Highly regioselective cyclotrimerization of 1-perfluoroalkylenynes catalyzed by nickel

Article abstract of DOI:10.1021/jo0056242

We report the highly regioselective cyclotrimerization of the 1-perfluoroalkylenynes in the presence of Ni(PPh₃)₄. The substituent effects on the reactivity of the enynes were investigated. We also succeeded in the nickel-catalyzed cocyclization of the 1-perfluoroalkylenynes with (trimethylsilyl)-acetylene. The possible structures of the intermediates of the cyclotrimerization and the reasons for the observed high regioselectivity were discussed.

Full text of DOI:10.1021/jo0056242

796
J . Org. Chem. 2001, 66, 796-802
High ly Regioselective Cyclotr im er iza tion of
1-P er flu or oa lk ylen yn es Ca ta lyzed by Nick el
Shinichi Saito,*,† Taishi Kawasaki,‡ Norie Tsuboya,‡ and Yoshinori Yamamoto*,‡
Institute for Chemical Reaction Science, Tohoku University, Sendai, 980-8578, J apan, and Department of
Chemistry, Graduate School of Science, Tohoku University, Sendai, 980-8578, J apan
ssaito@mail.cc.tohoku.ac.jp
Received August 27, 2000
We report the highly regioselective cyclotrimerization of the 1-perfluoroalkylenynes in the presence
of Ni(PPh3)4. The substituent effects on the reactivity of the enynes were investigated. We also
succeeded in the nickel-catalyzed cocyclization of the 1-perfluoroalkylenynes with (trimethylsilyl)-
acetylene. The possible structures of the intermediates of the cyclotrimerization and the reasons
for the observed high regioselectivity were discussed.
Unsaturated hydrocarbons undergo various reactions
in the presence of transition metal catalysts, and a large
number of useful reactions has been developed.1 Among
them, the transition metal-catalyzed cyclotrimerization
of alkynes is a well-known reaction (eq 1).2 The previous
studies have revealed that the high regioselectivity of the
reaction was achieved mainly in the (partially) intra-
molecular reactions, and it is difficult to achieve high
regioselectivity in the intermolecular reactions.
Recently, we reported the nickel-catalyzed zipper an-
nulation of 2-substituted enynes and realized the unique
reactivity of the electron-deficient enynes such as 2-per-
fluoroalkylenynes in the presence of nickel catalysts (eq
2).3 To examine the effect of the substitution pattern on
the reactivity of enynes, we carried out the reaction of
1-perfluoroalkylenynes in the presence of nickel catalysts
and observed the formation of cyclotrimerized products.
In this paper we report the highly regioselective cyclo-
trimerization of the 1-perfluoroalkylenynes in the pres-
ence of Ni(PPh3)4 (eq 3).
Resu lts
P r ep a r a tion of F lu or in a ted En yn es. The fluori-
nated enynes were prepared according to the procedures
shown in Schemes 1-3. Thus, monosubstituted perfluoro-
alkylenyne 1a and disubstituted perfluoroalkylenyne 1d
were prepared by the copper-mediated perfluorohexyl-
ation4 of (E)-1,2-diiodoethylene 85 followed by the Sono-
gashira coupling of the product 9 with alkynes (Scheme
1). Other disubstituted enynes (1b,c) were prepared from
the iodoperfluoroolefins 12, which were prepared by the
transition metal-catalyzed addition of 1-iodoperfluoro-
hexane to alkynes (Scheme 2).6 The procedure described
by Yamanaka et al.7 was generally followed to prepare
the 1-iodoperfluoroalkylolefin 16, which was converted
† Institute for Chemical Reaction Science.
‡ Department of Chemistry, Graduate School of Science.
(1) Collman, J . P.; Hegedus, L. S.; Norton, J . R.; Finke, R. G.
Principles and Applications of Organotransition Metal Chemistry;
University Science Books: Mill Valley, CA, 1987.
(2) Reviews: (a) Grothahn, D. B. Transition Metal Alkyne Com-
plexes: Transition Metal-Catalyzed Cyclotrimerization. In Compre-
hensive Organometallic Chemistry II; Abel, E. W.; Stone, F. G. A.;
Wilkinson, G., Eds., Hegedus, L. S., vol. Ed.; Pergamon: Oxford, 1995;
Vol. 12, pp 741-770. (b) Lautens, M.; Klute, W.; Tam, W. Chem. Rev.
1996, 96, 49-92. (c) Schore, N. E. Chem. Rev. 1988, 88, 1081-1119.
(d) Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23(8), 539-
644. (e) Maitlis, P. M. J . Organomet. Chem. 1980, 200, 161-176. (f)
Maitlis, P. M. Acc. Chem. Res. 1976, 9, 93-99. (g) Saito, S.; Yamamoto,
Y. Chem. Rev. 2000, 100, 2901-2916. For recent related examples,
see (h) Ozerov, O. V.; Ladipo, F. T.; Patrick, B. O. J . Am. Chem. Soc.
1999, 121, 7941-7942. (i) Sato, Y.; Ohshi, K.; Mori, M. Tetrahedron
Lett. 1999, 40, 5231-5234.
(4) Coe, P. L.; Milner, N. E.; Smith, J . A. J . Chem. Soc., Perkin
Trans. 1 1975, 654-656.
(5) Wright, M. E.; Lowe-Ma, C. K. Organometallics 1990, 9, 347-
(3) Saito, S.; Tanaka, T.; Koizumi, T.; Tsuboya, N.; Itagaki, H.;
Kawasaki, T.; Endo, S.; Yamamoto, Y. J . Am. Chem. Soc. 2000, 122,
1810-1811.
352.
(6) Ishihara, T.; Kuroboshi, M.; Okada, Y. Chem. Lett. 1986, 1895-
1896.
10.1021/jo0056242 CCC: $20.00 © 2001 American Chemical Society
Published on Web 01/10/2001

Highly Regioselective Cyclotrimerization
J . Org. Chem., Vol. 66, No. 3, 2001 797
Sch em e 1
Sch em e 3
2b, and (E)-2-phenyl-1-perfluorohexyl-1-buten-3-yne (1c)
cyclotrimerized to give 2c. Though the cyclotrimerization
of a 2,4-disubstituted enyne (1d ) proceeded in a highly
regioselective manner, the reactivity of 1d was low, and
the reaction was carried out at 50 °C for 28.5 h (entry
4). The formation of isomeric benzenes was not observed
in the reactions of 1b-d .
