderate yields, but the
formation of 3a was observed in all cases (Scheme 1). Unfor-
tunately, we couldn’t suppress the formation of 3a by modi-
fication of the reaction conditions; therefore, we decided to
use (Z)-2-fluoro-1-iodo-1-alkenes 3 to the Pd-catalyzed
cross-coupling reactions instead of (Z)-2-fluoro-1-alkenyl-
iodonium salts 1.
2.4. Pd-catalyzed cross-coupling reaction using
(Z)-2-fluoro-1-iodo-1-alkene (3)
Then, we attempted the Pd-catalyzed cross-coupling reac-
tions using (Z)-2-fluoro-1-iodo-1-dodecene (3a) and (Z)-a-
fluoro-b-iodostyrene (3b). By Pd-catalyzed cross-coupling
reactions, such as methoxycarbonylation, Heck reaction,
Stille reaction, Sonogashira reaction, and Suzuki–Miyaura
reaction19 using (Z)-2-fluoro-1-iodoalkenes 3, a variety of
(Z)-2-fluoro-1-alkene derivatives (5 and 13–17) were syn-
thesized stereoselectively in good yields (Table 4). By using
our methodology for the fluoroalkenes synthesis, we have
succeeded in the stereoselective synthesis of the fluorinated
analogues of insect sex pheromones and reported in a recent
paper.20
O
C10H21
+ 3a
1a
F
O
Pd cat.
13a, 70%
(3E,5Z) / (3E,5E) = 96 : 4
8%
n-Bu
C10H21
3. Conclusions
+ 3a
1a
F
n-Bu
Pd cat.
14a, 65%
19%
(Z)-2-Fluoro-1-alkenyl(phenyl)iodonium salts 1were stereo-
selectively synthesized in good yields by an HF addition to
1-alkynyl(phenyl)iodonium salts 2 with diluted hydrofluoric
acid or Et3N–3HF. Pd-catalyzed cross-coupling reactions
using 1 gave (Z)-2-fluoro-1-alkene derivatives in fair yields.
The transformation of 1 to (Z)-2-fluoro-1-iodo-1-alkenes 3
was performed with a catalytic amount of CuI and a stoichio-
metric amount of KI. By Pd-catalyzed cross-coupling reac-
tions of 3, various (Z)-2-fluoro-1-alkene derivatives were
stereoselectively synthesized in good yields. We previously
reported that (E)-2-fluoro-1-alkenyliodonium salts were
stereoselectively synthesized by the reaction of terminal
alkynes with p-iodotoluene difluoride and their application
to the stereoselective synthesis of (E)-2-fluoro-1-alkenes.
Hence, we developed an efficient methodology for the
highly stereoselective synthesis of (E)- and (Z)-2-fluoro-1-
alkene derivatives from terminal alkynes via the fluoroalke-
nyliodonium salts.
Z / E > 99 : 1
SnBu3
Pd cat.
C10H21
+ 3a
11%
1a
F
15a, 69%
Z / E = 99 : 1
Scheme 1. Pd-catalyzed cross-coupling reactions using 1a.
2.3. Synthesis of (Z)-2-fluoro-1-iodo-1-alkenes (3) from
(Z)-2-fluoroalkenyliodonium salts (1)
The transformation of alkenyliodonium salts to iodoalkenes
with CuI and KI was first reported by Ochiai et al.7,14b They
proposed that the substitution reaction of iodine for iodonio
group can be catalyzed by CuI; however, excess amount of
CuI and KI were used in their procedure. We tried the syn-
thesis of 3a from 1a with a catalytic amount of CuI and a stoi-
chiometric amount of KI, and confirmed that the reaction
well proceeded with 5 mol % of CuI to give 3a in good yield
(Table 3, entry 2), although no reaction occurred without CuI
(entry 3). Under the reaction conditions listed in entry 2,
a variety of (Z)-fluoroiodoalkenes 3 were synthesized from
1 in good yields with retention of the stereochemistry
(entries 4–8).
4. Experimental
4.1. General
1
The chemical shifts, d, of H NMR (400 MHz), 19F NMR
(376 MHz), and 13C NMR (100 MHz) spectra were referred

M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
Table 4. Pd-catalyzed cross-coupling reactions 3a and 3b
8639
Substrate
Coupling reagent
CO, MeOH
Product
Yield (%)
88
Z/E
C10H21
Ph
COOMe
3a
5a
>99:1
F
COOMe
3b
3a
3b
3a
3b
3a
3b
3a
3b
3a
CO, MeOH
5b
77
77
76
88
83
86
83
88
85
81
>99:1
F
C10H21
COMe
13a
13b
14a
14b
15a
15b
16a
16b
17a
98:2 (3E,5Z)/(3E,5E)
96:4 (3E,5Z)/(3E,5E)
>99:1
COMe
COMe
F
Ph
COMe
F
C10H21
n-Bu
F
n-Bu
Ph
n-Bu
>99:1
F
n-Bu
C10H21
n-Bu3Sn
>99:1
F
Ph
n-Bu3Sn
Ph
>99:1(1Z,3E)/(1E,3E)
>99:1
Ph
F
C10H21
Ph
Ph-B(OH)2
Ph-B(OH)2
F
Ph
Ph
>99:1
F
C10H21
(HO)2B
n-Bu
>99:1 (5E,7Z)/(5E,7E)
n-Bu
F
Ph
(HO)2B
n-Bu
3b
17b
72
>99:1(1Z,3E)/(1E,3E)
n-Bu
F
to TMS (1H, 13C) and CFCl3 (19F). Et3N–2HF was prepared
as CH2Cl2 solution by the addition of Et3N to Et3N–3HF in
CH2Cl2 before use. Commercial CHCl3 was distilled before
use. Pd(PPh3)4,21 (E)-1-dodecenyl(phenyl)iodonium tetra-
fluoroborate (7),14b Et3N–5HF,22 tributylvinylstannane,23
tributylstyrylstannane,24 and (E)-1-hexenylboronic acid25
werepreparedaccordingtotheliteratures.1-Alkynyl(phenyl)-
iodonium tetrafluoroborates (2) were prepared from the
corresponding terminal alkynes by our method.8c The spec-
tral data for 1a,10 1c–g,10 2b,26 3a,10 5a,10 11,6b 12,6a and
14a10 were reported in the literatures.
(40 ml). The white suspension was left in a refrigerator for
2 h and clear upper liquid was removed by decantation.
The remained white solid was washed with hexane (5 ml)
again, separated by decantation, and dried in vacuo to
give (Z)-2-fluoro-1-dodecenyl(phenyl)iodonium tetrafluoro-
borate (1a)10 (72%, 171 mg, 0.36 mmol, Z/E>99:1).
4.3. Synthesis of 1a by the reaction of 2a with
hydrofluoric acid
In a TeflonÔ PFA vessel were placed 2a (228 mg,
0.5 mmol), CHCl3 (2 ml), and a 20% hydrofluoric acid
(500 mg, 5 mmol) at room temperature, and the mixture
was vigorously stirred at 60 ꢀC for 6 h. The reaction mixture
was poured into a 0.5 M aq NaBF4 (20 ml) and extracted
with CH2Cl2 (10 ml) four times. The combined organic
phase was dried over MgSO4 and concentrated under
reduced pressure. The resulting viscous oil was dissolved
in CH2Cl2 (1 ml) and a white suspension was formed by
the addition of hexane (40 ml). The white suspension was
left in a refrigerator for 2 h and the clear upper liquid was re-
moved by decantation. The remained precipitate was washed
with hexane (40 ml) again, separated from hexane by decan-
tation, and dried in vacuo to give pure 1a (84%, 200 mg,
0.42 mmol, Z/E>99:1).
