Stereoselective synthesis of 2-iodo-1-perfluoroalkyl-2(Z)-alkenes and E or Z-4-perfluoroalkylmethyl-4-en-2-ynol via Na2S2O4-promoted radical addition reaction of perfluoroalkyl iodides with allenes and the palladium-catalyzed kinetic resolution with Sonogashira coupling reaction

Article abstract of DOI:10.1016/j.tet.2008.04.057

A Na₂S₂O₄-promoted radical addition reaction of perfluoroalkyl iodides with allenes has been studied in which a Z/E mixture of 2-iodo-1-perfluoroalkyl-2-alkenes 3 were afforded in 52-69% yields. A kinetic resolution using Sonogashira coupling reaction in MeCN using Et₂NH as the base was developed to synthesize the 2-iodo-1-perfluoroalkyl-2(Z)-alkenes (Z-3) and E-4-perfluoroalkylmethylalk-4-en-2-ynols (E-5) stereoselectively. A complete Sonogashira coupling procedure in Et₂NH at 40 °C was also developed affording a mixture of E and Z-4-perfluoroalkylmethyl-4-en-2-ynols (E-5 and Z-5), which may be easily separated by chromatography on silica gel.

Full text of DOI:10.1016/j.tet.2008.04.057

Tetrahedron 64 (2008) 6500–6509
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Stereoselective synthesis of 2-iodo-1-perfluoroalkyl-2(Z)-alkenes and
E or Z-4-perfluoroalkylmethyl-4-en-2-ynol via Na2S2O4-promoted
radical addition reaction of perfluoroalkyl iodides with allenes and the
palladium-catalyzed kinetic resolution with Sonogashira coupling reaction
*
Zhichao Ma, Shengming Ma
Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A Na2S2O4-promoted radical addition reaction of perfluoroalkyl iodides with allenes has been studied in
which a Z/E mixture of 2-iodo-1-perfluoroalkyl-2-alkenes 3 were afforded in 52–69% yields. A kinetic
resolution using Sonogashira coupling reaction in MeCN using Et2NH as the base was developed to
synthesize the 2-iodo-1-perfluoroalkyl-2(Z)-alkenes (Z-3) and E-4-perfluoroalkylmethylalk-4-en-2-ynols
(E-5) stereoselectively. A complete Sonogashira coupling procedure in Et2NH at 40 ꢀC was also developed
affording a mixture of E and Z-4-perfluoroalkylmethyl-4-en-2-ynols (E-5 and Z-5), which may be easily
separated by chromatography on silica gel.
Received 11 February 2008
Received in revised form 13 April 2008
Accepted 15 April 2008
Available online 18 April 2008
Keywords:
Radical addition
Allenes
Ó 2008 Elsevier Ltd. All rights reserved.
Perfluoroalkyl iodides
Kinetic resolution
Sonogashira coupling
1. Introduction
our group, we had developed a Na2S2O4-promoted radical addition
reaction, which gave the radical addition products in the E/Z ratio of
Organofluorine compounds have been receiving significant at-
tention in medicinal chemistry, agrochemistry, and material sci-
ence.1 Because of the small size and strong electronegativity, when
the fluorine atom is introduced to the molecules, the physico-
chemical properties and biological activities would change dra-
matically.1a,b,2 Consequently, many efforts have been directed
toward the development of methodologies for the preparation of
organofluorine compounds. One of the most practical and conve-
nient routes for the introduction of F-containing group to organic
skeleton is the radical addition reaction of perfluoroalkyl iodides to
unsaturated carbon–carbon multiple bonds. Although the addition
reactions of perfluoroalkyl halides to alkenes and alkynes have
been well explored,3–5 the radical addition of perfluoroalkyl iodides
of allenes using radical addition conditions has not been well
established.6 In addition, the known protocols lack the stereo-
selectivity usually required by modern synthetic organic chemistry.
For instance, Ogawa and co-workers had developed a procedure of
radical perfluoroalkylation of allenes initiated by light, in which the
E/Z ratio of addition products was ranged from 63:37 to 20:80.6a,b In
36:64–27:73.7 Very recently, Liu and his co-workers also reported
a Na2S2O4-promoted radical iodoperfluoroalkylation reaction of
1,2-propadienyl diphenyl phosphine oxide, 1,2-propadienyl diethyl
phosphonate, and ethyl 2,3-butadienoate.6c To find a method for
the stereoselective synthesis of 2-iodo-1-perfluoroalkylalkene, the
sequential Na2S2O4-promoted radical addition reaction and the
subsequent palladium-catalyzed Sonogashira coupling reaction
have been investigated in our group. In this paper, we wish to re-
port the details of these studies.
2. Results and discussion
After optimizing the conditions, we used a combination of
Na2S2O4 and NaHCO3 as the radical initiator and 1,4-dioxane/H2O
(3:1) as the solvent to study the scope of the radical addition re-
actions between perfluoroalkyl iodides and various allenes.7 The
results were summarized in Table 1. It can be concluded that allenes
containing n-C4F9I, n-C6F13I, c-C6H11 group can readily react with
either n-C4F9, n-C6F13, or Cl(CF2)4I to smoothly generate the radical
addition products, i.e., 2-iodo-1-perfluoroalkyl-2-alkenes 3 in 52–
69% yields with E/Z ratios ranging from 27:63 to 36:64. The for-
mation of the regioisomers 30 is ꢁ3%.
* Corresponding author. Fax: þ86 21 64167510.
E-mail address: masm@mail.sioc.ac.cn (S. Ma).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.04.057

Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
6501
Table 1
this table, it should be noted that the coupling products E-5 may be
produced smoothly while the isolated yield of Z-5 was less than 4%
(entries 1–5, 7–11, and 13, Table 2). When Rf contains a chlorine
atom, i.e., Cl(CF2)4, the ratio of E-5 and Z-5 was not very good (entry
6, Table 2). When R1¼Bn, the reaction should be carried out at
Na2S2O4/NaHCO3-initiated radical addition of perfluoroalkyl iodides with different
allenesa
I
R
R
I
Na2S2O4/NaHCO3
+ RfI
+
R
1,4-dioxane/H2O = 3/1
40~45 °C, 3 h
a higher temperature (entries 1 and 12, Table 2); When Rf is n-C6F13
,
Rf
Rf
1
3
2
3'
0.7 equiv of propargyl alcohol was used to achieve the resolution
(entries 2, 5, 8, and 11, Table 2). In addition, 2-methyl-3-butyn-2-ol
may also be used for this kinetic resolution procedure (entries 12
and 13, Table 2).
Entry
R
Rf
Yield of
E/Z ratio
of 3c
Yield of
30 (%)
3b (%)
b
1
2
3
4
5
6
7
8
Bn (1a)
Bn (1a)
n-C4F9 (2a)
n-C6F13 (2b)
n-C4F9 (2a)
n-C4F9 (2a)
n-C6F13(2b)
Cl(CF2)4 (2c)
n-C4F9 (2a)
n-C6F13 (2b)
n-C4F9 (2a)
n-C4F9 (2a)
n-C6F13 (2b)
64 (3a)
55 (3b)
52 (3c)
50 (3d)
55 (3e)
60 (3f)
66 (3g)
61 (3h)
52 (3i)
61 (3j)
63 (3k)
36:64
37:63
33:67
30:70
30:70
27:73
30:70
28:72
28:72
31:69
30:70
1 (3a0)
1 (3b0)
2 (3c0)
2 (3d0)
2 (3e0)
3 (3f0)
3 (3g0)
3 (3h0)
2 (3i0)
1 (3j0)
1 (3k0)
Subsequently, we tried to synthesize both Z-5 and E-5 from the
radical addition products 3. Based on the previous study of Sono-
gashira coupling reaction of 3 with propargyl alcohol, we further
optimized the reaction conditions. Using 1.2 equiv of K2CO3 or
Et2NH the reaction in CH3CN only gave a poor combined yield of the
coupling product 5ga (entries 1–3, Table 3). The reaction in Et3N
only afforded E-5 and Z-5 in 38% combined yield (entry 4, Table 3).
However, it’s fortunate to observe that when secondary amines
such as (i-Pr)2NH, piperidine, or Et2NH is used as the solvent, the
reaction is much more effective (entries 5–7, Table 3). After
studying the effect of the amounts of the catalysts and the reaction
temperature, finally we defined 3 mol % Pd(PPh3)2Cl2/CuI in Et2NH
at 40 ꢀC as the standard conditions (entry 10, Table 3). By column
chromatography on silica gel, Z-5 and E-5 can be easily separated,
thus the Z-5 may also be prepared through this Sonogashira cou-
pling reaction.
Some such typical results were summarized in Table 4. All the
reactions underwent smoothly to afford the products in good
yields: even with R1¼Bn, the reaction of 3a and 3b afforded the
products Z/E-5aa and Z/E-5ba in 64% and 61% combined yields
(entries 1 and 2, Table 4). In addition, when 2-methyl-3-butyn-2-ol
was used in this procedure, the reaction also produced the coupling
products Z- or E-5ab, 5gb, 5ib, and 5jb smoothly in good yields
(entries 11–14, Table 4).
n-C4H9 (1b)
n-C5H11 (1c)
n-C5H11 (1c)
n-C7H15 (1d)
n-C7H15 (1d)
n-C7H15 (1d)
n-C8H17 (1e)
c-C6H11 (1f)
c-C6H11 (1f)
9
10
11
a
1/2/Na2S2O4/NaHCO3¼1:1.5:1.5:1.5 (molar ratio).
b
Isolated yield. The E and Z isomers could not be separated by chromatography on
silica gel.
c
Determined by 1H NMR (400 MHz) analysis.
Because of the difficulty in separating the E and Z isomers,
we tried to conduct a kinetic resolution via the Sonogashira
coupling reaction8 of the Z/E mixture with propargyl alcohol. In
fact, it was found that the E-isomer is more reactive to afford
the corresponding coupling product E-5 while the Z-3 remained.
Due to the big difference of polarity of these two classes of
compounds, they can be easily separated via chromatography on
silica gel.
After some optimization, we defined the standard reaction
conditions as conducting the reaction with a molar ratio of 3/4/
Et2NH/Pd(PPh3)2Cl2/CuI¼1:0.6:0.6:0.035:0.035 in CH3CN. A num-
ber of 2-iodo-1-perfluoroalkyl-2-alkenes were examined with
monitoring by GC or NMR. These results were summarized in Table
2. Pure iodides Z-3 were formed and isolated in good yields. From
In conclusion, we have developed a mild, good-yielding, and
stereoselective method for the synthesis of Z-1-perfluoroalkyl-2-
iodo-2-alkenes and E/Z-4-perfluoroalkylmethylalk-4-en-2-ynols.
From the readily available allenes9 and perfluoroalkyl iodides,
Table 2
Kinetic resolution of different 2-iodo-1-perfluoroalkyl-2-alkenes by the Pd(0)-catalyzed Sonogashira coupling reaction with propargylic alcoholsa
R2 R2
OH
R2 R2
OH
R1
I
R2
R2
HO
R1
I
R1
Pd(PPh3)2Cl2/CuI
Et2NH, CH3CN
+
+
+
Rf
Rf
R1
Rf
Rf
4a R2 = H
3
Z-3
E-5
Z-5
4b R2 = Me
Entry
R1
Rf
R2
Temp (ꢀC)/time (min)
Yield of Z-3b (%)
Yield of E-5b (%)
Yield of Z-5b (%)
1
2
3
4
5
6
Bn
Bn
n-C4F9 (3a)
n-C6F13 (3b)
n-C4F9 (3c)
n-C4F9 (3d)
n-C6F13 (3e)
Cl(CF2)4 (3f)
n-C4F9 (3g)
n-C6F13 (3h)
n-C4F9 (3i)
n-C4F9 (3j)
n-C6F13 (3k)
n-C4F9 (3a)
n-C4F9 (3g)
H
13/30
0/100
0/75
0/60
0/120
0/60
43 (Z-3a)
42 (Z-3b)
49 (Z-3c)
48 (Z-3d)
57 (Z-3e)
68 (Z-3f)
58 (Z-3g)
73 (Z-3h)
61 (Z-3i)
61 (Z-3j)
53 (Z-3k)
35 (Z-3a)
30 (Z-3g)
34 (E-5aa)
26 (E-5ba)
26 (E-5ca)
23 (E-5da)
29 (E-5ea)
23 (E-5fa)
22 (E-5ga)
19 (E-5ha)
23 (E-5ia)
24 (E-5ja)
25 (E-5ka)
33 (E-5ab)
29 (E-5gb)
4 (Z-5aa)
2 (Z-5ba)
3 (Z-5ca)
1 (Z-5da)
2 (Z-5ea)
7 (Z-5fa)
1 (Z-5ga)
d(Z-5ha)
2 (Z-5ia)
2 (Z-5ja)
3 (Z-5ka)
7 (Z-5ab)
4 (Z-5gb)
Hc
H
n-C4H9
n-C5H11
n-C5H11
n-C7H15
n-C7H15
n-C7H15
n-C8H17
c-C6H11
c-C6H11
Bn
H
Hc
H
7
H
0/60
8d
9
Hc
H
0/150
0/120
0/60
0/150
10/120
11/80
10
11
12
13
H
Hc
Mec
Mec
n-C7H15
a
3/4/Et2NH/Pd(PPh3)2Cl2/CuI¼1:0.6:0.6:0.035:0.035 (molar ratio).