To examine the effect of fluorine atom on the reactivity
of conjugated enynes, we carried out the reaction of a
1-fluoroenyne and observed the regioselective formation
of 1,2,4-trisubstituted benzenes. Thus, 1-fluoro-1-tetra-
decafluoropentyl-1-butene-3-yne (1e) cyclotrimerized in
the presence of Ni(PPh3)4 to give 1,2,4-trisubstituted
benzene 2e in 78% yield (entry 5). Compared to the
reaction of 1a , the rate of this reaction was slower. The
result is in contrast to the result of the reaction of 1,1-
difluoroenyne 1h : in the reaction of 1h , the formation
of a zipper annulation product 4, together with the
cyclotrimerized product 2h , was observed (eq 4).3
Sch em e 2
to 1-fluoro-1-perfluoroalkylenyne 17 by the Sonogashira
coupling, followed by the deprotection of the trimethyl-
silyl group (Scheme 3). The fluoroenynes 1a -e were
subjected to the nickel-catalyzed reaction.
Ni(0)-Ca ta lyzed Cyclotr im er iza tion of P er flu or o-
h exylen yn es. (E)-1-Perfluorohexyl-1-butene-3-yne (1a )
cyclotrimerized in the presence of a catalytic amount (10
mol %) of Ni(PPh3)4, which was prepared in situ from
Ni(cod)2 and PPh3, to give the 1,2,4-trisubstituted ben-
zene (2a ) in good yield (Table 1, entry 1). The reaction
proceeded in a highly regioselective manner, and only a
trace amount of the isomeric 1,3,5-trisubstututed benzene
(3a ) was detected in the reaction mixture. The formation
of a zipper annulation product (eq 2)3 was not observed.
We also carried out the reaction of disubstituted enynes
such as 1b-d , and the reaction of these enynes also
proceeded (Table 1, entries 2-4). Thus, (E)-2-hexyl-1-
perfluorohexyl-1-buten-3-yne (1b) cyclotrimerized to give
To examine the effect of other electron-withdrawing
groups on the reactivity of enynes, we carried out the
reaction of a cyanoenyne 1f. The corresponding 1,2,4-
trisubstituted benzene was isolated in a regioselective
manner (entry 6). On the other hand, the formation of a
significant amount of the 1,3,5-trisubstituted benzene 3,
together with the 1,2,4-trisubstituted benzene 2g, was
observed in the reaction of a methoxycarbonylenyne 1g
(entry 7). It is noteworthy that the [4 + 2] cycloaddition
(benzannulation) of 1f proceeded in the presence of
Pd(PPh3)4.8
Ni(0)-Ca ta lyzed Cocyclotr im er iza tion of (E)-2-
H exyl-1-p er flu or oh exyl-1-b u t en -3-yn e (1b ) w it h
(7) Yamanaka, H.; Araki, T.; Kuwabara, M.; Fukunishi, K.; Nomura,
M. Nihon Kagaku Kaishi 1986, 10, 1321-1328.

798 J . Org. Chem., Vol. 66, No. 3, 2001
Ta ble 1. Ni(0)-Ca ta lyzed Regioselective Cyclotr im er iza tion of F lu or oen yn es
Saito et al.
enyne
R1Z
reaction conditions
temp (°C) time (h)
entry
R1E
R2
R4
product
yield (%)
1
2
3
4
5
6
7
1a
1b
1c
1d
1e
1f
n-C6F13
n-C6F13
n-C6F13
n-C6F13
(CF2)7H
CN
H
H
H
H
F
H
H
H
H
rt
rt
rt
50
rt
rt
0.25
2
0.25
28.5
5.5
3.5
2a
2b
2c
2d
2e
2f
65a
88
67
47
78
n-C6H13
Ph
H
H
n-C5H11
H
n-C6H13
H
H
H
H
79
1g
COOMe
n-C6H13
80
30
2g
60 (16)b
a
b
A trace amount of isomeric 1,3,5-trisubstituted benzene 3a was isolated. Yield of the isomeric 1,3,5-trisubstituted benzene 3g.
Alk yn es. It is generally accepted that the cyclotrimer-
ization proceeds via the matallacyclopentadiene inter-
mediate, which was formed by the addition of two alkyne
molecules to the metal complex.2 The insertion (addition)
of the third alkyne moiety occurs, and substituted
benzene would be formed as the final product (eq 1). Since
the regioselective formation of the trisubstituted ben-
zenes was observed in the reactions we carried out, the
metallacyclopentadiene intermediate would be formed
regioselectively. However, the regiochemistry of the
matallacyclopentadiene in this reaction was not clear. To
determine the structure of the intermediate, which would
be closely related to the intermediate of the zipper
annulation reaction,3 we carried out the cocyclotrimer-
ization of (E)-2-hexyl-1-perfluorohexyl-1-buten-3-yne (1b)
with alkynes.
To isolate the cocyclodimerized product in a more
selective manner, we used a less reactive alkyne as a
substrate for the reaction. Compound 1b (1 equiv) and
(trimethylsilyl)acetylene (10 equiv) reacted in the pres-
ence of Ni(PPh3)4 (0.1 equiv) for 3.5 h and the formation
of a cocyclotrimer 7 was observed (eq 6). It is noteworthy
that 7 was the only cocyclotrimerized compound we
isolated and other benzene derivatives were not isolated.
Compound 7 was formed by the 2:1 cocyclotrimerization
of 1b with (trimethylsilyl)acetylene.
We chose enyne 1b, which is a moderately reactive
enyne, as a substrate, and carried out the cocyclotri-
merization in the presence of acetylene.1i Enyne 1b co-
cyclotrimerized with acetylene (1 atm) in the presence
of Ni catalyst, and the formation of a mixture of 2b, 5
and 6 was observed (eq 5). Compound 5 was formed by
the 2:1 cocyclotrimerization of 1b with acetylene, while
6 was formed by the 1:2 cocyclotrimerization of 1b with
acetylene.
Discu ssion s
It is difficult to achieve high regioselectivity in the
intermolecular cyclotrimerization of alkynes, and suc-
cessful examples have been reported in a limited number
of reactions.2 The Ni(0)-catalyzed cyclotrimerization of
alkylenynes has been reported, and the formation of the
cyclotrimerized compounds was observed, though the
reaction was carried out at elevated temperatures (50-
100 °C) and the isolated yields of cyclotrimerized products
were low.8 Our study revealed that the reaction of
1-perfluoroalkylenynes proceeded in highly regioselective
manner, and the benzene derivatives are isolated in good
(8) Meriwether, L. S.; Colthup, G. W.; Kennerly, G. W.; Reusch, R.