4.2. Synthesis of (Z)-2-fluoro-1-dodecenyl(phenyl)iodo-
nium tetrafluoroborate (1a) by the reaction of 2a with
Et3N–3HF
In a TeflonÔ PFA vessel were placed 1-dodecynyl(phenyl)-
iodonium tetrafluoroborate (2a) (228 mg, 0.5 mmol) and
Et3N–3HF (805 mg, 5 mmol) at room temperature, and the
mixture was stirred at 40 ꢀC for 8 h. The reaction mixture
was poured into water (100 ml) and extracted with CH2Cl2
(10 ml) four times. The combined organic phase was dried
over MgSO4 and concentrated under reduced pressure. The
resulting viscous oil was dissolved in CH2Cl2 (1 ml) and
a white suspension was formed by the addition of hexane

8640
M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
4.4. (Z)-2-Fluoro-2-phenylethenyl(phenyl)iodonium
tetrafluoroborate (1b)
[HR FABMS Calcd for C17H23ClI (MꢁBF4): 389.0533.
Found: M+ꢁBF4, 389.0545]. Found: C, 42.91; H, 4.76%.
Calcd for C17H23BClF4I: C, 42.85; H, 4.86%.
Mp 136.5–137.0 ꢀC, dH (DMSO-d6) 7.53–7.77 (8H, m), 7.94
[1H, d, 3JH–F(olefin) 37.5 Hz, 1-H], 8.17 (2H, d, J 8.03 Hz); dF
4.9. 2-(10,10-Dimethyl-9-oxoundecanyl)ethynyl-
(phenyl)iodonium tetrafluoroborate (2f)
3
(DMSO-d6) ꢁ83.80 [1F, d, JH–F(olefin) 37.5 Hz, 2-F]; dC
2
(DMSO-d6) 80.4 (d, JC–F 21.5 Hz, 1-C), 115.4, 125.9 (2C,
d, 3JC–F 7.4 Hz, ortho), 127.4 (d, 2JC–F 28.0 Hz, ipso), 129.3
Oil, dH (CDCl3) 1.13–1.37 (17H, m), 1.51–1.63 (4H, m),
2.47 (2H, t, J 7.1 Hz, 10-H), 2.65 (2H, t, J 7.1 Hz, 3-H),
7.53–8.07 (5H, m, Ph); dC (CDCl3) 16.0, 20.8, 23.7, 26.4
(3C), 27.5, 28.5, 28.6, 29.0, 29.1, 36.4, 44.1, 114.0, 114.6,
132.7 (2C), 132.9, 133.8 (2C), 216.4; n (neat)/cmꢁ1 3093,
2930, 2857, 2182, 1702, 1469, 1445, 1366, 1067, 985,
740, 676; [HR FABMS Calcd for C21H30IO (MꢁBF4):
425.1341. Found: M+ꢁBF4, 425.1344]. Found: C, 49.19;
H, 5.91%. Calcd for C21H30BF4IO: C, 49.25; H, 5.90%.
1
(2C), 131.8 (2C), 132.0, 132.5, 135.0 (2C), 164.6 (d, JC–F
261.8 Hz, 2-C); n (KBr)/cmꢁ1 3113, 1625, 1575, 1496,
1470, 1445, 1290, 1084, 1037, 987, 796, 768, 740, 677, 651,
634, 603, 521; [HR FABMS Calcd for C14H11FI (MꢁBF4):
324.9890. Found: M+ꢁBF4, 324.9868]. Found: C, 40.63; H,
2.67%. Calcd for C14H11BF5I: C, 40.82; H, 2.69%.
4.5. 1-Dodecynyl(phenyl)iodonium tetrafluoroborate
(2a)
4.10. 10-Isopropoxycarbonyl-1-decynyl(phenyl)-
iodonium tetrafluoroborate (2g)
Mp 41.5–42.2 ꢀC, dH (CDCl3) 0.88 (3H, t, J 7.1 Hz, 12-H),
1.19–1.39 (14H, m), 1.55–1.63 (2H, m, 4-H), 2.65 (2H, t,
J 7.1 Hz, 3-H), 7.53–8.07 (5H, m, Ph); dC (CDCl3) 14.1,
16.0, 20.8, 22.6, 27.6, 28.7, 28.9, 29.2, 29.3, 29.5, 31.8,
114.1, 114.6, 132.7 (2C), 132.9, 133.8 (2C); n (KBr)/cmꢁ1
3051, 2924, 2853, 2168, 1470, 1441, 1069, 1038, 987,
738, 678, 650; [HR FABMS Calcd for C18H26I (MꢁBF4):
369.1079. Found: M+ꢁBF4, 369.1096]. Found: C, 47.42;
H, 5.81%. Calcd for C18H26BF4I: C, 47.40; H, 5.75%.
Oil, dH (CDCl3) 1.20–1.39 (14H, m), 1.56–1.61 (4H, m),
2.25 (2H, t, J 7.3 Hz, 10-H), 2.65 (2H, t, J 7.1 Hz, 3-H),
4.97–5.03 (1H, m, iPr), 7.54–8.07 (5H, m, Ph); dC (CDCl3)
16.3, 20.5, 21.6 (2C), 24.6, 27.2, 28.3, 28.4, 28.61, 28.64,
34.4, 67.3, 113.1, 114.3, 132.4 (2C), 132.7, 133.8 (2C),
173.4; n (neat)/cmꢁ1 3090, 3062, 2980, 2932, 2857, 2182,
1726, 1691, 1469, 1445, 1375, 1182, 1107, 985, 741, 676;
[HR FABMS Calcd for C20H28IO2 (MꢁBF4): 427.1134.
Found: M+ꢁBF4, 427.1134]. Found: C, 46.50; H, 5.43%.
Calcd for C20H28BF4IO2: C, 46.72; H, 5.49%.
4.6. 3,3-Dimethyl-1-butynyl(phenyl)iodonium
tetrafluoroborate (2c)
Mp 189.6–190.5 ꢀC, dH (CDCl3) 1.33 (9H, s, tBu), 7.55–8.05
(5H, m, Ph); dC (CDCl3) 15.7, 29.9 (3C), 30.2, 114.8, 121.4,
132.77 (2C), 132.83, 133.5 (2C); n (KBr)/cmꢁ1 3097, 2977,
2932, 2871, 2192, 2155, 1560, 1470, 1446, 1366, 1286,
1253, 1051, 921, 743, 675, 645; [HR FABMS Calcd for
C12H14I (MꢁBF4): 285.0140. Found: M+ꢁBF4, 285.0146].
Found: C, 38.55; H, 3.74%. Calcd for C12H14BF4I: C,
38.75; H, 3.79%.