Isolated yield.
b
c
3/4/Et2NH/Pd(PPh3)2Cl2/CuI¼1:0.7:0.7:0.035:0.035 (molar ratio).
d
Z/E¼97:3, which was determined by 1H NMR (400 MHz) analysis.

6502
Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
Table 3
Optimization of the reaction conditions for the complete Sonogashira coupling reaction of 2-iodo-1-perfluoroalkyl-2-alkenes with propargyl alcohol
OH
n-C7H15
(CF2)3CF3
OH
cat. Pd(PPh3)2Cl2/CuI
x mol%
Z-5ga
n-C7H15
I
+
HO
base, solvent,
t °C
(CF2)3CF3
3g
4a
(CF2)3CF3
n-C7H15
E-5ga
Entry
Base
Solvent
4a (equiv)
Temp (ꢀC)
Time (h)
Cat. (x mol %)
Isolated yield
Z-5ga (%)
E-5ga (%)
a
1
2
3
4
5
6
7
8
K2CO3
CH3CN
CH3CN
CH3CN
1.2
1.2
2
60
60
60
60
60
60
60
60
60
40
40
20
24
47.5
11
28
9.5
10
10
10.5
22
11.5
17.5
10
3
3
3
3
3
3
5
3
1
3
1
3
12
26
29
23
48
48
49
51
46
53
46
45
4
13
14
15
16
20
19
18
19
21
23
16
Et2NHa
Et2NHb
Et3N
Hexahydropyridine
(i-Pr)2NH
Et2NH
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
Et2NH
Et2NH
9
10
11
12
Et2NH
Et2NH
Et2NH
a
1.2 equiv of the base was used.
2 equiv of the base was used.
b
a mixture of E and Z isomers of 1-perfluoroalkyl-2-iodo-2-alkenes
was formed by radical addition reaction, which may be kinetically
resolved to afford Z-1-perfluoroalkyl-2-iodo-2-alkenes and E-4-
perfluoroalkylmethylalk-4-en-2-ynols via the Sonogashira cou-
pling in MeCN using Et2NH as the base. In addition, a complete
Sonogashira coupling in Et2NH at 40 ꢀC was realized to produce
both E- and Z-4-perfluoroalkylmethylalk-4-en-2-ynols, which can
be separated by chromatography on silica gel. Further studies in
this area are being conducted in our laboratory.
3. Experimental section
3.1. The Na2S2O4-promoted radical addition reaction of RfI
with allenes1
3.1.1. 3-Iodo-5,5,6,6,7,7,8,8,8-nonafluoro-1-phenyl-2-octene (3a)
Typical procedure. To
3.01 mmol), NaHCO3 (253.4 mg, 3.02 mmol), and 10 mL of 1,4-di-
a mixture of Na2S2O4 (523.6 mg,
oxane were added 4-phenyl-1,2-butadiene 1a (258.8 mg,
Table 4
Synthesis of various 4-perfluoroalkylmethyl-4-en-2-ynols by Sonogashira coupling reaction of 2-iodo-1-perfluoroalkyl-2-alkenes with propargylic alcoholsa
R2 R2
OH
R2 R2
OH
R1
I
R2
R2
HO
Pd(PPh3)2Cl2 /CuI (3 mol%)
Et2NH, 40 °C
+
R1
Rf
+
Rf
R1
Rf
3
4a R2 = H
4b R2 = Me
Z-5
E-5
Entry
R1
Rf
R2
Isolated yields
Z-5 (%)
E-5 (%)
1
2
3
4
5
6
7
8
Bn
Bn
n-C4F9 (3a)
H
H
H
H
H
H
H
H
H
H
Me
Me
Me
Me
44 (Z-5aa)
40 (Z-5ba)
57 (Z-5ca)
58 (Z-5da)
55 (Z-5ea)
53 (Z-5ga)
51 (Z-5ha)
54 (Z-5ia)
68 (Z-5ja)
60 (Z-5ka)
53 (Z-5ab)
58 (Z-5gb)
58 (Z-5ib)
59 (Z-5jb)
20 (E-5aa)
21 (E-5ba)
24 (E-5ca)
24 (E-5da)
24 (E-5ea)
21 (E-5ga)
34 (E-5ha)
24 (E-5ia)
25 (E-5ja)
26 (E-5ka)
27 (E-5ab)
24 (E-5gb)
19 (E-5ib)
28 (E-5jb)
n-C6F13 (3b)
n-C4F9 (3c)
n-C4F9 (3d)
n-C6F13 (3e)
n-C4F9 (3g)
n-C6F13 (3h)
n-C4F9 (3i)
n-C4F9 (3j)
n-C6F13 (3k)
n-C4F9 (3a)
n-C4F9 (3g)
n-C4F9 (3i)
n-C4F9 (3j)
n-C4H9
n-C5H11
n-C5H11
n-C7H15
n-C7H15
n-C8H17
c-C6H11
c-C6H11
Bn
9
10
11
12
13
14b
n-C7H15
n-C8H17
c-C6H11
a
3/4¼1:1.2 (molar ratio). Unless otherwise stated, the reaction was carried out at 40 ꢀC.
b
The reaction was carried out at 60 ꢀC.

Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
6503
1.99 mmol), 2a (1.0482 g, 3.03 mmol), 2 mL of 1,4-dioxane, and
4 mL of H2O sequentially. The mixture was stirred at 40–45 ꢀC for
9 h as monitored by TLC, quenched with 10 mL of brine, extracted
with diethyl ether (40 mLꢂ3), and dried over anhydrous Na2SO4.
Evaporation and column chromatography on silica gel (eluent:
petroleum ether) afforded a Z/E mixture of 3a (612.7 mg, 65%, Z/
isomer, t, J¼6.8 Hz, 0.73H)], 3.39 (t, JH–F¼17.6 Hz, 2H), [2.17 (Z-iso-
mer, q, J¼7.1 Hz, 1.47H), 2.04 (E-isomer, q, J¼7.2 Hz, 0.53H)], 1.49–
1.36 (m, 2H), 1.36–1.19 (m 8H), 0.94–0.79 (m, 3H). The E/Z mixture
was submitted to the kinetic resolution step without further
characterization.
E¼36:64). 1H NMR (400 MHz, CDCl3):
d
7.37–7.28 (m, 2H), 7.28–7.20
3.1.7. 6-Iodo-1,1,1,2,2,3,3,4,4-nonafluoro-6-tetradecene (3g)
(m, 2H), 7.20–7.14 (m, 1H), [6.84 (E-isomer, t, J¼7.6 Hz, 0.36H); 6.04
(Z-isomer, t, J¼6.6 Hz, 0.64H)], 3.61–3.37 (m, 4H). The E/Z mixture
was submitted to the kinetic resolution step without further
characterization.
The reaction of 1d (70.0 mg, 0.51 mmol), 2a (265.9 mg,
0.77 mmol), Na2S2O4 (131.1 mg, 0.75 mmol), and NaHCO3 (63.0 mg,
0.75 mmol) in 4 mL of mixed solvent of 1,4-dioxane and H2O
(3:1 v/v) for 3 h afforded 3g (169.8 mg, 69%, E/Z¼30:70). 1H NMR
(400 MHz, CDCl3):
d
[6.65 (E-isomer, t, J¼7.6 Hz, 0.30H), 5.83
3.1.2. 3-Iodo-1-phenyl-5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-2-
decene (3b)
(Z-isomer, t, J¼6.8 Hz, 0.70H), 3.40 (t, JH–F¼17.6 Hz, 2H), [2.17 (Z-
isomer, q, J¼7.2 Hz, 1.40H), 2.04 (E-isomer, q, J¼7.3 Hz, 0.60H)],
1.49–1.36 (m, 2H), 1.36–1.20 (m, 8H), 0.94–0.82 (m, 3H). The E/Z
mixture was submitted to the kinetic resolution step without fur-
ther characterization.
The reaction of 1a (262.0 mg, 2.02 mmol), 2b (1.3529 g,
3.03 mmol), Na2S2O4 (525.0 mg, 3.02 mmol), and NaHCO3
(255.2 mg, 3.04 mmol) in 16 mL of mixed solvent of 1,4-dioxane
and H2O (3:1 v/v) for 4 h afforded 3b (651.4 mg, 56%, E/Z¼37:63). 1H
NMR (400 MHz, CDCl3):
d
7.35–7.28 (m, 2H), 7.28–7.18 (m, 2H),
3.1.8. 8-Iodo-1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-
hexadecene (3h)
7.18–7.13 (m, 1H), [6.83 (E-isomer, t, J¼7.6 Hz, 0.37H); 6.03 (Z-iso-
mer, t, J¼6.8 Hz, 0.63H)], 3.60–3.36 (m, 4H). The E/Z mixture was
submitted to the kinetic resolution step without further
characterization.
The reaction of 1d (415.6 mg, 3.01 mmol), 2b (2.0754 g,
4.65 mmol), Na2S2O4 (786.7 mg, 4.52 mmol), and NaHCO3
(376.8 mg, 4.49 mmol) in 12 mL of mixed solvent of 1,4-dioxane
and H2O (3:1 v/v) for 2.5 h afforded 3h (1.1276 g, 64%, E/Z¼28:72).
3.1.3. 6-Iodo-8,8,9,9,10,10,11,11,11-nonafluoro-5-undecene (3c)
The reaction of 1b (95.4 mg, 0.99 mmol), 2a (515.4 mg,
1.49 mmol), Na2S2O4 (261.4 mg,1.50 mmol), and NaHCO3 (126.0 mg,
1.50 mmol) in 8 mL of mixed solvent of 1,4-dioxane and H2O (3:1
v/v) for 3 h afforded 3c (238.2 mg, 54%, E/Z¼33:67). 1H NMR
1H NMR (400 MHz, CDCl3):
d
[6.65 (E-isomer, t, J¼7.8 Hz, 0.28H),
5.83 (Z-isomer, t, J¼6.8 Hz, 0.72H)], 3.39 (t, JH–F¼17.4 Hz, 2H), [2.17
(Z-isomer, q, J¼7.6 Hz, 1.45H), 2.04 (E-isomer, q, J¼7.2 Hz, 0.55H)],
1.49–1.36 (m, 2H), 1.36–1.18 (m 8H), 0.93–0.82 (m, 3H). The E/Z
mixture was submitted to the kinetic resolution step without fur-
ther characterization.
(400 MHz, CDCl3):
d
[6.65 (E-isomer, t, J¼7.8 Hz, 0.33H), 5.82
(Z-isomer, t, J¼6.8 Hz, 0.67H)], 3.39 (t, JH–F¼17.2 Hz, 2H), [2.18
(Z-isomer, q, J¼7.2 Hz, 1.34H), 2.04 (E-isomer, q, J¼7.2 Hz, 0.66H)],
1.48–1.28 (m, 4H), 0.95–0.84 (m, 3H). The E/Z mixture was submitted
to the kinetic resolution step without further characterization.