N. J . Org. Chem. 1961, 26, 5155-5163.

Highly Regioselective Cyclotrimerization
J . Org. Chem., Vol. 66, No. 3, 2001 799
Sch em e 4
Ch a r t 1
ally accepted mechanism of the cyclotrimerization reac-
tion,2 it is possible to attribute the high regioselectivity
to the highly regioselective formation of the nickelacyclo-
pentadienes. Considering the result of the reaction of 1b
with (trimethylsilyl)acetylene, the structure of the inter-
mediate will be limited (Scheme 4). Several intermediates
would be postulated as the intermediates of this reaction,
though three of them could produce the cocyclodimerized
product 7 which was isolated in the reaction. Metalla-
cycles such as 21 and 22 would not give 7, and the
formation of 23 or 24 is unlikely because it is well-known
that the Me3Si group generally occupy the R-position of
the metallacycles (Chart 1).2d Though we could not
completely exclude the possibility of the formation of 18
or 20 as the intermediate of this reaction, we assume that
19 is the intermediate in this reaction since no 2:1
cocyclotrimerization of 1b with (trimethylsilyl)acetylene
was observed in this reaction: if 18 or 20 was formed in
the reaction, the 2:1 cocyclotrimerization of 1b with
(trimethylsilyl)acetylene should occur (Scheme 4).12,13
Thus, the structure of the intermediate would be 19. The
result of this reaction provided an indirect evidence for
the structure of the metallacycle in the cyclotrimerization
of 1b and the zipper annulation of 1h and 2-perfluoro-
hexyl-1-butenyne.3
yields. The high reactivity of the conjugated enynes was
also observed, and this result is in accordance with our
postulation that the reactivity of the electron-deficient
hydrocarbons is significantly enhanced in the Pd(0)- or
Ni(0)-catalyzed reactions.3,9
Compared to the reaction of monosubstituted enyne 1a ,
the reaction of disubstituted enyne 1b proceeded more
sluggishly (Table 1, entry 2). We assume that the
reactivity of 1b was reduced because an electron-donating
group (alkyl group) was introduced to the enyne. Alter-
natively, the introduction of another substituent might
have caused a steric repulsion between the catalyst and
the substrate, which might have resulted in the lower
rate of the reaction. On the other hand, when we
introduced a phenyl group, which is a weak electron-
withdrawing group, to the enyne, the electronic effect and
the steric effect seem to be canceled out. As a result, the
rate of reaction of phenylenyne 1c was comparable to that
of the monosubstituted enyne 1a . The reactivity of 1d
was much lower compared to those of 1a ,b, probably
because the substituent was directly attached to the
“reactive” triple bond: the substituent would cause a
stronger steric repulsion during the reaction (entry 4).
It would also be possible to explain the low reactivity of
1g in terms of the strong steric effect (entry 7). Generally,
the reactivity of the perfluoroalkyl enynes seems to be
higher than that of other electron-deficient enynes in this
reaction (entry 3 vs 6, and entry 4 vs 7). The introduction
of a fluorine atom resulted in the reduced reactivity of
the enyne, probably because of the strong electron-
donating ability of the fluorine atom through the reso-
nance effect (entry 5).10,11
Though we expected that a bicyclic compound (zipper
annulation product) similar to 4 would be isolated in the
reactions of 1, we did not detect the bicyclic compound
in the reactions. We assume that the large steric hin-
drance between the 1-perfluoroalkyl group and the ligand
(PPh3) inhibited the reductive elimination of the Ni
species from the nickelacycle (Scheme 5).14,15
The low regioselectivity was observed in the cyclotri-
merization of a methoxycarbonylenyne 1g (entry 7). We
assume that the formation of the 1,3,5-trisubstituted
benzene was induced by the relatively strong resonance
effect of the methoxycarbonyl group.16 Thus, the elec-
tronic structure of the triple bond of 1g is different from
other enynes because of the relatively strong resonance
effect,9,17 and the formation of the isomeric nickelacycle
occurred. The nickelacycle similar to 27 would be formed
(12) This type of the reaction was observed in the cocyclotrimeriza-
tion of 1b with acetylene, which is a less sterically demanding alkyne
(eq 5).
(13) Favorable electronic interaction would also be expected in the
reaction of electron-deficient nickelacycle 19 with (trimethylsilyl)-
acetylene.
The high regioselectivity observed in the cyclotrimer-
ization indicates that the intermediates were formed in
highly regioselective manners. On the basis of the gener-
(14) In fact, we did not isolate the zipper annlation product in the
Ni(0)-catalyzed reactions of various 1-substituted enynes except for
1h .
(15) Alternatively, the result might be explained in terms of the
smaller electronic effects of the substitutents attached to the C-1
position on the reactive triple bond.
(16) Field value (F) ) 0.34, resonance value (R) ) 0.11.
(17) F ) 0.42, R ) 0.06 (values of CF2CF2CF3). F ) 0.51, R ) 0.15
(values of CN).
(9) (a) Saito, S.; Tsuboya, N.; Chounan, Y.; Nogami, T.; Yamamoto,
Y. Tetrahedron Lett. 1999, 40, 7529-7532. (b) Saito, S.; Chounan, Y.;
Nogami, T.; Fukushi, T.; Tsuboya, N.; Yamada, Y.; Kitahara, H.;
Yamamoto, Y. J . Org. Chem. 2000, 64, 5350-5354.
(10) Field value (F) ) 0.45, resonance value (R) ) -0.39. The values
shown in this paper were collected from ref 11.
(11) Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165-
195.

800 J . Org. Chem., Vol. 66, No. 3, 2001
Saito et al.
Sch em e 5
observed in these reactions was explained in terms of the
highly regioselective formation of the nickelacycles.
Exp er im en ta l Section
Compounds 1f9 and 1g19 were prepared according to the
literature.
1-Iod o-3,3,4,4,5,5,6,6,7,7,8,8,8-tr id eca flu or o-(1E)-eth yl-
en e (9). The general procedure4 was followed to prepare 9. A
mixture of perfluorohexyl iodide (29.0 g, 65 mmol), copper
powder (9.7 g, 153 mmol), and (E)-1,2-diiodoethylene 85 (30.8
g, 110 mmol) in DMF (45 mL) was heated at 120 °C for 71 h
under an argon atmosphere. The cooled mixture was poured
into ether, and the precipitate was removed by filtration. The
filterate was washed with water, 10% aq Na2SO3 and brine.