4.11. Synthesis of (Z)-2-fluoro-1-iodo-1-dodecene (3a)
from 1a
To a DMF solution (4 ml) of 1a (238 mg, 0.5 mmol) were
added CuI (4.8 mg, 0.025 mmol) and KI (83 mg,
0.5 mmol), and the mixture was stirred at room temperature
for 36 h. The reaction mixture was poured into 3 M aq
NH4Cl (15 ml) and extracted with ether (10 ml) three times.
The combined organic phase was dried over MgSO4 and
concentrated under reduced pressure. In order to remove
the generated iodobenzene, the reaction mixture was kept
at 40 ꢀC and 0.01 mmHg for 1 h. The product 3a10 was iso-
lated by column chromatography (silica gel, hexane) in 89%
yield (139 mg, Z/E>99:1).
4.7. 3-Cyclohexyl-1-propynyl(phenyl)iodonium
tetrafluoroborate (2d)
Mp 86.2–87.2 ꢀC, dH (CDCl3) 0.94–1.30 (5H, m), 1.56–1.77
(6H, m), 2.57 (2H, d, J 6.6 Hz, 3-H), 7.54–8.07 (5H, m, Ph);
dC (CDCl3) 16.4, 25.8 (2C), 25.8, 28.5, 32.6 (2C), 36.9,
113.6, 114.8, 132.8 (2C), 132.9, 133.7 (2C); n (KBr)/cmꢁ1
3086, 2928, 2849, 2185, 1562, 1473, 1446, 1417, 1327,
1275, 1070, 891, 765, 738, 676, 650; [HR FABMS Calcd
for C15H18I (MꢁBF4): 325.0453. Found: M+ꢁBF4,
325.0470]. Found: C, 43.83; H, 4.42%. Calcd for
C15H18BF4I: C, 43.73; H, 4.40%.
4.12. (Z)-2-Fluoro-1-iodo-2-phenylethene (3b)
Oil, dH (CDCl3) 6.08 [1H, d, 3JH–F(olefin) 34.4 Hz, 1-H], 7.36–
3
7.52 (5H, m, Ph); dF (CDCl3) ꢁ90.62 [1F, d, JH–F(olefin)
2
34.4 Hz]; dC (CDCl3) 53.4 (d, JC–F 28.8 Hz, 1-C), 124.6
3
4
(2C, d, JC–F 5.8 Hz, ortho), 128.7 (2C, d, JC–F 1.7 Hz,
meta), 129.8, 130.9 (d, 2JC–F 28.9 Hz, ipso), 163.1 (d, 1JC–F
251.9 Hz, 2-C); n (neat)/cmꢁ1 3095, 3058, 1629, 1574,
1495, 1445, 1281, 1187, 1034, 1015, 791, 768, 741, 687,
606; [HR EIMS Calcd for C8H6FI (M): 247.9498. Found:
M+, 247.9480]. Found: C, 38.78; H, 2.48%. Calcd for
C8H6FI: C, 38.74; H, 2.44%.
4.8. 11-Chloro-1-undecynyl(phenyl)iodonium
tetrafluoroborate (2e)
Mp 47.7–48.4 ꢀC, dH (CDCl3) 1.21–1.44 (10H, m), 1.55–
1.63 (2H, m, 4-H), 1.72–1.79 (2H, m, 10-H), 2.64 (2H, t,
J 7.3 Hz, 3-H), 3.53 (2H, t, J 6.8 Hz, 11-H), 7.52–8.07
(5H, m, Ph); dC (CDCl3) 15.9, 20.9, 26.8, 27.6, 28.69,
28.73, 28.8, 29.2, 32.6, 45.2, 114.2, 114.6, 132.8 (2C),
132.9, 133.8 (2C); n (KBr)/cmꢁ1 3050, 2992, 2925, 2854,
2166, 1562, 1470, 1441, 1305, 1051, 988, 740, 679, 650;
4.13. (Z)-3-Cyclohexyl-2-fluoro-1-iodo-1-propene (3d)
Oil, dH (CDCl3) 0.85–1.30 (5H, m), 1.52–1.62 (6H, m), 2.22
(2H, dd, 3JH–F 20.0, J 7.0 Hz, 3-H), 5.14 [1H, d, 3JH–F(olefin)

M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
8641
3
34.6 Hz, 1-H]; dF (CDCl3) ꢁ79.22 [1F, d, JH–F(olefin)
4.18. Synthesis of methyl (Z)-3-fluoro-2-tridecenoate
(5a) from 1a
34.6 Hz]; dC (CDCl3) 26.0 (2C), 26.2, 32.7 (2C), 34.9,
40.6 (d, JC–F 26.4 Hz, 3-C), 51.3 (d, JC–F 26.4 Hz, 1-C),
2
2
165.5 (d, JC–F 261.0 Hz, 2-C); n (neat)/cmꢁ1 3091, 2924,
In a glass round-bottom flask fitted with a balloon (3 L) were
placed PdCl2 (1.8 mg, 0.01 mmol), NaHCO3 (42 mg,
0.5 mmol), and MeOH (4 ml). After complete replacement
of the atmosphere in the flask with CO, the balloon was filled
with CO. Then a MeOH solution (1 ml) of 1a (238 mg,
0.5 mmol) was added and the mixture was stirred at room
temperature for 2 h. The reaction mixture was poured into
3 M aq NH4Cl (15 ml) and extracted with ether (10 ml) three
times. The combined organic phase was dried over MgSO4
and concentrated under reduced pressure. The product
5a10 was isolated by column chromatography (silica gel,
hexane–diethyl ether) in 73% yield (89 mg, Z/E>99:1).
Oil, dH (CDCl3) 0.88 (3H, t, J 7.1 Hz, 13-H), 1.21–1.37
1
2851, 1655, 1448, 1425, 1285, 1242, 1193, 1119, 962,
939, 896, 871, 746; [HR EIMS Calcd for C9H14FI (M):
268.0124. Found: M+, 268.0136].
4.14. (Z)-11-Chloro-2-fluoro-1-iodo-1-undecene (3e)
Oil, dH (CDCl3) 1.30–1.54 (12H, m), 1.73–1.80 (2H, m,
4-H), 2.33 (2H, dt, JH–F 16.6, J 7.3 Hz, 3-H), 3.53 (2H, t,
3
3
J 6.8 Hz, 11-H), 5.17 [1H, d, JH–F(olefin) 34.7 Hz, 1-H]; dF
(CDCl3) ꢁ79.87 [1F, dt, JH–F 16.6, JH–F(olefin) 34.7 Hz];
3
3
dC (CDCl3) 25.8, 26.8, 28.6, 28.8, 29.0, 29.2, 32.6, 32.7
(d, JC–F 27.2 Hz, 3-C), 45.1, 50.6 (d, JC–F 27.2 Hz, 1-C),
2
2
166.6 (d, JC–F 261.0 Hz, 2-C); n (neat)/cmꢁ1 3092, 2929,
(14H, m), 1.52–1.59 (2H, m, 5-H), 2.26 (2H, dt, JH–F
17.3, J 7.6 Hz, 4-H), 3.72 (3H, s, OMe), 5.18 [1H, d,
1
3
2855, 1656, 1464, 1429, 1257, 1116, 875, 748, 724, 650;
[HR EIMS Calcd for C11H19ClFI (M): 332.0204. Found:
M+, 332.0178].