3.1.9. 6-Iodo-1,1,1,2,2,3,3,4,4-nonafluoro-6-pentadecene (3i)
The reaction of 1e (152.8 mg, 1.01 mmol), 2a (519.0 mg,
1.50 mmol), Na2S2O4 (262.6 mg, 1.51 mmol), and NaHCO3
(125.7 mg, 1.50 mmol) in 8 mL of mixed solvent of 1,4-dioxane and
H2O (3:1 v/v) for 3 h afforded 3i (269.2 mg, 54%, E/Z¼28:72). 1H
3.1.4. 6-Iodo-1,1,1,2,2,3,3,4,4-nonafluoro-6-dodecene (3d)
The reaction of 1c (111.0 mg, 1.01 mmol), 2a (525.3 mg,
1.52 mmol), Na2S2O4 (261.6 mg, 1.50 mmol), and NaHCO3
(124.9 mg, 1.49 mmol) in 8 mL of mixed solvent of 1,4-dioxane and
H2O (3:1 v/v) for 3 h afforded 3d (237.4 mg, 52%, E/Z¼30:70). 1H
NMR (400 MHz, CDCl3):
d
[6.65 (E-isomer, t, J¼7.6 Hz, 0.28H), 5.82
(Z-isomer, t, J¼6.8 Hz, 0.72H), 3.39 (t, JH–F¼17.6 Hz, 2H), [2.17 (Z-
isomer, q, J¼7.6 Hz, 1.44H), 2.03 (E-isomer, q, J¼7.6 Hz, 0.56H)],
1.48–1.36 (m, 2H), 1.36–1.20 (m, 10H), 0.88 (t, J¼6.8 Hz, 3H). The E/Z
mixture was submitted to the kinetic resolution step without fur-
ther characterization.
NMR (400 MHz, CDCl3):
d
[6.66 (E-isomer, t, J¼7.6 Hz, 0.30H), 5.84
(Z-isomer, t, J¼6.6 Hz, 0.70H)], 3.40 (t, JH–F¼17.6 Hz, 2H), [2.18 (Z-
isomer, q, J¼7.1 Hz, 1.40H), 2.05 (E-isomer, q, J¼7.2 Hz, 0.60H)],
1.50–1.37 (m, 2H), 1.37–1.23 (m, 4H), 0.97–0.83 (m, 3H). The E/Z
mixture was submitted to the kinetic resolution step without fur-
ther characterization.
3.1.10. 1-Cyclohexyl-2-iodo-4,4,5,5,6,6,7,7,7-nonafluoro-1-
heptene (3j)
The reaction of 1f (120.1 mg, 0.98 mmol), 2a (522.2 mg,
1.51 mmol), Na2S2O4 (262.2 mg, 1.51 mmol), and NaHCO3
(128.1 mg, 1.53 mmol) in 8 mL of mixed solvent of 1,4-dioxane and
H2O (3:1 v/v) for 3 h afforded 3j (287.0 mg, 62%, E/Z¼31:69). 1H
3.1.5. 7-Iodo-9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-7-
tetradecene (3e)
The reaction of 1c (223.2 mg, 2.03 mmol), 2b (1.3711 g,
3.07 mmol), Na2S2O4 (520.5 mg, 2.99 mmol), and NaHCO3
(253.0 mg, 3.01 mmol) in 8 mL of mixed solvent of 1,4-dioxane and
H2O (3:1 v/v) for 3 h afforded 3e (643.3 mg, 57%, E/Z¼30:70). 1H
NMR (400 MHz, CDCl3):
d
[6.49 (E-isomer, d, J¼10.0 Hz, 0.31H), 5.63
(Z-isomer, d, J¼8.4 Hz, 0.69H)], [3.41 (E-isomer, t, J¼17.8 Hz), 3.36
(Z-isomer, t, J¼17.6 Hz), 2H], [2.32–2.20 (Z-isomer, m, 0.69H), 2.16–
2.03 (E-isomer, m, 0.31H)],1.80–1.58 (m, 5H),1.40–1.03 (m, 5H). The
E/Z mixture was submitted to the next step without further
characterization.
NMR (400 MHz, CDCl3):
d
[6.66 (E-isomer, t, J¼7.4 Hz, 0.30H), 5.83
(Z-isomer, t, J¼6.8 Hz, 0.70H)], 3.40 (t, JH–F¼17.4 Hz, 2H), [2.17 (Z-
isomer, q, J¼7.2 Hz, 1.40H), 2.04 (E-isomer, q, J¼7.6 Hz, 0.60H)],
1.50–1.37 (m, 2H), 1.37–1.22 (m, 4H), 0.96–0.82 (m, 3H). The E/Z
mixture was submitted to the kinetic resolution step without fur-
ther characterization.
3.1.11. 1-Cyclohexyl-2-iodo-4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-
nonene (3k)
The reaction of 1f (121.0 mg, 0.99 mmol), 2b (665.4 mg,
1.49 mmol), Na2S2O4 (260.6 mg, 1.50 mmol), and NaHCO3
(128.1 mg, 1.53 mmol) in 8 mL of mixed solvent of 1,4-dioxane and
H2O (3:1 v/v) for 3 h afforded 3k (360.1 mg, 64%, E/Z¼30:70). 1H
3.1.6. 1-Chloro-6-iodo-1,1,2,2,3,3,4,4-octafluoro-6-tetradecene (3f)
The reaction of 1d (68.7 mg, 0.50 mmol), 2c (280.0 mg,
0.77 mmol), Na2S2O4 (130.4 mg, 0.75 mmol), and NaHCO3 (64.4 mg,
0.77 mmol) in 4 mL of mixed solvent of 1,4-dioxane and H2O (3:1
v/v) for 3 h afforded 3f (156.3 mg, 63%, E/Z¼27:73). 1H NMR
NMR (400 MHz, CDCl3):
d
[6.49 (E-isomer, d, J¼10.0 Hz, 0.28H), 5.63
(Z-isomer, d, J¼8.4 Hz, 0.72H)], [3.39 (E-isomer, t, J¼17.8 Hz), 3.36
(Z-isomer, t, J¼17.4 Hz), 2H], [2.30–2.19 (Z-isomer, m, 0.69H), 2.17–
2.04 (E-isomer, m, 0.30H)], 1.82–1.59 (m, 5H), 1.40–1.04 (m, 5H).
(400 MHz, CDCl3):
d
[6.65 (E-isomer, t, J¼7.8 Hz, 0.27H), 5.83 (Z-

6504
Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
The E/Z mixture was submitted to the kinetic resolution step
without further characterization.
1438, 1358, 1318, 1237, 1208, 1183, 1138, 1101, 1067, 1015; EA calcd
for C19H13F13O: C, 45.25; H, 2.60. Found: C, 45.22; H, 2.68.
3.2.3. Synthesis of 6-iodo-8,8,9,9,10,10,11,11,11-nonafluoro-5(Z)-
undecene (Z-3c) and 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-
non-4(E) or (Z)-en-2-ynol (5ca)
3.2. The kinetic resolution of 3 via Sonogashira coupling
reaction
The reaction of 3c (132.8 mg, 0.30 mmol, E/Z¼33:67), 4a
(10.2 mg, 0.18 mmol), Pd(PPh3)2Cl2 (7.4 mg, 1.06ꢂ10ꢃ2 mmol,
3.5 mol %), CuI (2.0 mg, 1.05ꢂ10ꢃ2 mmol, 3.5 mol %), and Et2NH
(13.1 mg, 0.18 mmol) in 0.6 mL of CH3CN for 75 min afforded Z-3c
(65.6 mg, 49%), Z-5ca (3.3 mg, 3%), and E-5ca (29.2 mg, 26%).
3.2.1. Synthesis of 3-iodo-5,5,6,6,7,7,8,8,8-nonafluoro-1-phenyl-
2(Z)-octene (Z-3a) and 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-
6-phenylhex-4(E) or (Z)-en-2-ynol (5aa)
Typical procedure. To a Schlenk tube containing a mixture of
Pd(PPh3)2Cl2 (6.2 mg, 8.84ꢂ10ꢃ3 mmol, 3.5 mol %) and CuI (1.7 mg,
9.47ꢂ10ꢃ3 mmol. 3.8 mol %) was added 3a (118.7 mg, 0.25 mmol, E/
Z¼36:64) under a nitrogen atmosphere. Then a solution of Et2NH
(11.1 mg, 0.15 mmol) and 4a (8.5 mg, 0.15 mmol) in 0.5 mL of
CH3CN was added. The resulting mixture was stirred at room
temperature for 30 min as monitored by GC, quenched with 10 mL
of brine, extracted with diethyl ether (25 mLꢂ3), and dried over
anhydrous Na2SO4. Evaporation and column chromatography on
silica gel afforded Z-3a (eluent: petroleum ether, 50.9 mg, 43%), Z-
5aa (eluent: petroleum ether/ethyl acetate¼10:1, 4.0 mg, 4%), and
E-5aa (eluent: petroleum ether/ethyl acetate¼10:1, 33.9 mg, 34%).
Compound Z-3c. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.83 (t,
J¼6.8 Hz, 1H), 3.39 (t, JH–F¼17.6 Hz, 2H), 2.18 (q, J¼6.8 Hz, 2H), 1.48–
1.29 (m, 4H), 0.92 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d
145.5, 86.0, 45.1 (t, JC–F¼20.8 Hz), 36.8, 30.0, 22.2, 13.9; MS (EI,
70 eV) m/z (%): 442 (Mþ, 91.59), 55 (100); IR (neat, cmꢃ1): 2962,
2934, 2863, 1638, 1467, 1425, 1346, 1236, 1135, 1098, 1023; HRMS
calcd for C11H12F9I (Mþ): 441.9840, found: 441.9836.
Compound Z-5ca was fully characterized using the sample
prepared in Section 3.3.3.
Compound E-5ca. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.25 (t,
J¼7.6 Hz, 1H), 4.37 (s, J¼4.8 Hz, 2H), 2.94 (t, JH–F¼18.0 Hz, 2H), 2.11
Compound Z-3a. Liquid; 1H NMR (400 MHz, CDCl3):
d 7.33 (t,
(q, J¼7.2 Hz, 2H), 1.80 (br s, 1H), 1.44–1.27 (m, 4H), 0.90 (t, J¼7.2 Hz,
J¼7.8 Hz, 2H), 7.28–7.17 (m, 3H), 6.04 (t, J¼6.6 Hz, 1H), 3.56 (d,
3H); 13C NMR (CDCl3, 100 MHz):
d
146.5, 110.0 (t, JC–F¼3.1 Hz), 86.7,
J¼6.4 Hz, 2H), 3.46 (t, JH–F¼17.6 Hz, 2H); 13C NMR (CDCl3,100 MHz):
84.8, 51.5, 32.1 (t, JC–F¼22.1 Hz), 30.8, 28.6, 22.2, 13.8; MS (EI, 70 eV)
m/z (%): 370 (Mþ, 83.81), 313 (100); IR (neat, cmꢃ1): 3333, 2962,
2932, 2864, 2223, 1628, 1461, 1350, 1236, 1135, 1098, 1024; HRMS
calcd for C14H15F9ONa (MþNaþ): 393.0871, found: 393.0873.
d
143.9, 137.9, 128.7, 128.4, 126.7, 87.4, 45.2 (t, JC–F¼21.7 Hz), 43.4;
MS (EI, 70 eV) m/z (%): 476 (Mþ, 4.37), 91 (100); IR (neat, cmꢃ1):
1603, 1234, 1133; EA calcd for C14H10F9I: C, 35.32; H, 2.12. Found: C,
35.13; H, 2.11.
Compound Z-5aa was fully characterized using the sample
prepared in Section 3.3.1.