The organic layer was dried over MgSO4 and evaporated. The
mixture was cooled in a refrigerator, and the unreacted 8,
which crystallized out, was removed by filteration. The mixture
was further purified by distillation (70 °C/33 mmHg) to give 9
(5.2 g, 17%) as a colorless oil: 1H NMR (300 MHz, CDCl3)
7.43-7.37 (m, 1H), 6.76-6.63 (m, 1H); 13C NMR (75 MHz,
CDCl3) 131.9 (dd, J C-F ) 24.0, 24.0 Hz), 123.5-104.3 (m), 91.1
(dd, J C-F ) 11.5, 11.5 Hz); IR (neat) 3080, 1614, 1366, 1292,
1240, 1202, 1146, 1121, 1067 cm-1
; HRMS Calcd for
C8H2F13I: 471.8992. Found: 471.8969. Anal. Calcd for
C8H2F13I: C, 20.36; H, 0.43. Found: C, 20.65; H, 0.60.
5,5,6,6,7,7,8,8,9,9,10,10,10-Tr id eca flu or o-1-t r im et h yl-
silyl-(3E)-bu ten -1-yn e (10). To a mixture of Pd(PPh3)4 (60
mg, 0.052 mmol) and CuI (20 mg, 0.105 mol) was added a
mixture of Et2NH (4.8 mL, dried with KOH) and 9 (1.89 g, 4.0
mmol) under an argon atmosphere at room temperature. The
temperature was raised to 40 °C, (trimethylsilyl)acetylene was
added slowly, and the mixture was stirred for 20 min. The
mixture was cooled, poured into iced water, and extracted with
pentane. The combined organic layer was washed with 2 N
aq HCl, dried over MgSO4, and evaporated carefully to give a
yellow oil. The oil was further purified by silica gel column
chromatography (hexane) to give 10 (1.41 g, 80%) as a colorless
oil: 1H NMR (300 MHz, CDCl3) 6.31-6.24 (m, 1H), 6.16-6.02
(m, 1H), 0.20 (s, 9H); 13C NMR (75 MHz, CDCl3) 127.2 (dd,
J C-F ) 22.7, 22.7 Hz), 123.4-104.2 (m) 120.9 (dd, J C-F ) 11.2,
11.2 Hz), 103.6, 99.3, -0.5; IR (neat) 2966, 2905, 2164, 1638,
1412, 1240, 1202, 1146, 1128, 1078, 1051 cm-1; HRMS Calcd
for C13H11F13Si: 442.0421. Found: 442.0411. Anal. Calcd for
Sch em e 6
C
13H11F13Si: C, 35.30; H, 2.51. Found: C, 35.48; H, 2.63.
5,5,6,6,7,7,8,8,9,9,10,10,10-Tr id eca flu or o-(3E)-bu ten -1-
yn e (1a ). To a mixture of KF (0.45 g, 7.8 mmol) in MeOH (19
mL) was slowly added 10 (2.3 g, 5.2 mmol) at 0 °C under an
argon atmosphere, and the mixture was kept stirring for 30
min. Water was added, and the mixture was extracted with
pentane. The organic layer was washed with brine and dried
over MgSO4. Pentane was removed at normal pressure, and
the residue was further purified by distillation to give 1a (0.45
g, 23%) as a colorless oil: 1H NMR (300 MHz, CDCl3) 6.31-
6.11 (m, 2H), 3.26 (m, 1H); 13C NMR (67.8 MHz, CDCl3) 128.7
(dd, J C-F ) 22.6, 22.6 Hz), 123.5-104.2 (m), 84.7 (m), 78.4; IR
(neat) 3317, 1641, 1364, 1240, 1202, 1146, 1124, 1069 cm-1
;
HRMS Calcd for C10H3F13: 370.0027. Found: 370.0009. Anal.
Calcd for C10H3F13: C, 32.45; H, 0.82. Found: C, 32.29; H, 1.11.
1,1,2,2,3,3,4,4,5,5,6,6,6-Tr id eca flu or o-(7E)-h exa d ecen -9-
yn e (1d ). To the mixture of Pd(PPh3)4 (15 mg, 0.013 mmol)
and CuI (5 mg, 0.026 mmol) was added a mixture of Et2NH
(1.2 mL, dried over KOH) and 10 (0.47 g, 1 mmol) under an
argon atmosphere at 40 °C. Trimethylsilylacethlene was added
slowly, and the mixture was stirred for 3 h. The mixture was
cooled, poured into iced water, and extracted with pentane.
The organic layer was washed with 2 N aq HCl, dried over
MgSO4, and evaporated to give an orange oil. The oil was
further purified by silica gel column chromatography (hexane)
to give 1d (0.24 g, 51%) as a colorless oil: 1H NMR (300 MHz,
CDCl3) 6.30-6.23 (m, 1H), 6.03-5.90 (m, 1H), 2.33 (dd, J )
6.5, 6.5 Hz, 2H), 1.56-1.49 (m, 2H), 1.38-1.23 (m, 6H), 0.88
in the reaction of 1g, and the isomeric 1,3,5-trisubstituted
benzene 3g would be isolated (Scheme 6).18
Con clu sion s
We have shown that the Ni(0)-catalyzed cyclotrimer-
ization of 1-perfluoroalkylenynes proceeded under mild
conditions, and the 1,2,4-trisubstituted benzenes were
isolated in high regioselectivity. We also carried out the
cocyclization of an enyne with alkynes and isolated the
cocyclotrimerized products. The high regioselectivity
(18) The increased steric effects could be another possible explana-
tion for the observed low regioselectivity in the reaction of 1g. We thank
the referee for pointing out this possibility.
(19) Krause, N. Chem. Ber. 1990, 123, 2173-2180.

Highly Regioselective Cyclotrimerization
J . Org. Chem., Vol. 66, No. 3, 2001 801
(dd, J ) 6.8, 6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3) 125.2
(dd, J C-F ) 22.4, 22.4 Hz), 121.7 (dd, J C-F ) 11.2, 11.2 Hz),
123.1-104.8 (m), 99.3, 76.2, 31.4, 28.6, 28.3, 22.6, 19.5, 13.9;
IR (neat) 2963, 2936, 2864, 2224, 1639, 1472, 1458, 1364, 1240,
122.0 (dd, J C-F ) 21.2, 21.2 Hz), 119.6-106.6 (m), 83.1, 82.9;
19F NMR (254 MHz, CDCl3) -126.7 to -126.6 (m, 2F), -123.4
(m, 4F), -122.2 to -122.1 (m, 2F), -105.3 to -105.2 (m, 2F),
-81.3 (dd, J ) 9.2, 9.2 Hz, 3F); IR (neat) 3312, 3088, 3065,
3030, 2106, 1624, 1238, 1202, 1146, 1123, 1070 cm-1; HRMS
Calcd for C16H7F13: 446.0339. Found: 446.0315. Anal. Calcd
for C16H7F13: C, 43.07; H, 1.58. Found: C, 43.12; H, 1.75.