3JH–F(olefin) 33.1 Hz, 2-H]; dF (CDCl3) ꢁ79.53 [1F, dt,
3
3JH–F 17.3, JH–F(olefin) 33.1 Hz]; dC (CDCl3) 14.1, 22.7,
25.5, 28.8, 29.2, 29.3, 29.4, 29.5, 31.9, 33.0 (d, JC–F
24.1 Hz, 4-C), 51.3, 98.4 (d, JC–F 6.0 Hz, 2-C), 164.3,
2
2
4.15. (Z)-12,12-Dimethyl-2-fluoro-1-iodo-11-oxo-
1-tridecene (3f)
1
172.4 (d, JC–F 281.1 Hz, 3-C); n (neat)/cmꢁ1 2951, 2926,
2855, 1736, 1685, 1466, 1436, 1349, 1278, 1217, 1137,
1033, 889, 833, 722; [HR EIMS Calcd for C13H22FO
(MꢁOMe): 213.1655. Found: M+ꢁOMe, 213.1648]. Found:
C, 68.78; H, 10.42%. Calcd for C14H25FO2: C, 68.82; H,
10.31%.
Oil, dH (CDCl3) 1.13 (9H, s), 1.20–1.36 (8H, m), 1.48–1.58
(4H, m), 2.33 (2H, dt, 3JH–F 16.8, J 7.3 Hz, 3-H), 2.47 (2H, t,
J 7.3 Hz, 10-H), 5.17 [1H, d, JH–F(olefin) 34.6 Hz, 1-H]; dF
3
3
3
(CDCl3) ꢁ79.85 [1F, dt, JH–F 16.8, JH–F(olefin) 34.6 Hz];
dC (CDCl3) 23.8, 25.8, 26.4 (3C), 28.6, 29.0, 29.2, 29.3,
32.7 (d, JC–F 26.4 Hz, 3-C), 36.4, 44.1, 50.6 (d, JC–F
2
2
Under the same reaction conditions, methyl (E)-2-tridece-
noate (8) (90%, E/Z>99:1) and methyl (E)-3-fluoro-2-
tridecenoate (11) (91%, Z/E¼2:98) were prepared from
(E)-1-dodecenyl(phenyl)iodonium tetrafluoroborate (7) and
(E)-2-fluoro-1-dodecenyl(phenyl)iodonium tetrafluorobo-
rate (10), respectively.
1
26.4 Hz, 1-C), 166.6 (d, JC–F 261.8 Hz, 2-C), 216.0;
n (neat)/cmꢁ1 3092, 2930, 2855, 1704, 1656, 1476,
1464, 1365, 1259, 1117, 1067, 988, 875, 747; [HR
EIMS Calcd for C15H26FIO (M): 368.1012. Found: M+,
368.1039].
4.16. (Z)-10-Isopropoxycarbonyl-2-fluoro-1-iodo-
1-decene (3g)
4.19. Synthesis of 5a from 3a
In a round-glass flask fitted with a balloon (3 L) were placed
PdCl2(PPh3)2 (7.0 mg, 0.01 mmol), Et3N (50 mg, 0.5 mmol),
and MeOH (5 ml). After complete replacement of the atmo-
sphere in the flask with CO, the balloon was filled with CO,
and 3a (156 mg, 0.5 mmol) was added into the flask. After
stirring at 60 ꢀC for 48 h, the reaction mixture was poured
into 3 M aq NH4Cl (15 ml) and extracted with ether (10 ml)
three times. The combined organic phase was dried over
MgSO4 and concentrated under reduced pressure. The prod-
uct 5a was isolated by column chromatography (silica gel,
hexane–ether) in 88% yield (107 mg, Z/E>99:1).
Oil, dH (CDCl3) 1.22–1.30 (14H, m), 1.48–1.64 (4H, m),
2.26 (2H, t, J 7.8 Hz, 10-H), 2.33 (2H, dt, JH–F 16.6,
3
3
J 7.6 Hz, 3-H), 4.96–5.05 (1H, m), 5.17 [1H, d, JH–F(olefin)
34.6 Hz, 1-H]; dF (CDCl3) ꢁ79.93 [1F, dt, JH–F 16.6,
3
3JH–F(olefin) 34.6 Hz]; dC (CDCl3) 21.8 (2C), 24.9, 25.8,
28.6, 28.97 (2C), 29.03, 32.7 (d, JC–F 27.3 Hz, 3-C), 34.6,
2
2
1
50.7 (d, JC–F 27.2 Hz, 1-C), 67.3, 166.6 (d, JC–F
261.0 Hz, 2-C), 173.3; n (neat)/cmꢁ1 3092, 2979, 2931,
2856, 1730, 1657, 1467, 1373, 1252, 1181, 1146, 1111,
962, 876, 824, 748; [HR EIMS Calcd for C14H24FIO2 (M):
370.0805. Found: M+, 370.0818].
The methoxycarbonylations of 9 and 12 were carried out
under the same reaction conditions.
4.17. 1,2,2-Trifluorododecane (4)
Oil, dH (CDCl3) 0.88 (3H, t, J 6.8 Hz, 12-H), 1.27–1.56 (16H,
m), 1.87–2.00 (2H, m, 3-H), 4.42 (2H, dt, 3JH–F 11.4, 2JH–F
46.6 Hz, 1-H); dF (CDCl3) ꢁ234.95 to ꢁ235.29 (1F, m),
ꢁ109.44 to ꢁ109.64 (2F, m); dC (CDCl3) 14.1, 21.5 (t,
3JC–F 4.1 Hz, 4-C), 22.7, 29.3 (3C), 29.4, 29.6, 31.9, 33.0
(t, JC–F 23.9 Hz, 3-C), 81.5 (dt, JC–F 37.1, JC–F
177.6 Hz, 1-C), 121.1 (dt, 2JC–F 22.3, 1JC–F 241.2 Hz, 2-C);
n (neat)/cmꢁ1 2960, 2926, 2856, 1466, 1381, 1280, 1196,
1137, 1060, 928; [HR EIMS Calcd for C12H23F3 (M):
224.1752. Found: M+, 224.1768].
4.20. Methyl (Z)-3-fluoro-3-phenyl-2-propenoate (5b)
Prepared from 3b as described for 5a in 77% yield
(Z/E>99:1). Oil, dH (CDCl3) 3.80 (3H, s, COOMe), 5.92
[1H, d, 3JH–F(olefin) 33.4 Hz, 2-H], 7.42–7.68 (5H, m, Ph); dF
2
2
1
3
(CDCl3) ꢁ96.25 [1F, d, JH–F(olefin) 33.4 Hz]; dC (CDCl3)
2
3
51.6, 96.8 (d, JC–F 7.4 Hz, 2-C), 125.6 (2C, JC–F 8.2 Hz,
ortho), 128.9 (2C), 130.5 (d, JC–F 25.60 Hz, ipso), 131.6,
2
164.5, 166.4 (d, JC–F 277.6 Hz, 3-C); n (neat)/cmꢁ1 3090,
2997, 2952, 2844, 1727, 1662, 1496, 1450, 1435, 1339,
1

8642
M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
1285, 1192, 1167, 1057, 1004, 828, 770, 688; [HR EIMS
Calcd for C10H9FO2 (M): 180.0586. Found: M+, 180.0586].