3.2.4. Synthesis of 6-iodo-1,1,1,2,2,3,3,4,4-nonafluoro-6(Z)-
dodecene (Z-3d) and 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-
dec-4(E) or (Z)-en-2-ynol (5da)
Compound E-5aa. Liquid; 1H NMR (400 MHz, CDCl3):
d 7.33 (t,
J¼7.4 Hz, 2H), 7.25 (t, J¼7.8 Hz, 1H), 7.17 (d, J¼7.2 Hz, 2H), 6.43
(t, J¼7.2 Hz, 1H), 4.39 (s, 2H), 3.50 (d, J¼7.6 Hz, 2H), 3.08 (t,
JH–F¼18.4 Hz, 2H), 1.65 (br s, 1H); 13C NMR (CDCl3, 100 MHz):
The reaction of 3d (114.5 mg, 0.25 mmol, E/Z¼30:70), 4a
(8.3 mg, 0.15 mmol), Pd(PPh3)2Cl2 (6.2 mg, 8.84ꢂ10ꢃ3 mmol,
3.5 mol %), CuI (1.8 mg, 9.47ꢂ10ꢃ3 mmol, 3.8 mol %), and Et2NH
(11.1 mg, 0.15 mmol) in 0.5 mL of CH3CN for 60 min afforded Z-3d
(54.8 mg, 48%), Z-5da (0.5 mg, 2%), and E-5da (21.7 mg, 23%).
d
144.1, 138.3, 128.8, 128.4, 126.6, 111.0, 86.3, 85.6, 51.5, 34.9, 32.3 (t,
JC–F¼22.2 Hz); MS (EI, 70 eV) m/z (%): 404 (Mþ, 1.68), 153 (100); IR
(neat, cmꢃ1): 3333, 2222, 1234, 1133, 741; EA calcd for C17H13F9O: C,
50.51; H, 3.24. Found: C, 50.20; H, 3.26.
Compound Z-3d. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.84 (t,
J¼7.0 Hz, 1H), 3.40 (t, JH–F¼17.6 Hz, 2H), 2.18 (q, J¼7.1 Hz, 2H), 1.52–
1.40 (m, 2H), 1.40–1.21 (m, 4H), 0.91 (t, J¼6.4 Hz, 3H); 13C NMR
3.2.2. Synthesis of 3-iodo-1-phenyl-5,5,6,6,7,7,8,8,9,9,10,10,10-
tridecafluoro-2(Z)-decene (Z-3b) and 6-phenyl-4-(20,20,30,30,40,
40,50,50, 60,60,70,70,70-tridecafluoro-heptyl)hex-4(E) or (Z)-
en-2-ynol (5ba)
(CDCl3, 100 MHz):
d
145.6, 86.0, 45.1 (t, JC–F¼21.2 Hz), 37.0, 31.2,
27.5, 22.5, 13.9; IR (neat, cmꢃ1): 2931, 1638, 1235, 1134; MS (EI,
70 eV) m/z (%): 456 (Mþ, 53.66), 287 (100); HRMS calcd for
C
12H14F9INa (MþNaþ): 478.9889, found: 478.9881.
The reaction of 3b (173.6 mg, 0.30 mmol, E/Z¼37:63), 4a
(11.9 mg, 0.21 mmol), Pd(PPh3)2Cl2 (7.3 mg, 1.04ꢂ10ꢃ2 mmol,
3.5 mol %), CuI (2.0 mg, 1.05ꢂ10ꢃ2 mmol, 3.5 mol %), and Et2NH
(15.3 mg, 0.21 mmol) in 0.6 mL of CH3CN for 100 min afforded Z-3b
(73.3 mg, 42%), Z-5ba (3.6 mg, 2%), and E-5ba (39.7 mg, 26%).
Compound Z-5da was fully characterized using the sample
prepared in Section 3.3.4.
Compound E-5da. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.26 (t,
J¼7.6 Hz, 1H), 4.38 (s, 2H), 2.95 (t, JH–F¼18.4 Hz, 2H), 2.12 (q,
J¼7.5 Hz, 2H), 1.65 (br s, 1H), 1.49–1.36 (m, 2H), 1.36–1.24 (m, 4H),
Compound Z-3b. Liquid; 1H NMR (400 MHz, CDCl3):
d
7.31 (t,
0.90 (t, J¼7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.6, 110.0,
J¼7.2 Hz, 2H), 7.27–7.14 (m, 3H), 6.02 (t, J¼6.8 Hz, 1H), 3.54 (d,
86.7, 84.8, 51.5, 32.2 (t, JC–F¼22.2 Hz), 31.3, 28.9, 28.3, 22.4, 13.9; IR
(neat, cmꢃ1): 3333, 2932, 2222, 1236, 1134, 1025; MS (EI, 70 eV) m/z
(%): 384 (Mþ, 19.21), 43 (100); EA calcd for C15H17F9O: C, 46.88; H,
4.46. Found: C, 47.15; H, 4.58.
J¼7.2 Hz, 2H), 3.44 (t, JH–F¼17.4 Hz, 2H); 13C NMR (CDCl3, 100 MHz):
d
143.9, 137.9, 128.7, 128.4, 126.6, 87.4, 45.2 (t, JC–F¼20.7 Hz), 43.4;
MS (EI, 70 eV) m/z (%): 576 (Mþ, 15.24), 449 (100); IR (neat, cmꢃ1):
3030, 2923, 1637, 1603, 1496, 1454, 1425, 1351, 1240, 1207, 1145,
1117, 1076, 1029; HRMS calcd for C16H10F13I (Mþ): 575.9620, found:
575.9615.
3.2.5. Synthesis of 7-iodo-9,9,10,10,11,11,12,12,13,13,14,14,14-
tridecafluoro-6(Z)-tetradecene (Z-3e) and 4-(20,20,30,30,40,40,50,50,
60,60,70,70,70-tridecafluoroheptyl)-dec-4(E) or (Z)-en-2-ynol (5ea)
The reaction of 3e (139.7 mg, 0.25 mmol, E/Z¼30:70), 4a
(9.7 mg, 0.173 mmol), Pd(PPh3)2Cl2 (6.2 mg, 8.84ꢂ10ꢃ3 mmol,
3.5 mol %), CuI (1.8 mg, 9.47ꢂ10ꢃ3 mmol, 3.8 mol %), and Et2NH
(12.7 mg, 0.174 mmol) in 0.5 mL of CH3CN for 120 min afforded Z-
3e (79.5 mg, 57%), Z-5ea (2.3 mg, 2%), and E-5ea (35.3 mg, 29%).
Compound Z-5ba was fully characterized using the sample
prepared in Section 3.3.2.
Compound E-5ba. Solid, mp: 42–43 ꢀC (hexane); 1H NMR
(400 MHz, CDCl3):
d
7.31 (t, J¼7.6 Hz, 2H), 7.24 (t, J¼7.4 Hz, 1H), 7.17
(d, J¼7.6 Hz, 2H), 6.42 (t, J¼7.6 Hz, 1H), 4.38 (s, 2H), 3.49 (d,
J¼7.2 Hz, 2H), 3.07 (t, JH–F¼18.4 Hz, 2H), 1.65 (br s, 1H); 13C NMR
(CDCl3, 100 MHz):
d
144.1, 138.3, 128.7, 128.3, 126.6, 111.0, 86.3, 85.6,
Compound Z-3e. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.83 (t,
51.4, 34.9, 32.3 (t, JC–F¼20.9 Hz); MS (EI, 70 eV) m/z (%): 504 (Mþ,
J¼6.6 Hz, 1H), 3.39 (t, JH–F¼17.4 Hz, 2H), 2.17 (q, J¼7.6 Hz, 2H), 1.51–
5.89), 153 (100); IR (KBr, cmꢃ1): 3432, 3034, 2925, 2223, 1636, 1498,
1.39 (m, 2H), 1.39–1.24 (m, 4H), 0.90 (t, J¼6.8 Hz, 3H); 13C NMR

Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
6505
(CDCl3, 100 MHz):
d
145.6, 86.1, 45.2 (t, JC–F¼21.7 Hz), 37.0, 31.2,
3.2.8. Synthesis of 8-iodo-1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-
8(Z)-hexadecene (Z-3h) and 4-(20,20,30,30,40,40,50,50,60,60,70,70,70-
tridecafluoroheptyl)dodec-4(E) or (Z)-en-2-ynol (5ha)
27.5, 22.5, 13.9; MS (EI, 70 eV) m/z (%): 556 (Mþ, 36.75), 55 (100); IR
(neat, cmꢃ1): 2961, 2932, 2861, 1639, 1469, 1426, 1350, 1239, 1207,
1145, 1122, 1099, 703; HRMS calcd for C14H14F13I (Mþ): 555.9933,
found: 555.9943.
The reaction of 3h (146.4 mg, 0.25 mmol, E/Z¼28:72), 4a
(10.0 mg, 0.179 mmol), Pd(PPh3)2Cl2 (6.2 mg, 8.84ꢂ10ꢃ3 mmol,
3.5 mol %), CuI (1.8 mg, 9.47ꢂ10ꢃ3 mmol, 3.8 mol %), and Et2NH
(13.0 mg, 0.178 mmol) in 0.5 mL of CH3CN for 150 min afforded Z-
3h (106.6 mg 73%, Z/E¼97:3), and E-5ha (24.1 mg, 19%).
Compound Z-5ea was fully characterized using the sample
prepared in Section 3.3.5.
Compound E-5ea. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.25 (t,
J¼7.6 Hz, 1H), 4.37 (s, 2H), 2.94 (t, JH–F¼18.4 Hz, 2H), 2.10 (q,
Compound Z-3h. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.83 (t,
J¼7.6 Hz, 2H), 1.89 (br s, 1H), 1.46–1.35 (m, 2H), 1.35–1.22 (m, 4H),
J¼6.8 Hz, 1H), 3.39 (t, JH–F¼17.6 Hz, 2H), 2.17 (q, J¼7.6 Hz, 2H), 1.51–
0.88 (t, J¼6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.5, 110.0,
1.39 (m, 2H), 1.39–1.20 (m, 8H), 0.89 (t, J¼6.8 Hz, 3H); 13C NMR
86.6, 84.8, 51.4, 32.2 (t, JC–F¼21.9 Hz), 31.3, 28.9, 28.3, 22.4, 13.9; MS
(EI, 70 eV) m/z (%): 484 (Mþ, 39.17), 41 (100); IR (neat, cmꢃ1): 3316,
2962, 2933, 2863, 2223, 1459, 1358, 1240, 1205, 1145, 1121, 1099,
1024; HRMS calcd for C17H17F13O (Mþ): 484.1072, found: 484.1070.
(CDCl3,100 MHz):
d
145.6, 86.1, 45.2 (t, JC–F¼20.6 Hz), 37.1, 31.8, 29.1,
29.0, 27.9, 22.6, 14.0; MS (EI, 70 eV) m/z (%): 584 (Mþ, 35.27), 401
(100); IR (neat, cmꢃ1): 2959, 2929, 2858, 1638, 1467, 1426, 1351,
1239, 1206, 1145, 1122; HRMS calcd for C16H18F13I (Mþ): 584.0240,
found: 584.0220.
3.2.6. Synthesis of 1-chloro-6-iodo-1,1,2,2,3,3,4,4-octafluoro-6(Z)-
tetradecene (Z-3f) and 4-(50-chloro-20,20,30,30,40,40,50,50-
octafluoropentyl)dodec-4(E) or (Z)-en-2-ynol (5fa)
Compound E-5ha. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.25 (t,
J¼7.6 Hz, 1H), 4.37 (s, 2H), 2.94 (t, JH–F¼18.4 Hz, 2H), 2.11 (q,
J¼7.6 Hz, 2H), 1.63 (br s, 1H), 1.48–1.35 (m, 2H), 1.35–1.17 (m, 8H),
The reaction of 3f (207.0 mg, 0.41 mmol, E/Z¼27:73), 4a
(14.0 mg, 0.25 mmol), Pd(PPh3)2Cl2 (10.1 mg, 1.44ꢂ10ꢃ2 mmol,
3.5 mol %), CuI (2.8 mg, 1.47ꢂ10ꢃ2 mmol, 3.6 mol %), and Et2NH
(18.1 mg, 0.25 mmol) in 0.8 mL of CH3CN for 60 min afforded Z-3f
(140.5 mg, 68%), Z-5fa (11.5 mg, 7%), and E-5fa (41.3 mg, 23%).