1-Iod o-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-h e xa d e ca flu or o-
n on a n e (15). To a mixture of PPh3 (59.0 g, 225 mmol) and
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1-nonanol 14 (64.8
g, 150 mmol) was added DMF (188 mL) under an argon
atmosphere. To this mixture was slowly added a mixture of I2
(57.1 g, 225 mmol) and DMF (150 mL) under 60 °C while
stirring. When the addition was completed, the temperature
was raised to 100 °C, and the mixture was stirred at this
temperature for 18 h. Et2O was added, and the organic layer
was washed with Na2SO3 (10%, aqueous). The aqueous layer
was extracted with Et2O. The combined organic layer was
washed with saturated brine, dried over Na2SO4, and evapo-
rated. The resiude was further purified by silica gel column
chromatography (hexane) to give 15 (58.5 g, 72%) as white
1202, 1146, 1121, 1065 cm-1; HRMS Calcd for C16H15F13
454.0965. Found: 454.0982.
:
8-Iod o-1,1,2,2,3,3,4,4,5,5,6,6,6-t r id eca flu or o-(7E)-t et -
r a d ecen e (12b). The general procedure reported in a refer-
ence6 was followed to prepare 12b: yield 82%; colorless oil,
bp 91 °C (1.9 mmHg).
1-Iod o-2-p h en yl-3,3,4,4,5,5,6,6,7,7,8,8,8-t r id eca flu or o-
(1E)-octen e (12c). The general procedure reported in the
reference6 was followed to prepare 12c (yield 37%) as a lemon
1
yellow oil: bp 97 °C (1.9 mmHg); H NMR (300 MHz, CDCl3)
7.37-7.25 (m, 5H), 6.57 (dd, J ) 13.5, 13.5 Hz, 1H); 13C NMR
(75 MHz, CDCl3) 141.4, 129.3, 128.0, 127.0 (dd, J C-F ) 22.4,
22.4 Hz), 126.9, 124.1-105.7 (m), 112.8 (dd,J C-F ) 6.2, 6.2 Hz);
IR (KBr) 1643, 1491, 1445, 1400, 1366, 1342, 1256, 1217, 1196,
1140, 1117, 1065, 1030 cm-1. Anal. Calcd for C14H6F13I: C,
30.68; H, 1.10. Found: C, 30.98; H, 1.34.
3-Hexyl-1-tr im eth ylsilyl-5,5,6,6,7,7,8,8,9,9,10,10,10-tr i-
d eca flu or o-(3E)-bu ten -1-yn e (13b). To a mixture of Pd-
(PPh3)4 (105 mg, 0.091 mmol) and CuI (35 mg, 0.18 mmol) was
added a mixture of Et2NH (8.4 mL, dried over KOH) and 12b
(3.9 g, 7 mmol) under an argon atmosphere at 40 °C. Then
trimethylsilylacethlene was added dropwise, and the mixture
was stirred for 70 min. The mixture was cooled, poured into
iced water, and extracted with hexane. The organic layer was
washed with 2 N aq HCl, dried over MgSO4, and evaporated
to give an orange oil. The oil was further purified by silica gel
column chromatography (hexane) to give 13b (3.46 g, 94%) as
a colorless oil: 1H NMR (300 MHz, CDCl3) 5.81 (dd, J ) 15.6,
15.6 Hz, 1H), 2.33 (dd, J ) 6.5, 6.5 Hz, 1H), 1.56-1.52 (m,
2H), 1.29(s, broad, 6H),0.90-0.85 (m, 3H), 0.19 (s, 9H); 13C
NMR (75 MHz, CDCl3) 139.0 (dd, J C-F ) 5.3, 5.3 Hz), 123.0-
105.3 (m), 121.0 (dd, J C-F ) 23.3, 23.3 Hz), 103.9, 99.1, 32.3,
31.6, 28.8, 28.3, 22.5, 14.0, -0.4; IR (neat) 2963, 2934, 2864,
2152, 1628, 1456, 1364, 1313, 1240, 1202, 1146, 1121, 1105
cm-1; HRMS Calcd for C19H23F13Si: 526.1360. Found: 526.1359.
Anal. Calcd for C19H23F13Si: C, 43.34; H, 4.40. Found: C,
43.27; H, 4.48.
3-P h en yl-5,5,6,6,7,7,8,8,9,9,10,10,10-tr id eca flu or o-1-tr i-
m eth ylsilyl-(3E)-bu ten -1-yn e (13c). The procedure for the
preparation of 13b was generally followed. The mixture was
stirred for 40 min and worked up. Compound 13c (yield 95%)
was isolated as a pale lemon yellow oil: 1H NMR (300 MHz,
CDCl3) 7.35 (s, 5H), 6.11 (dd, J ) 15.1, 15.1 Hz, 1H), 0.18 (s,
9H); 13C NMR (75 MHz, CDCl3) 137.0 (dd, J C-F ) 5.0, 5.0 Hz),
135.4, 128.9, 128.1 (dd, J C-F ) 2.8, 2.8 Hz), 128.0, 120.9 (dd,
J C-F ) 20.8, 20.8 Hz), 119.5-107.3 (m), 104.0 (dd, J C-F ) 2.8,
2.8 Hz), 101.1; IR (neat) 3088, 3063, 3030, 2964, 2903, 2856,
2151, 1622, 1495, 1447, 1364, 1313, 1238, 1198, 1146, 1123
cm-1. Anal. Calcd for C19H15F13Si: C, 44.02; H, 2.92. Found:
C, 43.93; H, 3.10.
2-Hexyl-1,1,2,2,3,3,4,4,5,5,6,6,6-tr idecaflu or o-(7E)-bu ten -
9-yn e (1b). The procedure for the preparation of 1a was
generally followed. The mixture was stirred at rt for 2 h,
worked up, and purified to give 1b (100% yield) as a colorless
oil: 1H NMR (300 MHz, CDCl3) 5.86 (dd, J ) 15.5, 15.5 Hz,
1H), 3.10 (s, 1H), 2.35 (dd, J ) 7.7, 7.7 Hz, 2H), 1.57 (dd, J )
7.2, 7.2 Hz, 2H) 1.33-1.25 (m, 6H), 0.89-0.85 (m, 3H); 13C
NMR (75 MHz, CDCl3) 138.2 (dd, J C-F ) 5.6, 5.6 Hz), 123.0-
107.0 (m), 122.1 (dd, J C-F ) 23.3, 23.3 Hz), 82.8, 81.0, 32.3,
31.5, 28.8, 28.2, 22.5, 13.9; IR (neat) 3314, 2963, 2936, 2864,
2106, 1634, 1470, 1364, 1300, 1240, 1202, 1146, 1121, 1107
cm-1; HRMS Calcd for C16H15F13: 454.0965. Found: 454.0969.