ꢁ20 ꢀC, the reaction mixture was poured into 3 M aq NH4Cl
(15 ml), and extracted with ether (10 ml) three times. The
combined organic phase was dried over MgSO4 and concen-
trated under reduced pressure. The product 13a was isolated
by column chromatography (silica gel, hexane–diethyl
ether) in 70% yield [89 mg, (3E,5Z)/(3E,5E)¼96:4]. Oil,
dH (CDCl3) 0.88 (3H, t, J 7.1 Hz, 16-H), 1.23–1.35 (14H,
m), 1.54–1.57 (2H, m, 8-H), 2.25–2.33 (5H, m), 5.44 [1H,
4.21. (E)-1-Dodecenyl(phenyl)iodonium tetrafluoro-
borate (7)
Mp 36.0–36.5 ꢀC, dH (CDCl3) 0.88 (3H, t, J 7.1 Hz, 12-H),
1.19–1.32 (14H, m), 1.41–1.48 (2H, m, 4-H), 2.31–2.36
(2H, m, 3-H), 6.79 (1H, d, J 13.7 Hz, 1-H), 6.99 (1H, dt,
J 7.3, 13.7 Hz, 2-H), 7.48–8.02 (5H, m, Ph); dC (CDCl3)
14.1, 22.6, 27.6, 28.9, 29.2, 29.3, 29.4, 29.5, 31.8, 35.3,
96.5, 109.6, 132.4 (2C), 132.7, 135.6 (2C), 155.4; n (KBr)/
cmꢁ1 3052, 3002, 2918, 2850, 1469, 1444, 1067, 988,
739; [HR FABMS Calcd for C18H28I (MꢁBF4): 371.1236.
Found: M+ꢁBF4, 371.1220]. Found: C, 46.84; H, 6.03%.
Calcd for C18H28BF4I: C, 47.19; H, 6.16%.
3
dd, J 11.2, JH-F(olefin) 33.4 Hz, 5-H], 6.04 (1H, d,
J 15.9 Hz, 3-H), 7.42 (1H, dd, J 11.2, 15.9 Hz, 4-H); dF
3
3
(CDCl3) ꢁ92.13 [1F, dt, JH–F 17.7, JH–F(olefin) 33.4 Hz];
dC (CDCl3) 14.1, 22.6, 25.9, 26.7, 28.9, 29.2, 29.3, 29.4,
29.5, 31.9, 32.5 (d, JC–F 24.0 Hz, 7-C), 105.5 (d, JC–F
11.5 Hz, 5-C), 128.8 (d, 4JC–F 3.2 Hz, 3-C), 135.5 (d, 3JC–F
2
2
1
6.6 Hz, 4-C), 167.4 (d, JH–F 274.2 Hz, 6-C), 198.7;
n (neat)/cmꢁ1 3057, 2951, 2926, 2855, 1695, 1659, 1599,
1466, 1361, 1254, 1134, 982, 866, 722; [HR FABMS Calcd
for C16H27FO (MꢁBF4): 254.2046. Found: M+ꢁBF4,
254.2037].
4.22. Synthesis of (E)-2-fluoro-1-dodecenyl(phenyl)-
iodonium tetrafluoroborate (10)
To a CH2Cl2 solution (6 ml) of 1-dodecyne (332 mg,
2 mmol) was added an Et3N–5HF solution (22 ml) of p-
iodotoluene difluoride (768 mg, 3 mmol) at 0 ꢀC and the
mixture was stirred at 0 ꢀC for 2 h. The reaction mixture
was poured into water (30 ml) and extracted with CH2Cl2
(20 ml) three times. The combined organic phase was dried
over MgSO4 and concentrated under reduced pressure. The
resulting crude (E)-2-fluoro-1-dodecenyl(phenyl)iodonium
fluoride was dissolved in acetonitrile (10 ml) with AgBF4
(779 mg, 4 mmol) and the mixture was stirred at room tem-
perature for 1 h. The reaction mixture was poured into water
(30 ml) and extracted with CH2Cl2 (20 ml) three times. The
combined organic phase was dried over MgSO4 and concen-
trated under reduced pressure. The resulting viscous oil was
dissolved in CH2Cl2 (1 ml) and a white suspension was
formed by the addition of hexane (40 ml). The white suspen-
sion was left in a refrigerator for 2 h and clear upper liquid
was removed by decantation. The remained white solid
was washed with hexane (5 ml) again, separated by decanta-
tion, and dried in vacuo to give pure compound 10 (43%,
400 mg, 0.84 mmol, E/Z>99:1). Mp 71.8–72.4 ꢀC, dH
(CDCl3) 0.88 (3H, t, J 6.8 Hz, 12-H), 1.17–1.30 (14H, m),
1.47–1.54 (2H, m, 4-H), 2.79 (2H, dt, J 7.6, 3JH–F 22.2 Hz,
4.24. Synthesis of 13a from 3a
To a DMF solution (2.5 ml) of Pd(PPh3)4 (57.8 mg,
0.05 mmol) were added Et3N (505 mg, 5 mmol), methyl
vinyl ketone (88 mg, 1.25 mmol), and 3a (156 mg, 0.5
mmol) at room temperature and the mixture was stirred at
60 ꢀC for 4 h. The reaction mixture was poured into 3 M
aq NH4Cl (15 ml) and extracted with ether (10 ml) three
times. The combined organic phase was dried over MgSO4
and concentrated under reduced pressure. The product 13a
was isolated by column chromatography (silica gel, hex-
ane–diethyl ether) in 77% yield (98 mg, Z/E¼98:2).
4.25. (3E,5Z)-6-Fluoro-6-phenyl-3,5-hexadien-2-one
(13b)
Prepared from 3b as described for 13a in 76% yield (Z/E¼
96:4). Mp 89.2–90.0 ꢀC, dH (CDCl3) 2.35 (3H, s, Me),
6.24 (1H, d, J 15.9 Hz, 3-H), 6.27 [1H, dd, J 11.2, 3JH–F(olefin)
33.2 Hz, 5-H], 7.42–7.65 (6H, m); d (CDCl3) ꢁ108.44 [1F,
F
3
2
d, JH–F(olefin) 33.2 Hz]; dC (CDCl3) 27.0, 104.8 (d, JC–F
13.3 Hz, 5-C), 124.9 (2C, d, JC–F 7.4 Hz, ortho), 128.8
3
4
3
3
(2C, d, JC–F 2.5 Hz, meta), 130.3 (d, JC–F 4.1 Hz, 3-C),
130.5, 130.7 (d, JC–F 26.4 Hz, ipso), 135.3 (d, JC–F
3-H), 6.72 [1H, d, JH–F(olefin) 14.4 Hz, 1-H], 7.46–7.98
(5H, m, Ph); dF (CDCl3) ꢁ65.89 [1F, dt, JH–F(olefin) 14.4,
2
3
3
1
3JH–F 22.2 Hz]; dC (CDCl3) 14.1, 22.6, 25.8, 28.9, 29.2,
29.26, 29.32, 29.5, 31.8, 32.2 (d, JC–F 23.9 Hz, 3-C), 78.3
(d, JC–F 47.9 Hz, 1-C), 112.1, 132.3 (2C), 132.5, 134.5
5.8 Hz, 4-C), 161.8 (d, JC–F 265.1 Hz, 6-C), 198.4;
n (KBr)/cmꢁ1 1658, 1631, 1363, 1292, 1257, 1008, 976,
768, 692; [HR FABMS Calcd for C12H11FO (M):
190.0794. Found: M+, 190.0808].
2
2
1
(2C), 176.2 (d, JC–F 286.5 Hz, 2-C); n (KBr)/cmꢁ1 3045,
2925, 2854, 1638, 1467, 1440, 1303, 1071, 993, 877, 797,
736, 684; [HR FABMS Calcd for C18H27FI (MꢁBF4):
389.1142. Found: M+ꢁBF4, 389.1154]. Found: C, 45.47;
H, 5.57%. Calcd for C18H27BF5I: C, 45.41; H, 5.72%.