0.88 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.6, 110.0,
86.7, 84.8, 51.5, 32.2 (t, JC–F¼21.8 Hz), 31.7, 29.1, 29.0, 28.9, 28.7, 22.6,
14.0; MS (EI, 70 eV) m/z (%): 512 (Mþ, 11.67), 441 (100); IR (neat,
cmꢃ1): 3333, 2955, 2930, 2859, 2223, 1460, 1358, 1239, 1206, 1145,
1121, 1099, 1066, 1023; HRMS calcd for C19H21F13O (Mþ): 512.1379,
found: 512.1404.
Compound Z-3f. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.82 (t,
J¼7.0 Hz, 1H), 3.39 (t, JH–F¼17.6 Hz, 2H), 2.17 (q, J¼7.1 Hz, 2H), 1.49–
1.39 (m, 2H), 1.39–1.20 (m, 8H), 0.89 (t, J¼6.6 Hz, 3H); 13C NMR
3.2.9. Synthesis of 6-iodo-1,1,1,2,2,3,3,4,4-nonafluoro-6(Z)-
pentadecene (Z-3i) and 4-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)tridec-4(E) or (Z)-en-2-ynol (5ia)
(CDCl3, 100 MHz):
d
145.5, 86.2, 45.2 (t, JC–F¼21.2 Hz), 37.1, 31.8,
29.1, 29.0, 27.9, 22.6, 14.1; IR (neat, cmꢃ1): 2928, 1638, 1189, 1134;
MS (EI, 70 eV) m/z (%): 502 (Mþ
(
37Cl), 9.15), 500 (Mþ
(
35Cl), 27.69),
The reaction of 3i (149.9 mg, 0.30 mmol, E/Z¼28:72), 4a
(10.0 mg, 0.179 mmol), Pd(PPh3)2Cl2 (7.5 mg, 1.07ꢂ10ꢃ2 mmol,
3.6 mol %), CuI (2.1 mg, 1.11ꢂ10ꢃ2 mmol, 3.7 mol %), and Et2NH
(13.1 mg, 0.179 mmol) in 0.6 mL of CH3CN for 120 min afforded Z-3i
(90.8 mg, 61%), Z-5ia (2.3 mg, 2%), and E-5ia (29.5 mg, 23%).
35
43 (100); HRMS calcd for C
538.9647.
H
ClF8IK (MþþK): 538.9646, found
14 18
Compound E-5fa. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.26 (t,
J¼7.4 Hz, 1H), 4.38 (s, 2H), 2.94 (t, JH–F¼18.4 Hz, 2H), 2.11 (q,
J¼7.3 Hz, 2H), 1.69 (br s, 1H), 1.45–1.35 (m, 2H), 1.35–1.19 (m, 8H),
Compound Z-3i. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.83 (t,
0.89 (t, J¼6.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d
146.5, 110.0,
J¼6.8 Hz, 1H), 3.39 (t, JH–F¼17.6 Hz, 2H), 2.17 (q, J¼7.2 Hz, 2H), 1.50–
86.7, 84.8, 51.5, 32.2 (t, JC–F¼21.9 Hz), 31.7, 29.1, 29.0, 28.9, 28.7, 22.6,
1.39 (m, 2H), 1.39–1.19 (m, 10H), 0.89 (t, J¼6.8 Hz, 3H); 13C NMR
14.0; IR (neat, cmꢃ1): 3331, 2929, 2222, 1190, 1133; MS (EI, 70 eV)
(CDCl3, 100 MHz):
d
145.5, 86.0, 45.2 (t, JC–F¼21.4 Hz), 37.1, 31.9,
m/z (%): 430 (Mþ
(
37Cl), 3.77), 428 (Mþ
(
35Cl), 11.43), 43 (100); EA
29.4, 29.2, 29.1, 27.9, 22.7, 14.1; MS (EI, 70 eV) m/z (%): 498 (Mþ,
47.07), 315 (100); IR (neat, cmꢃ1): 2958, 2928, 2857, 1638, 1466,
1425, 1345, 1236, 1135, 1103, 1022; HRMS calcd for C15H20F9I (Mþ):
498.0460, found: 498.0476.
calcd for C17H21ClF8O: C, 47.62; H, 4.94. Found: C, 47.95; H, 5.13.
3.2.7. Synthesis of 6-iodo-1,1,1,2,2,3,3,4,4-nonafluoro-6(Z)-
tetradecene (Z-3g) and 4-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)dodec-4(E) or (Z)-en-2-ynol (5ga)
Compound Z-5ia was fully characterized using the sample pre-
pared in Section 3.3.8.
The reaction of 3g (125.4 mg, 0.26 mmol, E/Z¼30:70), 4a
(8.7 mg, 0.16 mmol), Pd(PPh3)2Cl2 (6.4 mg, 9.13ꢂ10ꢃ3 mmol,
3.5 mol %), CuI (1.7 mg, 8.95ꢂ10ꢃ3 mmol, 3.4 mol %), and Et2NH
(11.6 mg, 0.16 mmol) in 0.5 mL of CH3CN for 60 min afforded Z-3g
(73.0 mg, 58%), Z-5ga (1.0 mg, 1%), and E-5ga (23.5 mg, 22%).
Compound E-5ia. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.25 (t,
J¼7.6 Hz, 1H), 4.37 (d, J¼5.6 Hz, 2H), 2.94 (t, JH–F¼18.8 Hz, 2H), 2.11
(q, J¼7.2 Hz, 2H), 1.67 (t, J¼5.6 Hz, 1H), 1.46–1.35 (m, 2H), 1.35–1.18
(m, 10H), 0.88 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.5,
110.0, 86.7, 84.9, 51.5, 32.2 (t, JC–F¼22.3 Hz), 31.8, 29.3, 29.19, 29.16,
28.9, 28.7, 22.6, 14.0; MS (EI, 70 eV) m/z (%): 426 (Mþ, 9.47), 341
(100); IR (neat, cmꢃ1): 3331, 2929, 2858, 2223, 1631, 1467, 1350,
1236, 1135, 1100, 1025; HRMS calcd for C18H23F9ONa (MþNaþ)
449.1497, found: 449.1505.
Compound Z-3g. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.84 (t,
J¼6.8 Hz, 1H), 3.40 (t, JH–F¼17.4 Hz, 2H), 2.18 (q, J¼7.2 Hz, 2H), 1.52–
1.40 (m, 2H), 1.40–1.22 (m, 8H), 0.90 (t, J¼6.8 Hz, 3H); 13C NMR
(CDCl3, 100 MHz):
d
145.6, 86.0, 45.1 (t, JC–F¼21.9 Hz), 37.0, 31.8,
29.1, 29.0, 27.8, 22.6, 14.1; IR (neat, cmꢃ1): 2928, 1628, 1235; MS (EI,
70 eV) m/z (%): 484 (Mþ, 33.55), 43 (100); HRMS calcd for
3.2.10. Synthesis of 1-cyclohexyl-2-iodo-4,4,5,5,6,6,7,7,7-
C
14H18F9INa (MþNaþ): 507.0189, found: 507.0202.
nonafluoro-1(Z)-heptene (Z-3j) and 5-cyclohexyl-4-(20,20,30,30,
40,40,50,50,50-nonafluoropentyl) pent-4(E) or (Z)-en-2-ynol (5ja)
The reaction of 3j (111.5 mg, 0.24 mmol, E/Z¼31:69), 4a (8.2 mg,
0.146 mmol), Pd(PPh3)2Cl2 (5.9 mg, 8.42ꢂ10ꢃ3 mmol, 3.5 mol %),
CuI (1.5 mg, 7.89ꢂ10ꢃ3 mmol, 3.3 mol %), and Et2NH (10.6 mg,
0.145 mmol) in 0.5 mL of CH3CN for 60 min afforded Z-3j (68.4 mg,
61%), Z-5ja (1.4 mg, 2%), and E-5ja (22.2 mg, 24%).
Compound Z-5ga was fully characterized using the sample
prepared in Section 3.3.6.
Compound E-5ga. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.26 (t,
J¼7.8 Hz, 1H), 4.38 (s, 2H), 2.95 (t, JH–F¼18.6 Hz, 2H), 2.11 (q,
J¼7.5 Hz, 2H), 1.59 (br s, 1H), 1.45–1.34 (m, 2H), 1.34–1.18 (m, 8H),
0.88, (t, J¼6.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.6, 109.9,
86.7, 84.8, 51.5, 32.1 (t, JC–F¼22.2 Hz), 31.7, 29.1, 29.0, 28.9, 28.7, 22.6,
14.0; IR (neat, cmꢃ1): 3334, 2929, 2222, 1235, 1134; MS (EI, 70 eV)
m/z (%): 412 (Mþ, 22.13), 43 (100); EA calcd for C17H21F9O: C, 49.52;
H, 5.13. Found: C, 49.40; H, 5.11.
Compound Z-3j. Liquid; 1H NMR (400 MHz, CDCl3):
J¼8.8 Hz, 1H), 3.37 (t, J¼17.4 Hz, 2H), 2.33–2.21 (m, 1H), 1.82–1.63
d 5.64 (d,
(m, 5H),1.41–1.09 (m, 5H); 13C NMR (CDCl3,100 MHz):
d 150.2, 83.4,
46.0, 45.2 (t, JC–F¼20.7 Hz), 31.1, 25.8, 25.4; IR (neat, cmꢃ1): 2929,

6506
Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
2854, 1636, 1450, 1233, 1133; MS (EI, 70 eV) m/z (%): 468 (Mþ,
27.28), 82 (100); HRMS calcd for C13H14F9I (Mþ): 467.9997, found:
467.9993.
(12.8 mg, 0.175 mmol) in 0.5 mL of CH3CN for 80 min afforded Z-3g
(36.0 mg, 30%), Z-5gb (4.2 mg, 4%), and E-5gb (32.1 mg, 29%).
Compound Z-5gb was fully characterized using the sample
prepared in Section 3.3.12.
Compound Z-5ja was fully characterized using the sample pre-
pared in Section 3.3.9.
Compound E-5gb. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.19 (t,
Compound E-5ja. Liquid; 1H NMR (400 MHz, CDCl3):
d
6.09 (d,
J¼7.6 Hz, 1H), 2.93 (t, JH–F¼18.0 Hz, 2H), 2.09 (q, J¼7.2 Hz, 2H), 1.98
J¼10.4 Hz, 1H), 4.37 (s, 2H), 2.95 (t, J¼18.4 Hz, 2H), 2.22–2.09 (m,
(br s, 1H), 1.52 (s, 6H), 1.44–1.34 (m, 2H), 1.34–1.18 (m, 8H), 0.88 (t,
1H), 1.81–1.56 (m, 6H), 1.35–1.03 (m, 5H); 13C NMR (CDCl3,
J¼6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 145.6, 110.0, 91.5, 83.1,
100 MHz):
d
151.4, 108.0, 86.7, 84.8, 51.4, 38.2, 32.2 (t, JC–F¼21.8 Hz),
65.5, 32.3 (t, JC–F¼21.8 Hz), 31.7, 31.3, 29.2, 29.0, 28.9, 28.7, 22.6,
14.0; MS (EI, 70 eV) m/z (%): 440 (Mþ, 4.01), 425 (100); IR (neat,
cmꢃ1): 3357, 2930, 2859, 2222, 1460, 1349, 1236, 1167, 1134, 1089,
1026, 880, 741; HRMS calcd for C19H25F9ONa (MþNaþ): 463.1654,
found: 463.1662.
32.1, 25.7, 25.4; IR (neat, cmꢃ1): 3345, 2929, 2855, 2218, 1629, 1234,
1133,1025; MS (ESI) m/z: 418.8 (MþNaþ); EA calcd for C16H17F9O: C,
48.49; H, 4.32. Found: C, 48.64; H, 4.59.