Anal. Calcd for C16H15F13: C, 42.30; H, 3.33. Found: C, 42.23;
H, 3.46.
3-P h en yl-5,5,6,6,7,7,8,8,9,9,10,10,10-tr id eca flu or o-(3E)-
bu ten -1-yn e (1c). The procedure for the preparation of 1a
was generally followed. The mixture was stirred at rt for 30
min, worked up, and purified to give 1c (83% yield) as a
colorless oil: 1H NMR (300 MHz, CDCl3) 7.36 (s, 5H), 6.18 (dd,
J ) 15.0, 15.0 Hz, 1H), 3.30 (s, 1H); 13C NMR (75 MHz, CDCl3)
136.2 (dd, J C-F ) 5.6, 4.3 Hz), 135.0, 129.2, 128.12, 128.05,
1
powder: mp 23.9-24.3 °C; H NMR (300 MHz, CDCl3) 6.04
(dddd, J ) 52, 52, 5.1, 5.1, Hz, 1H), 3.61 (dd, J ) 17.3, 17.3
Hz, 2H); 13C NMR (75 MHz, CDCl3) 118.4-105.4 (m), 107.6
(dddd, J C-F ) 255, 255, 31.5, 31.5 Hz), -4.3 (dd, J C-F ) 26.1,
26.1 Hz); IR (KBr) 1242, 1207, 1180, 1146 cm-1; HRMS Calcd
for C9H3F16I: 541.9022. Found: 541.9022. Anal. Calcd for
C9H3F16I: C, 19.94; H, 0.56. Found: C, 19.96; H, 0.78.
1-Iod o-2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-p en ta d eca flu or o-(1Z)-
n on en e (16). To a mixture of DMSO (40 mL) and 15 (21.5 g,
39.6 mmol) was added dropwise a solution of KOH (3.16 g) in
Et2O (40 mL) and for 30 min under an argon atmosphere, and
the mixture was stirred for 50 min. Water was added, and the
mixture was extracted with Et2O. The organic layer was
washed with brine, dried over Na2SO4, and evaporated. The
residue was further purified by distillation to give 16 (18.7 g,
90%) as a colorless oil: 1H NMR (300 MHz, CDCl3) 6.64 (d, J
) 30.8 Hz, 1H), 6.04 (dddd, J ) 52, 52, 5.1, 5.1 Hz, 1H); 13C
NMR (75 MHz, CDCl3) 152.4 (ddd, J C-F ) 264, 29.8, 29.8 Hz),
114.9-105.8 (m), 107.7 (dddd, J C-F ) 255, 255, 31.5, 31.5 Hz),
65.1 (m); IR (neat) 3107, 1663, 1402, 1315, 1265, 1207, 1146,
1070, 1011 cm-1; HRMS Calcd for C9H2F15I: 521.8960.
Found: 521.8961. Anal. Calcd for C9H2F15I: C, 20.71; H, 0.39.
Found: C, 20.92; H, 0.50.
4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-P en t a d eca flu or o-1-t r i-
m eth ysilyl-(3Z)-u n d ecen -1-yn e (17). To a mixture of Pd-
(PPh3)4 (75 mg, 0.065 mmol) and CuI (25 mg, 0.13 mmol) was
added a mixture of Et2NH (6.0 mL, dried over KOH) and 16
(2.6 g, 5 mmol) under an argon atmosphere at 40 °C. Tri-
methylsilylacetylene was added slowly, and the mixture was
stirred for 2 h. The mixture was cooled, poured into iced water,
and extracted with pentane. The organic layer was washed
with 2 N aq HCl, dried over MgSO4, and evaporated to give
brown oil. The oil was further purified by silica gel column
chromatography (pentane) to give 17 (2.0 g, 83%) as a colorless
oil: 1H NMR (300 MHz, CDCl3) 6.04 (dddd, J ) 52, 52, 5.1,
5.1 Hz, 1H), 5.72 (d, J ) 29 Hz, 1H), 0.21 (s, 9H); 13C NMR
(75 MHz, CDCl3) 153.7 (ddd, J C-F ) 277, 28.8, 28.8 Hz), 114.8-
106.6 (m), 108.2, 107.7 (dddd, J
) 255, 255, 31.6, 31.6 Hz),
C-F
97.5 (dd, J C-F ) 14.6, 5.9 Hz), 92.3, -0.7; IR (neat) 3076, 2966,
2905, 2156, 1672, 1402, 1356, 1256, 1209, 1167, 1146, 1065
cm-1. Anal. Calcd for C14H11F15Si: C, 34.16; H, 2.25. Found:
C, 34.01; H, 2.18.
4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-P en t a d eca flu or o-(3Z)-
u n d ecen -1-yn e (1e). The procedure for the preparation of 1a
was generally followed. The mixture was stirred at rt for 15
min, worked up, and purified to give 1e (72% yield) as a pale
yellow oil: 1H NMR (300 MHz, CDCl3) 6.04 (dddd, J ) 52, 52,
5.1, 5.1 Hz, 1H), 5.72 (dd, J ) 29.0, 2.6 Hz, 1H), 3.42 (m, 1H);
13C NMR (75 MHz, CDCl3) 155.0 (ddd, J C-F ) 278, 28.9, 28.9
Hz), 115.1-106.7 (m), 107.8 (dddd, J C-F ) 255, 255, 31.6, 31.6
Hz), 96.6 (dd, J C-F ) 14.3, 6.2 Hz), 88.6 (d, J C-F ) 6.8 Hz),
71.9; 19F NMR (254 MHz, CDCl3) -137.5 (d, J ) 55.5 Hz, 2F),
-129.8 (s, 2F), -123.8 (m, 2F), -123.3 (m, 2F), -122.5 (m,
4F), -118.8 (dd, J ) 24.0, 12.9 Hz, 2F), -113.9 (m, 1F); IR

802 J . Org. Chem., Vol. 66, No. 3, 2001
Saito et al.