4.26. Synthesis of (Z)-8-fluoro-7-octadecen-5-yne (14a)
from 1a
A DMF solution (5 ml) of Pd(OAc)2 (5.6 mg, 0.025 mmol)
and PPh3 (13.1 mg, 0.05 mmol) was stirred at room temper-
ature for 10 min and then CuI (15.2 mg, 0.08 mmol), hex-1-
yne (49 mg, 0.6 mmol), Et3N (76 mg, 0.75 mmol), and
a DMF solution (1 ml) of 1a (238 mg, 0.5 mmol) were
added. After stirring for 15 min at room temperature, the
reaction mixture was poured into 3 M aq NH4Cl (15 ml),
and extracted with ether (10 ml) three times. The combined
organic phase was dried over MgSO4 and concentrated
under reduced pressure. The product 14a10 was isolated by
4.23. Synthesis of (3E,5Z)-6-fluoro-3,5-hexadecadien-
2-one (13a) from 1a
To a mixture of Pd(OAc)2 (5.6 mg, 0.025 mmol) and KI
(4.2 mg, 0.025 mmol) in DMF (1.5 ml) were added 1.2 M
aq NaHCO3 (0.5 ml, 0.60 mmol) and methyl vinyl ketone
(88 mg, 1.25 mmol) at room temperature. The reaction mix-
ture was then cooled to ꢁ20 ꢀC and a DMF solution (1 ml) of
1a (238 mg, 0.5 mmol) was added. After stirring for 12 h at

M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
8643
column chromatography (silica gel, hexane) in 65% yield
(86 mg, Z/E>99:1).
tributylvinylstannane (270 mg, 0.85 mmol) at room temper-
ature. The reaction mixture was stirred at 60 ꢀC for 0.5 h,
then poured into 3 M aq NH4Cl (15 ml), and extracted
with ether (10 ml) three times. The combined organic phase
was dried over MgSO4 and concentrated under reduced
pressure. The product 15a was isolated by column chroma-
tography (silica gel, hexane) in 86% yield (91 mg,
Z/E>99:1).
4.27. Synthesis of 14a from 3a
A mixture of Pd(OAc)2 (5.6 mg, 0.025 mmol) and PPh3
(13 mg, 0.05 mmol) in DMF (5 ml) was stirred at room tem-
perature for 10 min and then CuI (15 mg, 0.08 mmol), hex-
1-yne (62 mg, 0.75 mmol), Et3N (150 mg, 1.5 mmol), and
3a (156 mg, 0.5 mmol) were added. After stirring at 30 ꢀC
for 2 h, the reaction mixture was poured into 3 M aq
NH4Cl (15 ml), and extracted with ether (10 ml) three times.
The combined organic phase was dried over MgSO4 and
concentrated under reduced pressure. The product 14a was
isolated by column chromatography (silica gel, hexane) in
88% yield (117 mg, Z/E>99:1).
4.31. (1Z,3E)-1-Fluoro-1,4-diphenyl-1,3-butadiene (15b)
Prepared from 3b with tributylstyryltin as described for 15a
in 83% yield (Z/E>99:1). Mp 132.5–133.0 ꢀC, dH (CDCl3)
6.29 [1H, dd, J 11.0, JH–F(olefin) 34.8 Hz, 2-H], 6.66 (1H,
3
d, J 15.8 Hz, 4-H), 7.21–7.60 (11H, m); dF (CDCl3)
ꢁ118.26 [1F, d, 3JH–F(olefin) 34.8 Hz]; dC (CDCl3) 106.9 (d,
3
2JC–F 13.3 Hz, 2-C), 120.9 (d, JC–F 5.0 Hz, 3-C), 123.9
(2C, d, JC–F 7.4 Hz, ortho), 126.5 (2C), 127.7, 128.6
(2C), 128.7 (2C), 128.9, 132.0 (d, JC–F 26.4 Hz, ipso),
3
4.28. (Z)-1-Fluoro-1-phenyl-1-octen-3-yne (14b)
3
4
1
Prepared from 3b as described for 14a in 83% yield (Z/E>
99:1). Oil, dH (CDCl3) 0.94 (3H, t, J 7.3 Hz, 8-H), 1.44–
1.61 (4H, m), 2.40–2.44 (2H, m, 5-H), 5.57 [1H, dt, JH–H
132.3 (d, JC–F 3.3 Hz, 4-C), 137.3, 157.0 (d, JC–F
255.3 Hz, 1-C); n (KBr)/cmꢁ1 3060, 3033, 3020, 2997,
1634, 1488, 1444, 1320, 1280, 994, 965, 863, 748, 687,
653, 617; [HR EIMS Calcd for C16H13F (M): 224.1001.
Found: M+, 224.1005].
5
3
2.4, JH–F(olefin) 33.4 Hz, 2-H], 7.34–7.54 (5H, m, Ph); dF
(CDCl3) ꢁ106.77 [1F, d, JH–F(olefin) 33.4 Hz]; dC (CDCl3)
3
4
13.6, 19.5, 22.0, 30.8, 73.1 (d, JC–F 3.3 Hz, 4-C), 87.6 (d,
3
2JC–F 16.6 Hz, 2-C), 97.8 (d, JC–F 5.8 Hz, 3-C), 123.9
(2C, d, JC–F 7.4 Hz, ortho), 128.6 (2C, d, JC–F 1.6 Hz,
4.32. Synthesis of (Z)-2-fluoro-1-phenyl-1-dodecene
(16a) from 3a
3
4
2
meta), 129.6, 131.3 (d, JC–F 26.4 Hz, ipso), 164.2 (d,
1JC–F 258.6 Hz, 1-C); n (neat)/cmꢁ1 3058, 2958, 2932,
2872, 2221, 1643, 1496, 1448, 1326, 1286, 1038, 1018,
830, 760, 688; [HR EIMS Calcd for C14H15F (M):
202.1158. Found: M+, 202.1148].
To a mixture of PdCl2(PPh3)2 (18 mg, 0.025 mmol) and phe-
nylboronic acid (73 mg, 0.6 mmol) in benzene (5 ml) were
added 2 M aq K2CO3 (0.3 ml, 0.6 mmol) and 3a (156 mg,
0.5 mmol) at room temperature. After stirring at 80 ꢀC for
1.5 h, the reaction mixture was poured into 3 M aq NH4Cl
(15 ml), and extracted with diethyl ether (10 ml) three times.