3.2.11. Synthesis of 1-cyclohexyl-2-iodo-4,4,5,5,6,6,7,7,8,8,9,9,9-
tridecafluoro-1(Z)-nonene (Z-3k) and 5-cyclohexyl-4-(20,20,30,30,40,
40,50,50,60,60,70,70,70-tridecafluoroheptyl)pent-4(E) or (Z)-
en-2-ynol (5ka)
3.3. Synthesis of various 4-perfluoroalkylmethyl-4-en-2-
ynols by Sonogashira coupling reaction of 2-iodo-1-
perfluoroalkyl-2-alkenes
The reaction of 3k (170.3 mg, 0.30 mmol, E/Z¼30:70), 4a
(11.9 mg, 0.21 mmol), Pd(PPh3)2Cl2 (7.5 mg, 1.07ꢂ10ꢃ2 mmol,
3.6 mol %), CuI (2.1 mg, 1.11ꢂ10ꢃ2 mmol, 3.7 mol %), and Et2NH
(15.2 mg, 0.21 mmol) in 0.6 mL of CH3CN for 150 min afforded Z-3k
(90.6 mg, 53%), Z-5ka (3.8 mg, 3%), and E-5ka (37.6 mg, 25%).
3.3.1. Synthesis of 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-6-
phenylhex-4(Z)-en-2-ynol (Z-5aa) and 4-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)-6-phenylhex-4(E)-en-2-ynol (E-5aa)
Typical Procedure. Under nitrogen atmosphere, to a Schlenk tube
containing a mixture of Pd(PPh3)2Cl2 (6.5 mg, 9.27ꢂ10ꢃ3 mmol,
3.1 mol %) and CuI (1.7 mg, 8.95ꢂ10ꢃ3 mmol, 3.0 mol %) were added
3a (144.1 mg, 0.30 mmol, E/Z¼36:64), 4a (21.0 mg, 0.375 mmol),
and 1.2 mL of Et2NH sequentially. This mixture was degassed using
freeze–pump–thaw cycles and then was heated at 40 ꢀC under ni-
trogen. After 7 h, the reaction was complete as monitored by TLC,
the mixture was quenched with 10 mL of brine, diluted with 80 mL
diethyl ether, washed by brine (10 mLꢂ3), and the organic layer
was dried over anhydrous Na2SO4. Evaporation and column chro-
matography on silica gel (eluent: petroleum ether/ethyl
acetate¼10:1) afforded E-5aa (53.7 mg, 44%) and Z-5aa (25.0 mg,
20%).
Compound Z-3k. Liquid; 1H NMR (400 MHz, CDCl3):
d
5.63 (d,
J¼8.4 Hz, 1H), 3.36 (t, JH–F¼17.2 Hz, 2H), 2.36–2.19 (m, 1H), 1.85–
1.58 (m, 5H), 1.42–1.03 (m, 5H); 13C NMR (CDCl3, 100 MHz):
150.2,
d
83.5, 46.1, 45.3 (t, JC–F¼20.4 Hz), 31.1, 25.8, 25.5; MS (EI, 70 eV) m/z
(%): 568 (Mþ, 5.96), 82 (100); IR (neat, cmꢃ1): 2929, 2855, 1636,
1451, 1426, 1351, 1239, 1145, 1121, 1096, 1068, 703; HRMS calcd for
C
15H14F13I (Mþ): 567.9933, found: 567.9936.
Compound Z-5ka was fully characterized using the sample
prepared in Section 3.3.10.
Compound E-5ka. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.08 (d,
J¼10.8 Hz, 1H), 4.36 (s, 2H), 2.94 (t, JH–F¼18.8 Hz, 2H), 2.22–2.08 (m,
1H), 1.85–1.50 (m, 6H), 1.36–1.01 (m, 5H); 13C NMR (CDCl3,
100 MHz):
d
151.5, 107.9, 86.7, 84.8, 51.4, 38.3, 32.3 (t, JC–F¼21.7 Hz),
Compound Z-5aa. Liquid; 1H NMR (400 MHz, CDCl3):
d 7.32 (t,
32.1, 25.6, 25.4; MS (EI, 70 eV) m/z (%): 496 (Mþ, 19.63), 67 (100); IR
(neat, cmꢃ1): 3322, 2930, 2856, 2222, 1629, 1451, 1358, 1240, 1207,
1145, 1122, 1024; HRMS calcd for C18H17F13O (Mþ): 496.1072, found:
496.1073.
J¼7.4 Hz, 2H), 7.28–7.17 (m, 3H), 6.12 (t, J¼7.4 Hz, 1H), 4.46 (s, 2H),
3.70 (d, J¼7.2 Hz, 2H), 2.94 (t, JH–F¼18.4 Hz, 2H), 1.85 (br s, 1H); 13
C
NMR (CDCl3, 100 MHz):
d 144.3, 138.9, 128.6, 128.4, 126.4, 111.3,
92.2, 82.8, 51.5, 37.9 (t, JC–F¼22.3 Hz), 37.0; MS (EI, 70 eV) m/z (%):
404 (Mþ, 4.27), 153 (100); IR (neat, cmꢃ1): 3363, 3031, 2924, 2181,
1668, 1599, 1496, 1455, 1345, 1233, 1133, 1105, 1030; HRMS calcd for
3.2.12. Synthesis of 3-iodo-5,5,6,6,7,7,8,8,8-nonafluoro-1-phenyl-
2(Z)-octene (Z-3a) and 2-methyl-5-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)-7-phenylhept-5(E) or (Z)-en-3-yn-2-ol (5ab)
The reaction of 3a (119.5 mg, 0.25 mmol, E/Z¼36:64), 4b
(14.9 mg, 0.177 mmol), Pd(PPh3)2Cl2 (6.0 mg, 8.56ꢂ10ꢃ3 mmol,
3.4 mol %), CuI (1.7 mg, 8.95ꢂ10ꢃ3 mmol, 3.6 mol %), and Et2NH
(12.8 mg, 0.175 mmol) in 0.5 mL of CH3CN for 120 min afforded Z-
3a (42.0 mg 35%), Z-5ab (8.0 mg, 7%), and E-5ab (36.2 mg, 33%).
Compound Z-5ab was fully characterized using the sample
prepared in Section 3.3.11.
C
17H13F9ONa (MþNaþ): 427.0715, found: 427.0707.
3.3.2. Synthesis of 6-phenyl-4-(20,20,30,30,40,40,50,50, 60,60,70,70,70-
tridecafluoro-heptyl)hex-4(Z)-en-2-ynol (Z-5ba) and 6-phenyl-4-
(20,20,30,30,40,40,50,50,60,60,70,70,70-tridecafluoroheptyl)hex-4(E)-en-2-
ynol (E-5ba)
The reaction of 3b (175.1 mg, 0.30 mmol, E/Z¼37:63), 4a
(20.5 mg, 0.37 mmol), Pd(PPh3)2Cl2 (6.2 mg, 8.84ꢂ10ꢃ3 mmol,
2.9 mol %), and CuI (2.0 mg,1.05ꢂ10ꢃ2 mmol, 3.5 mol %) in 1.2 mL of
Et2NH for 9.5 h afforded Z-5ba (61.7 mg, 40%) and E-5ba (32.3 mg,
21%).
Compound E-5ab. Liquid; 1H NMR (400 MHz, CDCl3):
d 7.32 (t,
J¼7.2 Hz, 2H), 7.24 (t, J¼7.4 Hz, 1H), 7.16 (d, J¼7.6 Hz, 2H), 6.36 (t,
J¼7.6 Hz, 1H), 3.47 (d, J¼7.2 Hz, 2H), 3.05 (t, JH–F¼18.4 Hz, 2H), 2.00
Compound Z-5ba. Liquid; 1H NMR (400 MHz, CDCl3):
d 7.31 (t,
(br s, 1H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz):
d
143.3, 138.4,
J¼7.2 Hz, 2H), 7.27–7.17 (m, 3H), 6.11 (t, J¼7.6 Hz, 1H), 4.44 (s, 2H),
128.7, 128.4, 126.6, 111.0, 92.2, 82.7, 65.4, 34.9, 32.5 (t, JC–F¼21.9 Hz),
31.2; MS (EI, 70 eV) m/z (%): 432 (Mþ, 2.66), 399 (100); IR (neat,
cmꢃ1): 3381, 3031, 2984, 2934, 2222, 1604, 1496, 1455, 1349, 1236,
1133, 1098, 1028; HRMS calcd for C19H17F9ONa (MþNaþ): 455.1028,
found: 455.1016.
3.70 (d, J¼7.6 Hz, 2H), 2.94 (t, JH–F¼18.4 Hz, 2H), 2.30 (br s, 1H); 13
C
NMR (CDCl3, 100 MHz):
d 144.2, 138.9, 128.6, 128.4, 126.4, 111.4,
92.3, 82.7, 51.3, 38.0 (t, JC–F¼21.7 Hz), 37.0; MS (EI, 70 eV) m/z (%):
504 (Mþ, 2.52), 153 (100); IR (neat, cmꢃ1): 3329, 3031, 2924, 2222,
1603, 1496, 1453, 1430, 1351, 1238, 1205, 1145, 1036; HRMS calcd for
C
19H13F13O (Mþ): 504.0759, found: 504.0761.
3.2.13. Synthesis of 6-iodo-1,1,1,2,2,3,3,4,4-nonafluoro-6(Z)-
tetradecene (Z-3g) and 2-methyl-5-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)tridec-5(E) or (Z)-en-3-yn-2-ol (5gb)
3.3.3. Synthesis of 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)non-
4(Z)-en-2-ynol (Z-5ca) and 4-(20,20,30,30,40,40,50,50,50-
The reaction of 3g (120.9 mg, 0.25 mmol, E/Z¼30:70), 4b
(14.8 mg, 0.176 mmol), Pd(PPh3)2Cl2 (6.1 mg, 8.70ꢂ10ꢃ3 mmol,
3.5 mol %), CuI (1.7 mg, 8.95ꢂ10ꢃ3 mmol, 3.6 mol %), and Et2NH
nonafluoropentyl)non-4(E)-en-2-ynol (E-5ca)
The reaction of 3c (175.1 mg, 0.40 mmol, E/Z¼33:67), 4a
(27.2 mg, 0.49 mmol), Pd(PPh3)2Cl2 (8.7 mg, 1.24ꢂ10ꢃ2 mmol,

Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
6507
3.1 mol %), and CuI (2.2 mg, 1.16ꢂ10ꢃ2 mmol, 2.9 mol %) in 1.6 mL of
3.3.7. Synthesis of 4-(20,20,30,30,40,40,50,50,60,60,70,70,70-
tridecafluoroheptyl)dodec-4(Z)-en-2-ynol (Z-5ha) and 4-
(20,20,30,30,40,40,50,50,60,60,70,70,70-tridecafluoroheptyl)dodec-4(E)-en-
2-ynol (E-5ha)
Et2NH for 9 h afforded Z-5ca (83.9 mg, 57%) and E-5ca (35.6 mg,
24%).
Compound Z-5ca. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.94 (t,
J¼7.2 Hz, 1H), 4.42 (s, 2H), 2.86 (t, JH–F¼18.4 Hz, 2H), 2.33 (q,
The reaction of 3h (177.0 mg, 0.30 mmol, E/Z¼28:72), 4a
(20.7 mg, 0.37 mmol), Pd(PPh3)2Cl2 (6.1 mg, 8.70ꢂ10ꢃ3 mmol,
2.9 mol %), and CuI (1.8 mg, 9.47ꢂ10ꢃ3 mmol, 3.2 mol %) in 1.2 mL
of Et2NH for 11 h afforded Z-5ha (78.4 mg, 51%) and E-5ha
(52.8 mg, 34%).
J¼7.2 Hz, 2H), 2.01 (br s, 1H), 1.45–1.27 (m, 4H), 0.90 (t, J¼6.8 Hz,
3H); 13C NMR (CDCl3, 100 MHz):
d 146.9, 110.1, 91.7, 83.1, 51.5, 37.9
(t, JC–F¼21.9 Hz), 30.7, 30.5, 22.2, 13.8; MS (EI, 70 eV) m/z (%): 370
(Mþ, 41.68), 341 (100); IR (neat, cmꢃ1): 3330, 2962, 2934, 2863,
2223, 1624, 1431, 1344, 1301, 1235, 1134, 1099, 1024; HRMS calcd for
Compound Z-5ha. Liquid; 1H NMR (400 MHz, CDCl3)
d 5.94 (t,
C
14H15F9ONa (MþNaþ): 393.0871, found: 393.0873.