(neat) 3315, 3086, 2124, 1678, 1402, 1358, 1207, 1167, 1146,
8.2 Hz, 1H), 7.67 (dd, J ) 8.3, 1.3 Hz,1H), 6.50 (d, J ) 32.8
Hz, 1H), 6.47 (d, J ) 33.0 Hz, 1H), 6.40 (d, J ) 34.8 Hz, 1H),
6.04 (dddd, J ) 52, 52, 5.1, 5.1 Hz, 1H), 6.03 (dddd, J ) 52,
52, 5.1, 5.1 Hz, 2H); 13C NMR (75 MHz, THF-d8) 147.3 (ddd,
J C-F ) 271, 28.3, 28.3 Hz), 147.2 (ddd, J C-F ) 270, 28.8, 28.8
Hz), 146.9 (ddd, J C-F ) 270, 28.6, 28.6 Hz), 132.3-130.4 (m),
116.2-105.5 (m); 19F NMR (254 MHz, CDCl3) -137.6 to -137.4
(m, 6F), -129.9 to -129.8 (m, 6F), -123.9 to -122.5 (m, 27F),
-118.1 to -117.8 (m, 6F); IR (KBr) 3086, 3013, 1692, 1497,
1402, 1369, 1275, 1198, 1157, 1142, 1086, 1018 cm-1. Anal.
Calcd for C33H9F45: C, 31.45; H, 0.72. Found: C, 31.27; H, 0.97.
(E)-3-[3,4-Bis{(E)-2-cya n o-1-p en tylvin yl}p h en yl]-oct-2-
en en itr ile (2f): yellow powder (58.0 mg, 79%), mp 75.4-78.3
°C;1H NMR (300 MHz, CDCl3) 7.42 (dd, J ) 8.0, 1.8 Hz, 1 H),
7.22 (d, J ) 8.0 Hz, 1H), 7.16 (d, J ) 1.8 Hz, 1H), 5.54 (s, 1H),
5.36 (s, 2H), 2.85 (t, J ) 7.6 Hz, 2H), 2.70 (bs, 4H), 1.45-1.26
(m, 18H), 0.87-0.82 (m, 9H); 13C NMR (75 MHz, CDCl3) 165.8,
165.4, 162.9, 138.8, 138.2, 137.7, 129.8, 127.1, 127.0, 117.0,
116.0, 115.8, 100.1, 99.9, 97.4, 35.5, 35.4, 33.6, 31.2, 31.1, 28.0,
27.7, 27.6, 22.14, 22.09, 13.74, 13.70; IR (KBr) 2953, 2928,
2860, 2214, 1609, 1468, 1456, 1404, 1379, 1325, 850, 826, 723
cm-1; HRMS. Calcd for C30H39N3: 441.3143. Found: 441.3147.
Anal. Calcd for C30H39N3: C, 81.59; H, 8.90; N, 9.51. Found:
C, 81.51; H, 9.12; N, 9.36.
(E)-3-[2,3,6-Tr ih exyl-4,5-b is{(E)-2-m et h oxyca r b on yl-
vin yl)p h en yl]a cr ylic a cid m eth yl ester (2g): yellow pow-
der (58.1 mg, 60%); mp 48.7-50.2 °C; 1H NMR (300 MHz,
CDCl3) 7.84 (d, J ) 16.3 Hz, 1H), 7.77 (d, J ) 16.3 Hz, 1H),
7.72 (d, J ) 16.3 Hz, 1H), 5.96 (d, J ) 16.3 Hz, 1H), 5.88 (d,
J ) 16.3 Hz, 2H), 3.80 (s, 3H), 3.77 (s, 3H), 3.76 (s, 3H), 2.52
(bs, 6H), 1.35-1.22 (m, 24H), 0.86-0.81 (m, 9H); 13C NMR (75
MHz, CDCl3) 166.51, 166.45, 166.38, 144.7, 144.4, 144.0, 139.5,
137.5, 136.9, 135.9, 134.1, 131.6, 125.3, 125.1, 124.5, 51.73,
51.68, 51.65, 31.31, 31.30, 31.2, 30.7, 30.5, 30.3, 30.1, 29.8, 29.7,
29.6, 29.2, 22.5, 22.4, 13.98, 13.95; IR (KBr) 2953, 2922, 2858,
1720, 1641, 1470, 1435, 1313, 1273, 1194, 1171, 1013, 986, 949,
858, 677 cm-1; HRMS. Calcd for C36H54O6: 582.3921. Found:
582.3886. Anal. Calcd for C36H54O6: C, 74.19; H, 9.34. Found:
C, 74.19; H, 9.40.
(E)-3-[2,4,6-Tr ih exyl-3,5-b is{(E)-2-m et h oxyca r b on yl-
vin yl}p h en yl]a cr ylic a cid m eth yl ester (3g): yellow pow-
der (16.0 mg, 16%); mp 43.5-47.1 °C; 1H NMR (300 MHz,
CDCl3) 7.76 (d, J ) 16.3 Hz, 3H), 5.91 (d, J ) 16.3 Hz, 3H),
3.75 (s, 9H), 2.47-2.41 (m, 6H), 1.33-1.16 (m, 24H), 0.78 (t, J
) 6.7 Hz, 9H); 13C NMR (75 MHz, CDCl3) 166.5, 144.3, 138.6,
132.9, 124.5, 51.8, 31.2, 31.0, 30.0, 29.3, 22.5, 14.0; IR (KBr)
2955, 2858, 1724, 1651, 1645, 1456, 1310, 1277, 1196, 1169,
989 cm-1; HRMS. Calcd for C36H54O6: 582.3921. Found:
582.3891. Anal. Calcd for C36H54O6: C, 74.19; H, 9.34. Found:
C, 74.26; H, 9.36.
1,2,4-Tr is(1-n on yl-2,2-diflu or oeth ylen yl)ben zen e (4): pale
yellow oil; 1H NMR (300 MHz, CDCl3) 7.27 (d, J ) 7.5 Hz,
1H), 7.19 (d, J ) 8.3 Hz, 1H), 7.14 (s, 1H), 2.39 (m, 2H), 2.24
(m, 4H), 1.26-1.24 (m, 42H), 0.87 (m, 9H); 13C NMR (75 MHz,
CDCl3) 157.6-149.3 (m), 133.5, 133.4, 132.2, 131.0, 130.8,
127.4 (dd, J C-F ) 3.1, 3.1 Hz), 92.2-91.4 (m), 31.9, 29.6, 29.3,
29.25, 29.19, 29.0, 28.2, 28.1, 27.8, 27.6, 27.5, 27.3, 22.7, 14.1;
19F NMR (254 MHz, CDCl3) -94.2 to -93.7 (m, 2F), -91.2 to
-91.6 (d, J ) 18.5 Hz, 2F), -90.2 to -90.0 (m, 2F); IR (neat)
2957, 2926, 2856, 1792, 1732, 1653, 1645, 1607 cm-1; HRMS
Calcd for C39H60F6: 642.4596. Found: 642.4622. Anal. Calcd
for C39H60F6: C, 72.86; H, 9.41. Found: C, 72.94; H, 9.16.