The combined organic phase was dried over MgSO4 and
concentrated under reduced pressure. The product 16a was
isolated by column chromatography (silica gel, hexane) in
88% yield (112 mg, Z/E>99:1). Oil, dH (CDCl3) 0.88 (3H,
t, J 6.7 Hz, 12-H), 1.21–1.63 (16H, m), 2.31 (2H, dt, J 7.6,
4.29. Synthesis of (Z)-4-fluoro-1,3-tetradecadiene (15a)
from 1a
To a DMF solution (2 ml) of Pd(PPh3)4 (28.9 mg,
0.025 mmol) were added a DMF solution (1 ml) of 1a
(238 mg, 0.5 mmol) and tributylvinylstannane (174 mg,
0.55 mmol) at room temperature. After stirring at room
temperature for 96 h, the reaction mixture was poured into
3 M aq NH4Cl (15 ml), and extracted with ether (10 ml) three
times. The combined organic phase was dried over MgSO4
and concentrated under reduced pressure. The product 15a
was isolated by column chromatography (silica gel, hexane)
in 69% yield (73 mg, Z/E¼99:1). Oil, dH (CDCl3) 0.88 (3H, t,
J 7.1 Hz, 14-C), 1.23–1.35 (14H, m), 1.47–1.54 (2H, m, 6-H),
3
3JH–F 18.3 Hz, 3-H), 5.45 [1H, d, JH–F(olefin) 39.5 Hz],
3
7.17–7.47 (5H, m, Ph); dF (CDCl3) ꢁ101.25 [1F, dt, JH–F
3
18.3, JH–F(olefin) 39.5 Hz]; dC (CDCl3) 14.1, 22.7, 26.4,
28.8, 29.1, 29.2, 29.3, 29.5, 29.6, 31.9, 108.0 (d, JC–F
28.9 Hz, 1-C), 126.6 (2C), 128.4 (3C), 134.4 (d, JC–F
2
3
1
14.1 Hz, ipso), 162.8 (d, JC–F 253.1 Hz, 2-C); n (neat)/
cmꢁ1 3059, 3026, 2926, 2854, 1691, 1496, 1466, 1346,
1149, 912, 882, 831, 751, 693; [HR EIMS Calcd for
C18H27F (M): 262.2097. Found: M+, 262.2094].
3
2.19 (2H, dt, J 7.6, JH–F 17.5 Hz, 5-H), 4.95 (1H, d,
J 10.5 Hz, 1-H), 5.10 (1H, dd, J 1.7, 17.1 Hz, 1-H), 5.25
3
[1H, dd, J 10.5, JH–F(olefin) 35.6 Hz, 3-H], 6.59 (1H, dt,
J 10.5, 17.1 Hz, 2-H); dF (CDCl3) ꢁ103.74 [1F, dt, JH–F
4.33. (Z)-2-Fluoro-1,2-diphenylethene (16b)
3
3
17.5, JH–F(olefin) 35.6 Hz]; dC (CDCl3) 14.1, 22.7, 26.1,
29.0, 29.3 (2C), 29.5, 29.6, 31.9, 32.0 (d, JC–F 25.6 Hz,
Prepared from 3b as described for 16a in 85% yield
(Z/E>99:1). Mp 92.5–93.2 ꢀC, dH (CDCl3) 6.31 [1H, d,
3JH–F(olefin) 39.5 Hz, 2-H], 7.23–7.65 (10H, m); dF (CDCl3)
ꢁ114.78 [1F, d, 3JH–F(olefin) 39.5 Hz]; dC (CDCl3) 105.8 (d,
2
5-C), 106.9 (d, 2JC–F 11.5 Hz, 3-C), 114.6 (d, 4JC–F 3.3 Hz,
3
1
1-C), 128.7 (d, JC–F 6.6 Hz, 2-C), 161.1 (d, JC–F
266.6 Hz, 4-C); n (neat)/cmꢁ1 3088, 2955, 2926, 2855,
1684, 1467, 1418, 1133, 994, 899, 861; [HR EIMS Calcd
for C14H25F (M): 212.1940. Found: M+, 212.1933].
3
2JC–F 9.9 Hz, 2-C), 124.3 (2C, d, JC–F 7.4 Hz, ortho),
127.3 (2C, d, 4JC–F 2.5 Hz, meta), 128.6 (3C), 128.9, 129.0
(2C), 132.9 (d, JC–F 28.1 Hz, ipso), 133.7 (d, JC–F
2
3
1
3.3 Hz, ipso), 157.2 (d, JC–F 258.5 Hz, 1-C); n (KBr)/
4.30. Synthesis of 15a from 3a
cmꢁ1 3089, 3054, 3020, 1653, 1494, 1449, 1333, 1282,
1199, 1077, 1033, 1011, 913, 830, 762, 687, 626; [HR
EIMS Calcd for C14H11F (M): 198.0845. Found: M+,
198.0845].
To a DMF solution (3 ml) of PdCl2(PPh3)2 (25 mg,
0.035 mmol) were added 3a (156 mg, 0.5 mmol) and

8644
M. Yoshida et al. / Tetrahedron 62 (2006) 8636–8645
4. For general fluoroalkene synthesis, see: (a) Okada, M.;
Nakamura, Y.; Saito, A.; Sato, A.; Horikawa, H.; Taguchi, T.
Tetrahedron Lett. 2002, 43, 5845; (b) Otaka, A.; Watanabe,
H.; Yukimasa, A.; Oishi, S.; Tamamura, H.; Fujii, N.
Tetrahedron Lett. 2001, 42, 5443; (c) Peng, S.; Qing, F.-L.;
Li, Y.-Q.; Hu, C.-M. J. Org. Chem. 2000, 65, 694; (d) Huang,
X.-H.; He, P.-Y.; Shi, G.-Q. J. Org. Chem. 2000, 65, 627; (e)
Brown, S. J.; Corr, S.; Percy, J. M. Tetrahedron Lett. 2000,
41, 5269; (f) Chevrie, D.; Lequeux, T.; Pommelet, J.-C. Org.
Lett. 1999, 1, 1539; (g) Percy, J. M.; Prime, M. E. J. Fluorine
Chem. 1999, 100, 147; (h) Lin, J.; Welch, J. T. Tetrahedron
Lett. 1998, 39, 9613; (i) Percy, J. M.; Wilkes, R. D.
Tetrahedron 1997, 53, 14749; (j) Hossain, M. A. Tetrahedron
Lett. 1997, 38, 49; (k) Eddarir, S.; Francesch, C.; Mestdagh,
H.; Rolando, C. Bull. Soc. Chim. Fr. 1997, 134, 741; (l)
Kuroboshi, M.; Yamada, N.; Takebe, Y.; Hiyama, T.