J¼7.6 Hz, 1H), 4.42 (d, J¼5.6 Hz, 2H), 2.87 (t, JH–F¼18.4 Hz, 2H), 2.32
(q, J¼7.2 Hz, 2H), 1.85 (t, J¼5.6 Hz, 1H), 1.48–1.35 (m, 2H), 1.35–1.19
3.3.4. Synthesis of 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)dec-
4(Z)-en-2-ynol (Z-5da) and 4-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)dec-4(E)-en-2-ynol (E-5da)
(m, 8H), 0.88 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.9,
110.1, 91.7, 83.1, 51.5, 38.1 (t, JC–F¼21.4 Hz), 31.8, 30.8, 29.1, 29.0, 28.6,
22.6,14.0; MS (EI, 70 eV) m/z (%): 512 (Mþ, 3.24), 441 (100); IR (neat,
cmꢃ1): 3330, 2959, 2929, 2859, 2224, 1461, 1432, 1350, 1315, 1239,
1206, 1145, 1121, 1101, 1024; HRMS calcd for C19H21F13O (Mþ):
512.1379, found: 512.1402.
The reaction of 3d (137.3 mg, 0.30 mmol, E/Z¼30:70), 4a
(20.5 mg, 0.37 mmol), Pd(PPh3)2Cl2 (6.4 mg, 9.13ꢂ10ꢃ3 mmol,
3.0 mol %), and CuI (1.8 mg, 9.41ꢂ10ꢃ3 mmol, 3.2 mol %) in 1.2 mL of
Et2NH for 7 h afforded Z-5da (67.0 mg, 58%) and E-5da (28.0 mg,
24%).
3.3.8. Synthesis of 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-
tridec-4(Z)-en-2-ynol (Z-5ia) and 4-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)tridec-4(E)-en-2-ynol (E-5ia)
Compound Z-5da. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.95 (t,
J¼7.2 Hz, 1H), 4.42 (s, 2H), 2.86 (t, JH–F¼18.0 Hz, 2H), 2.32 (q,
J¼6.8 Hz, 2H), 1.90 (br s, 1H), 1.48–1.36 (m, 2H), 1.36–1.20 (m, 4H),
The reaction of 3i (149.9 mg, 0.30 mmol, E/Z¼28:72), 4a
(19.9 mg, 0.36 mmol), Pd(PPh3)2Cl2 (6.3 mg, 8.99ꢂ10ꢃ3 mmol,
3.0 mol %), and CuI (1.6 mg, 8.42ꢂ10ꢃ3 mmol, 2.8 mol %) in 1.2 mL
of Et2NH for 7.5 h afforded Z-5ia (69.4 mg, 54%) and E-5ia (30.3 mg,
24%).
0.89 (t, J¼6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.8, 110.1,
91.8, 83.0, 51.5, 38.0 (t, JC–F¼21.4 Hz), 31.3, 30.8, 28.2, 22.4, 13.9; MS
(EI, 70 eV) m/z (%): 384 (Mþ, 10.25), 41 (100); IR (neat, cmꢃ1): 3319,
2961, 2932, 2861, 2224, 1460, 1432, 1344, 1235, 1134, 1100, 1025,
879, 742; HRMS calcd for C15H17F9O (Mþ): 384.1136, found:
384.1129.
Compound Z-5ia. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.94 (t,
J¼7.6 Hz, 1H), 4.42 (s, 2H), 2.86 (t, JH–F¼18.0 Hz, 2H), 2.32 (q,
J¼7.6 Hz, 2H), 1.84 (br s, 1H), 1.47–1.35 (m, 2H), 1.35–1.17 (m, 10H),
3.3.5. Synthesis of 4-(20,20,30,30,40,40,50,50,60,60,70,70,70-
tridecafluoroheptyl)-dec-4(Z)-en-2-ynol (Z-5ea) and 4-
(20,20,30,30,40,40,50,50,60,60,70,70,70-tridecafluoroheptyl)-dec-4(E)-en-2-
ynol (E-5ea)
0.87 (t, J¼6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.9, 110.0 (t,
JC–F¼2.7 Hz), 91.7, 83.1, 51.6, 38.0 (t, JC–F¼21.7 Hz), 31.8, 30.8, 29.4,
29.2, 29.1, 28.6, 22.7,14.1; MS (EI, 70 eV) m/z (%): 426 (Mþ, 0.97), 341
(100); IR (neat, cmꢃ1): 3320, 2958, 2928, 2858, 2224, 1631, 1460,
1431, 1380, 1344, 1301, 1235, 1134, 1102, 1023; HRMS calcd for
The reaction of 3e (141.5 mg, 0.25 mmol, E/Z¼30:70), 4a
(16.9 mg, 0.30 mmol), Pd(PPh3)2Cl2 (5.3 mg, 7.56ꢂ10ꢃ3 mmol,
3.0 mol %), and CuI (1.4 mg, 7.37ꢂ10ꢃ3 mmol, 2.9 mol %) in 0.5 mL
of Et2NH for 9.5 h afforded Z-5ea (67.9 mg, 55%) and E-5ea
(29.5 mg, 24%).
C
18H23F9ONa (MþNaþ) 449.1497, found: 449.1505.
3.3.9. Synthesis of 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-5-
cyclohexylpent-4(Z)-en-2-ynol (Z-5ja) and 4-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)-5-cyclohexylpent-4(E)-en-2-ynol (E-5ja)
The reaction of 3j (232.3 mg, 0.50 mmol, E/Z¼31:69), 4a (34.5 mg,
0.62 mmol), Pd(PPh3)2Cl2 (10.8 mg, 1.54ꢂ10ꢃ2 mmol, 3.1 mol %), and
CuI (3.0 mg, 1.58ꢂ10ꢃ3 mmol, 3.2 mol %) in 2 mL of Et2NH for 6 h
afforded Z-5ja (133.4 mg, 68%) and E-5ja (49.7 mg, 25%).
Compound Z-5ea. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.94 (t,
J¼7.6 Hz, 1H), 4.42 (s, 2H), 2.86 (t, JH–F¼18.2 Hz, 2H), 2.32 (q,
J¼7.2 Hz, 2H), 2.01 (br s, 1H), 1.47–1.36 (m, 2H), 1.36–1.23 (m, 4H),
0.88 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3,100 MHz):
d 146.9,110.1, 91.7,
83.0, 51.4, 38.0 (t, JC–F¼22.1 Hz), 31.3, 30.7, 28.2, 22.4, 13.9; MS (EI,
70 eV) m/z (%): 484 (Mþ, 27.00), 441 (100); IR (neat, cmꢃ1): 3320,
2961, 2933, 2862, 2224, 1632, 1461, 1432, 1350, 1316, 1240, 1206,
1145, 1121, 1100, 1067, 1032, 997; HRMS calcd for C17H17F13O (Mþ):
484.1072, found: 484.1065.
Compound Z-5ja. Solid, mp: 36–37 ꢀC (hexane); 1H NMR
(400 MHz, CDCl3):
18.0 Hz, 2H), 2.63–2.48 (m, 1H), 2.13 (br s, 1H), 1.80–1.56 (m, 5H),
1.40–1.00 (m, 5H); 13C NMR (CDCl3,100 MHz):
152.1,108.1 (t, JC–F
d
5.76 (d, J¼9.6 Hz,1H), 4.42 (s, 2H), 2.83 (t, JH–F¼
d
¼
2.8 Hz), 91.3, 83.0, 51.6, 39.8, 38.0 (t, JC–F¼22.2 Hz), 31.9, 25.8, 25.5;
MS (EI, 70 eV) m/z (%): 396 (Mþ, 28.85), 67 (100); IR (neat, cmꢃ1):
3317, 2929, 2854, 2222, 1450, 1344, 1301, 1234, 1133, 1091, 1032,
879, 742; EA calcd for C16H17F9O: C, 48.49; H, 4.32. Found: C, 48.62;
H, 4.48.
3.3.6. Synthesis of 4-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-
dodec-4(Z)-en-2-ynol (Z-5ga) and 4-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)dodec-4(E)-en-2-ynol (E-5ga)
The reaction of 3g (121.9 mg, 0.25 mmol, E/Z¼30:70), 4a
(16.9 mg, 0.30 mmol), Pd(PPh3)2Cl2 (5.3 mg, 7.56ꢂ10ꢃ3 mmol,
3.0 mol %), and CuI (1.4 mg, 7.37ꢂ10ꢃ3 mmol, 2.9 mol %) in 0.5 mL
of Et2NH for 7.5 h afforded Z-5ga (55.1 mg, 53%) and E-5ga (21.9 mg
21%).
3.3.10. Synthesis of 5-cyclohexyl-4-(20,20,30,30,40,40,50,50,60,60,70,70,70-
tridecafluoroheptyl)pent-4(Z)-en-2-ynol (Z-5ka) and 5-cyclohexyl-
4-(20,20,30,30,40,40,50,50,60,60,70,70,70-tridecafluoroheptyl)pent-4(E)-en-
2-ynol (E-5ka)
Compound Z-5ga. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.94 (t,
J¼7.2 Hz, 1H), 4.42 (s, 2H), 2.86 (t, JH–F¼18.4 Hz, 2H), 2.32 (q,
The reaction of 3k (224.6 mg, 0.40 mmol, E/Z¼30:70), 4a
(27.6 mg, 0.49 mmol), Pd(PPh3)2Cl2 (8.6 mg, 1.23ꢂ10ꢃ2 mmol,
3.1 mol %), and CuI (2.4 mg,1.26ꢂ10ꢃ2 mmol, 3.2 mol %) in 1.6 mL of
Et2NH for 11.5 h afforded Z-5ka (117.3 mg, 60%) and of E-5ka
(50.9 mg, 26%).
J¼7.2 Hz, 2H), 1.89 (br s, 1H), 1.46–1.35 (m, 2H), 1.35–1.18 (m, 8H),
0.87 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.9, 110.1 (t,
JC–F¼2.8 Hz), 91.7, 83.0, 51.5, 37.9 (t, JC–F¼21.9 Hz), 31.7, 30.8, 29.1,
29.0, 28.6, 22.6, 14.0; MS (EI, 70 eV) m/z (%): 412 (Mþ, 2.09), 341
(100); IR (neat, cmꢃ1): 3319, 2964, 2929, 2859, 2223, 1628, 1461,
1431, 1344, 1236, 1134, 1101, 1023; HRMS calcd for C17H21F9ONa
(MþNaþ): 435.1341, found: 435.1334.
Compound Z-5ka. Solid, mp: 52–53 ꢀC (hexane); 1H NMR
(400 MHz, CDCl3):
d
5.76 (d, J¼9.2 Hz,1H), 4.42 (s, 2H), 2.84 (t, JH–F¼
17.8 Hz, 2H), 2.63–2.48 (m, 1H), 2.07 (br s, 1H), 1.80–1.57 (m, 5H),

6508
Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
1.39–0.98 (m, 5H); 13C NMR (CDCl3, 100 MHz):
83.0, 51.5, 39.8, 38.2 (t, JC–F¼22.4 Hz), 32.0, 25.8, 25.5; MS (EI, 70 eV)
m/z (%): 496 (Mþ, 90.71), 67 (100); IR (KBr, cmꢃ1): 3231, 2927, 2857,
2222, 1451, 1352, 1242, 1185, 1138, 1090, 1066, 1035; EA calcd for
d
152.0, 108.2, 91.4,
29.17, 28.9, 28.7, 22.6, 14.0; MS (EI, 70 eV) m/z (%): 454 (Mþ, 3.10),
439 (100); IR (neat, cmꢃ1): 3354, 2958, 2929, 2858, 2221, 1629,
1460,1349,1236, 1220,1167,1134, 1090, 1026, 878, 732; HRMS calcd
for C20H27F9ONa (MþNaþ): 477.1810, found: 477.1816.
C
18H17F13O: C, 43.56; H, 3.45. Found: C, 43.75; H, 3.58.