Tetrahedron Lett. 1995, 36, 6271; (m) Clemenceau, D.;
Cousseau, J. Tetrahedron Lett. 1993, 34, 6903; (n) Barluenga,
4.34. Synthesis of (5E,7Z)-8-fluoro-5,7-octadecadiene
(17a) from 3a
To a mixture of Pd(PPh3)4 (29 mg, 0.025 mmol) and (E)-
hex-1-enylboronic acid (77 mg, 0.6 mmol) in benzene
(5 ml) was added an EtOH solution (0.5 ml) of KOH
(56 mg, 1 mmol) and 3a (156 mg, 0.5 mmol) at room tem-
perature. After stirring for 1 h at 80 ꢀC, the reaction mixture
was poured into 3 M aq NH4Cl (15 ml), and extracted with
diethyl ether (10 ml) three times. The combined organic
phase was dried over MgSO4 and concentrated under re-
duced pressure. The product 17a was isolated by column
chromatography (silica gel, hexane) in 83% yield (111 mg,
(5Z,7E)/(5E,7E)>99:1). Oil, dH (CDCl3) 0.86–0.91 (6H,
m), 1.21–1.51 (20H, m), 2.05–2.21 (4H, m), 5.17 [1H, dd,
3
J 10.7, JH–F(olefin) 36.3 Hz, 7-H], 5.57 (1H, dt, J 6.8,
15.6 Hz, 5-H), 6.22–6.29 (1H, m, 6-H); dF (CDCl3)
3
3
ꢁ106.88 [1F, dt, JH–F 17.7, JH–F(olefin) 36.3 Hz]; dC
ꢀ
ꢀ
J.; Campos, P. J.; Gonzalez, J. M.; Suarez, J. L. J. Org.
Chem. 1991, 56, 2234; (o) Barluenga, J.; Rodrıguez, M. A.;
(CDCl3) 13.9, 14.1, 22.2, 22.7, 26.2, 29.0, 29.3, 29.4, 29.5,
29.6, 31.9, 32.0 (d, JC–F 26.4 Hz, 9-C), 32.2, 32.5, 106.3
(d, JC–F 12.3 Hz, 7-C), 121.7 (d, JC–F 5.8 Hz, 6-C),
2
´
2
3
Campos, P. J. J. Org. Chem. 1990, 55, 3104; (p) Gillet, J. P.;
^
1
132.3, 159.2 (d, JC–F 260.2 Hz, 8-C); n (neat)/cmꢁ1 3039,
Sauvetre, R.; Normant, J. F. Synthesis 1982, 297.
5. For fluoroalkene synthesis by the Horner–Wadsworth–
Emmons reaction: (a) Zhang, X.; Burton, D. J. J. Fluorine
Chem. 2001, 112, 317; (b) Chen, C.; Wilcoxen, K.; Zhu,
Y.-F.; Kim, K.-I.; McCarthy, J. R. J. Org. Chem. 1999, 64,
3476; (c) Burton, D. J. J. Fluorine Chem. 1999, 100, 177; (d)
Chen, C.; Wilcoxen, K.; Strack, N.; McCarthy, J. R.
Tetrahedron Lett. 1999, 40, 827; (e) Percy, E.; Singh, M.;
Takahashi, T.; Takeuchi, Y.; Kirk, K. L. J. Fluorine Chem.
1998, 91, 5; (f) McCarthy, J. R.; Huber, E. W.; Le, T.-B.;
Laskovics, F. M.; Matthews, D. P. Tetrahedron 1996, 52, 45;
(g) Patrick, T. B.; Lanahan, M. V.; Yang, C.; Walker, J. K.;
Hutchinson, C. L.; Neal, B. E. J. Org. Chem. 1994, 59, 1210;
(h) Pirrung, M. C.; Rowley, E. G.; Holmes, C. P. J. Org.
Chem. 1993, 58, 5683; (i) McCarthy, J. R.; Matthews, D. P.;
Stemerick, D. M.; Huber, E. W.; Bey, P.; Lippert, B. J.;
Snyder, R. D.; Sunkara, P. S. J. Am. Chem. Soc. 1991, 113, 7539.
6. (a) Hara, S.; Yoshida, M.; Fukuhara, T.; Yoneda, N. Chem.
Commun. 1998, 965; (b) Hara, S.; Yamamoto, K.; Yoshida,
M.; Fukuhara, Y.; Yoneda, N. Tetrahedron Lett. 1999, 40,
7815; (c) Hara, S.; Yoshida, M.; Fukuhara, T.; Yoneda, N.
Tetrahedron Lett. 2000, 41, 3887; (d) Yoshida, M.; Nagahara,
D.; Fukuhara, T.; Yoneda, N.; Hara, S. J. Chem. Soc., Perkin
Trans. 1 2001, 2283; (e) Yoshida, M.; Ota, D.; Fukuhara, T.;
Yoneda, N.; Hara, S. J. Chem. Soc., Perkin Trans. 1 2002,
384; (f) Yoshida, M.; Yoshikawa, S.; Fukuhara, T.; Yoneda,
N.; Hara, S. Tetrahedron 2001, 57, 7143; (g) Yoshida, M.;
Kawakami, K.; Hara, S. Synthesis 2004, 2821.
2956, 2925, 2855, 1685, 1635, 1466, 1137, 969, 850, 722;
[HR EIMS Calcd for C18H33F (M): 268.2566. Found: M+,
268.2561].
4.35. (1Z,3E)-1-Fluoro-1-phenyl-1,3-octadiene (17b)
Prepared from 3b as described for 17a in 72% yield
[(1Z,3E)/(1E,3E)>99:1]. Oil, dH (CDCl3) 0.92 (3H, t,
J 7.1 Hz, 8-H), 1.30–1.46 (4H, m), 2.17 (2H, dt, J 7.1,
7.1 Hz, 5-H), 5.83 (1H, dt, J 7.1, 15.3 Hz, 4-H), 6.05 [1H,
3
dd, J 10.7, JH–F(olefin) 35.6 Hz, 2-H], 6.48 (1H, dd, J 10.7,
15.3 Hz, 3-H), 7.27–7.55 (5H, m, Ph); dF (CDCl3)
3
ꢁ121.19 [1F, d, JH–F(olefin) 35.6 Hz]; dC (CDCl3) 13.9,
2
22.3, 31.4, 32.8, 106.7 (d, JC–F 14.1 Hz, 2-C), 122.1 (d,
3
3JC–F 5.8 Hz, 3-C), 123.7 (2C, d, JC–F 7.4 Hz, ortho),
128.4 (2C), 128.5, 132.4 (d, JC–F 27.2 Hz, ipso), 135.7 (d,
2
1
4JC–F 3.3 Hz, 4-C), 155.1 (d, JC–F 251.9 Hz, 1-C);
n (neat)/cmꢁ1 3036, 2957, 2927, 2858, 1653, 1627, 1599,
1495, 1448, 1322, 1281, 994, 969, 761, 688; [HR EIMS
Calcd for C14H17F (M): 204.1314. Found: M+ 204.1313].
Acknowledgements
Financial support was partially provided by Forum on Iodine
Utilization (FIU).
7. (a) Ochiai, M.; Oshima, K.; Masaki, Y. Chem. Lett. 1994, 871;
(b) Ochiai, M.; Kitagawa, Y.; Toyonari, M.; Uemura, K.;
Oshima, K.; Shiro, M. J. Org. Chem. 1997, 62, 8001.
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