3.3.14. Synthesis of 6-cyclohexyl-2-methyl-5-(20,20,30,30,40,
40,50,50,50-nonafluoropentyl)hex-5(Z)-en-3-yn-2-ol (Z-5jb) and
6-cyclohexyl-2-methyl-5-(20,20,30,30,40,40,50,50,50-
3.3.11. Synthesis of 2-methyl-5-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)-7-phenyl-hept-5(Z)-en-3-yn-2-ol (Z-5ab) and 2-
methyl-5-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)-7-phenylhept-
5(E)-en-3-yn-2-ol (E-5ab)
nonafluoropentyl)hex-5(E)-en-3-yn-2-ol (E-5jb)
The reaction of 3j (140.8 mg, 0.30 mmol, E/Z¼31:69), 4b
(30.0 mg, 0.36 mmol), Pd(PPh3)2Cl2 (6.3 mg, 8.99ꢂ10ꢃ3 mmol,
3.0 mol %), and CuI (1.6 mg, 8.42ꢂ10ꢃ3 mmol, 2.8 mol %) in 0.6 mL
of Et2NH for 10.5 h afforded Z-5jb (75.1 mg 59%) and E-5jb
(35.4 mg, 28%).
The reaction of 3a (189.2 mg, 0.40 mmol, E/Z¼36:64), 4b
(40.3 mg, 0.48 mmol), Pd(PPh3)2Cl2 (8.4 mg, 1.20ꢂ10ꢃ2 mmol,
3.0 mol %), and CuI (2.3 mg, 1.21ꢂ10ꢃ2 mmol, 3.0 mol %) in 1.6 mL of
Et2NH for 8 h afforded Z-5ab (90.6 mg, 53%) and E-5ab (45.6 mg,
27%).
Compound Z-5jb. Solid, mp: 44–45 ꢀC (hexane); 1H NMR
Compound Z-5ab. Liquid; 1H NMR (400 MHz, CDCl3):
d
7.30 (t,
(400 MHz, CDCl3):
2H), 2.58–2.45 (m, 1H), 2.18 (s, 1H), 1.80–1.60 (m, 5H), 1.54 (s, 6H),
1.37–1.00 (m, 5H); 13C NMR (CDCl3,100 MHz):
151.4,108.5 (t, JC–F
d
5.74 (d, J¼9.2 Hz, 1H), 2.81 (t, JH–F¼18.0 Hz,
J¼7.4 Hz, 2H), 7.26–7.16 (m, 3H), 6.07 (t, J¼7.6 Hz, 1H), 3.67 (d,
J¼7.2 Hz, 2H), 2.91 (t, JH–F¼17.6 Hz, 2H), 2.25 (s, 1H), 1.57 (s, 6H); 13
C
d
¼
NMR (CDCl3, 100 MHz):
d
143.5, 139.0, 128.6, 128.4, 126.4, 111.5,
2.6 Hz), 98.1, 79.5, 65.6, 39.8, 38.1 (t, JC–F¼21.9 Hz), 31.9, 31.2, 25.8,
25.6; MS (EI, 70 eV) m/z (%): 424 (Mþ, 7.15), 381 (100); IR (neat,
cmꢃ1): 3390, 2983, 2931, 2855, 2222, 1633, 1451, 1345, 1236, 1167,
1134, 1089, 1027; HRMS calcd for C18H21F9ONa (MþNaþ): 447.1341,
found: 447.1340.
99.0, 79.3, 65.6, 38.1 (t, JC–F¼22.2 Hz), 37.0, 31.3; MS (EI, 70 eV) m/z
(%): 432 (Mþ, 0.52), 399 (100); IR (neat, cmꢃ1): 3379, 3031, 2984,
2934, 2222, 1603, 1495, 1454, 1344, 1235, 1133, 1103, 1027; HRMS
calcd for C19H17F9ONa (MþNaþ): 455.1028, found: 455.1024.
Compound E-5jb. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.02 (d,
3.3.12. Synthesis of 2-methyl-5-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)tridec-5(Z)-en-3-yn-2-ol (Z-5gb) and 2-methyl-
5-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)tridec-5(E)-en-3-yn-2-ol
(E-5gb)
J¼10.8 Hz, 1H), 2.93 (t, JH–F¼18.4 Hz, 2H), 2.20–2.08 (m, 1H), 1.96 (s,
1H), 1.80–1.55 (m, 5H), 1.52 (s, 6H), 1.38–1.02 (m, 5H); 13C NMR
(CDCl3, 100 MHz):
d
150.5, 108.0 (t, JC–F¼3.5 Hz), 91.4, 83.1, 65.5,
38.2, 32.4 (t, JC–F¼22.8 Hz), 32.1, 31.2, 25.6, 25.4; MS (EI, 70 eV) m/z
(%): 424 (Mþ, 6.28), 43 (100); IR (neat, cmꢃ1): 3353, 2983, 2930,
2855, 2222, 1451, 1350, 1234, 1166, 1135, 1079, 1026, 879, 733;
HRMS calcd for C18H21F9O (Mþ): 424.1449, found: 424.1452.
The reaction of 3g (194.2 mg, 0.40 mmol, E/Z¼30:70), 4b
(40.7 mg, 0.48 mmol), Pd(PPh3)2Cl2 (8.6 mg, 1.23ꢂ10ꢃ2 mmol,
3.1 mol %), and CuI (2.1 mg, 1.11ꢂ10ꢃ2 mmol, 2.8 mol %) in 1.6 mL of
Et2NH for 7 h afforded Z-5gb (103.2 mg, 58%) and E-5gb (41.6 mg,
24%).
Acknowledgements
Compound Z-5gb. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.90 (t,
J¼7.2 Hz, 1H), 2.84 (t, JH–F¼18.0 Hz, 2H), 2.29 (q, J¼7.2 Hz, 2H), 2.15
Financial support from the National Natural Science Foundation
of China (20672094) and Major State Basic Research and De-
velopment Program (2006CB806105) is greatly appreciated. S.M. is
a Qiu Shi Adjunct Professor at Zhejiang University. We thank Mr.
Wangqing Kong in this group for reproducing the results presented
in entry 1 of Table 1, entry 1 of Table 2, and entries 12 and 14 of
Table 4.
(s, 1H), 1.54 (s, 6H), 1.46–1.35 (m, 2H), 1.35–1.18 (m, 8H), 0.87 (t,
J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d 146.0, 110.4, 98.5, 79.5,
65.6, 38.2 (t, JC–F¼20.5 Hz), 31.8, 31.3, 30.7, 29.0, 28.5, 22.6, 14.0; MS
(EI, 70 eV) m/z (%): 440 (Mþ, 2.71), 341 (100); IR (neat, cmꢃ1): 3363,
2955, 2930, 2859, 2222, 1629, 1459, 1344, 1302, 1236, 1134, 1101,
1025; HRMS calcd for C19H25F9ONa (MþNaþ): 463.1654, found:
463.1659.
Supplementary data
3.3.13. Synthesis of 2-methyl-5-(20,20,30,30,40,40,50,50,50-
nonafluoropentyl)tetradec-5(Z)-en-3-yn-2-ol (Z-5ib) and 2-methyl-
5-(20,20,30,30,40,40,50,50,50-nonafluoropentyl)tetradec-5(E)-en-3-yn-
2-ol (E-5ib)
Copies of 1H and 13C NMR spectra of all compounds. This ma-
terial is available free of charge via the Internet. Supplementary
data associated with this article can be found in the online version,
at doi:10.1016/j.tet.2008.04.057.
The reaction of 3i (198.5 mg, 0.40 mmol, E/Z¼28:72), 4b
(41.9 mg, 0.50 mmol), Pd(PPh3)2Cl2 (8.4 mg, 1.20ꢂ10ꢃ2 mmol,
3.0 mol %), and CuI (2.3 mg, 1.21ꢂ10ꢃ2 mmol, 3.0 mol %) in 1.6 mL of
Et2NH for 12 h afforded Z-5ib (104.7 mg, 58%) and E-5ib (33.6 mg,
19%).
References and notes
1. For books and reviews, see: (a) Kirsch, P. Modern Fluoroorganic Chemistry, 1st ed.;
Wiley-VCH: Weinheim, Germany, 2004; (b) Wilkinson, J. A. Chem. Rev. 1992, 92,
505; (c) Ma, J.-A.; Cahard, D. Chem. Rev. 2004, 104, 6119.
2. (a) Iseki, K. Tetrahedron 1998, 54, 13887; (b) Resnati, G. Tetrahedron 1993, 49,
9385; (c) Shimizu, M.; Hiyama, T. Angew. Chem., Int. Ed. 2005, 44, 214.
3. For reviews, see: (a) Huang, W.-Y. J. Fluorine Chem. 1992, 58, 1; (b) Dolbier, W. R.,
Jr. Chem. Rev. 1996, 96, 1557; (c) Brace, N. O. J. Fluorine Chem. 1999, 93, 1; (d)
Brace, N. O. J. Fluorine Chem. 1999, 96, 101; (e) Brace, N. O. J. Fluorine Chem. 2001,
108, 147.
4. For some selected reports of addition reactions of perfluoroalkyl halides to
alkenes, see: (a) Lu, X.; Ma, S.; Zhu, J. Tetrahedron Lett. 1988, 29, 5129; (b)
Napoli, M.; Gambaretto, G. P. J. Fluorine Chem. 1997, 84, 101; (c) Bravo, A.;
Bjørsvik, H.-R.; Fontana, F.; Liguori, L.; Mele, A.; Minisci, F. J. Org. Chem. 1997,
62, 7128; (d) Guo, X.-C.; Chen, Q.-Y. J. Fluorine Chem. 1998, 88, 63; (e) Wu, F.-
H.; Huang, W.-Y. J. Fluorine Chem. 1998, 92, 85; (f) Guo, X.-C.; Chen, Q.-Y. J.
Fluorine Chem. 1999, 93, 81; (g) Long, Z.-Y.; Chen, Q.-Y. J. Org. Chem. 1999, 64,
4775; (h) Yoshida, M.; Ohkoshi, M.; Aoki, N.; Ohnuma, Y.; Iyoda, M. Tetrahe-
dron Lett. 1999, 40, 5731; (i) Uneyama, K. J. Organomet. Chem. 2000, 611, 158;
(j) Huang, X.-T.; Chen, Q.-Y. J. Org. Chem. 2001, 66, 4651; (k) Vincent, J.-M.;
Compound Z-5ib. Liquid; 1H NMR (400 MHz, CDCl3):
d 5.90 (t,
J¼7.6 Hz, 1H), 2.84 (t, JH–F¼18.4 Hz, 2H), 2.30 (q, J¼7.6 Hz, 2H), 2.13
(s, 1H), 1.54 (s, 6H), 1.46–1.35 (m, 2H), 1.35–1.18 (m, 10H), 0.87 (t,
J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d
146.1, 110.3 (t, JC–F
¼
2.4 Hz), 98.5, 79.6, 65.6, 38.1 (t, JC–F¼21.9 Hz), 31.8, 31.3, 30.7, 29.3,
29.2, 29.1, 28.5, 22.6, 14.0; MS (EI, 70 eV) m/z (%): 454 (Mþ, 2.19),
341 (100); IR (neat, cmꢃ1): 3355, 2959, 2929, 2858, 2223, 1630,
1459, 1431, 1343, 1302, 1236, 1221, 1167, 1134, 1101, 1025; HRMS
calcd for C20H27F9ONa (MþNaþ): 477.1810, found: 477.1825.
Compound E-5ib. Liquid; 1H NMR (400 MHz, CDCl3):
d 6.19 (t,
J¼7.6 Hz, 1H), 2.93 (t, JH–F¼18.4 Hz, 2H), 2.09 (q, J¼7.6 Hz, 2H), 1.98
(s, 1H), 1.52 (s, 6H), 1.46–1.34 (m, 2H), 1.34–1.17 (m, 10H), 0.88 (t,
J¼6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz):
d
145.6, 110.1 (t, JC–F
¼
3.3 Hz), 91.5, 83.1, 65.5, 32.4 (t, JC–F¼21.8 Hz), 31.8, 31.3, 29.3, 29.22,

Z. Ma, S. Ma / Tetrahedron 64 (2008) 6500–6509
6509
Rabion, A.; Yachandra, V. K.; Fish, R. H. Can. J. Chem. 2001, 79, 888; (l) Zou, X.
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