1040 cm-1; HRMS Calcd for C11H3F15
: 419.9995. Found:
419.9980. Anal. Calcd for C11H3F15: C, 31.45; H, 0.72. Found:
C,31.22; H, 0.91.
Nick el(0)-Ca ta lyzed Rea ction of Con ju ga ted En yn es.
A Rep r esen ta tive P r oced u r e. To a dark red mixture of
Ni(cod)2 (13.8 mg, 0.05 mmol) and PPh3 (53 mg, 0.2 mmol) in
dry toluene (0.25 mL) was added a solution of 1a (185 mg, 0.5
mmol) in dry toluene (0.25 mL) at room temperature, and the
mixture was stirred for 15 min. The mixture was passed
through a short alumina column (pentane) and evaporated.
The residue was further purified by MPLC (hexane) to give
2a (124 mg, 65%) as a pale yellow oil.
1,2,4-Tr is(3,3,4,4,5,5,6,6,7,7,8,8,8-t r id e ca flu or o-(1E )-
1
octen yl)ben zen e (2a ): pale yellow oil; H NMR (300 MHz,
CDCl3) 7.54-7.53 (m, 3H), 7.43-7.33 (m, 2H), 7.22-7.15 (m,
1H), 6.35-6.06 (m, 3H); 13C NMR (75 MHz, CDCl3) 138.0 (dd,
J C-F ) 9.4, 9.4 Hz), 136.5 (dd, J C-F ) 9.6, 9.6 Hz), 136.2 (dd,
J C-F ) 9.7, 9.7 Hz), 135.3, 134.6, 134.1, 128.6, 128.5, 127.5,
123.4-104.6 (m); 19F NMR (254 MHz, CDCl3) -126.8 (s, 6F),
-123.9 to -123.8 (m, 4F), -123.6 to -123.5 (m, 8F), -122.2
(s, 6F), -112.4 (s, 4F), -112.1 to -112.0 (m, 2F), -81.5 to
-81.4 (m, 9F); IR (neat) 1655, 1364, 1238, 1200, 1146, 1121,
1067 cm-1. Anal. Calcd for C30H9F39
Found: C, 32.17; H, 1.06.
: C, 32.45; H, 0.82.
1,2,4-Tr is(1-h exyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tr id eca flu or o-
1
(1E)-octen yl)ben zen e (2b): yellow oil; H NMR (300 MHz,
CDCl3) 7.32 (dd, J ) 8.0, 1.8 Hz, 1H), 7.17 (d, J ) 8.1 Hz, 1H),
7.08 (d, J ) 1.8 Hz, 1H), 5.63 (dd, J ) 15.8, 15.8 Hz, 1H), 5.56
(dd, J ) 15.2, 15.2 Hz, 2H), 2.70 (m, 2H), 2.56 (m, 4H), 1.27-
1.19 (m, 24H), 0.87-0.77 (m, 9H); 13C NMR (75 MHz, CDCl3)
157.5 (dd, J C-F ) 4.7, 4.7 Hz), 157.2 (dd, J C-F ) 4.7, 4.7 Hz),
155.5 (dd, J C-F ) 4.7, 4.7 Hz), 141.3, 139.6, 139.5, 130.1, 127.8,
126.8, 123.5-104.3 (m), 117.1, 117.0, 114.9, 32.3, 31.5-31.3
(m), 29.3, 29.2, 28.6, 28.5, 28.4, 22.5, 13.80, 13.77, 13.73; 19F
NMR (254 MHz, CDCl3) -126.7 (m, 6F), -123.8 (m, 6F),
-123.4 (m, 6F), -122.1 (m, 6F), -106.3 (m, 4F), -105.6 (dd,
J ) 29.6, 29.6 Hz, 2F), -81.4 to -81.2 (m, 9F); IR (neat) 2963,
2934, 2864, 1651, 1470, 1363, 1313, 1240, 1200, 1146, 1121,
1103 cm-1. Anal. Calcd for C48H45F39
Found: C, 42.30; H, 3.52.
:
C, 42.30; H, 3.33.
1,2,4-Tr is(1-ph en yl-3,3,4,4,5,5,6,6,7,7,8,8,8-tr idecaflu or o-
1
(1E)-octen yl)ben zen e (2c): yellow oil; H NMR (300 MHz,
CDCl3) 7.37-7.09 (m, 14H), 6.80 (dd, J ) 7.1 Hz, 2H), 6.68 (d,
J ) 7.5 Hz, 2H), 6.06 (dd, J ) 14.5, 14.5 Hz, 1H), 5.81 (dd, J
13
) 14.8, 14.8 Hz, 2H); C NMR (75 MHz, CDCl3) 153.9 (m),
153.4 (dd, J C-F ) 4.4, 3.7 Hz), 152.8 (dd, J C-F ) 4.4, 4.4 Hz),
141.9, 141.3, 141.0, 136.8, 136.7, 136.5, 130.9-127.8 (m),
123.4-104.7 (m); 19F NMR (254 MHz, CDCl3) -126.7 (m, 6F),
-123.8 to -123.3 (m, 12F), -122.1 (m, 6F), -105.3 to -105.0
(m, 4F), -104.4 (dd, J ) 25.9, 14.8 Hz, 2F), -81.4 to -81.3
(m, 9F); IR (neat) 3063, 3030, 1639, 1497, 1447, 1366, 1302,
1236, 1198, 1144, 1121, 1103, 1063 cm-1. Anal. Calcd for
C
48H21F39: C, 43.07; H, 1.58. Found: C, 43.31; H, 1.77.
3,5,6-Tr ih exyl-1,2,4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tr idecaflu or o-
(1E)-octen yl)ben zen e (2d ): brown powder, mp 26.4-27.3 °C;
1H NMR (300 MHz, CD3COCD3) 7.67-7.46 (m, 3H), 6.23-5.97
(m, 3H), 2.66-2.56 (m, 6H), 1.43-1.27 (m 24H), 0.88-0.85 (m,
9H); 13C NMR (75 MHz, CDCl3) 139.8-130.8 (m), 123.4-106.3
(m), 31.5-29.4 (m), 22.6, 22.5, 13.9, 13.7; 19F NMR (254 MHz,
CDCl3) -126.7 (m, 6F), -123.5 (m, 12F), -122.3 (m 6F),
-112.9 (dd, J ) 25.9, 11.1 Hz, 4F), -112.4 (m, 2F), -81.3 to
-81.2 (m, 9F); IR (KBr) 2963, 2932, 2860, 1655, 1560, 1466,
1366, 1242, 1204, 1146, 1123, 1067 cm-1. Anal. Calcd for
Ack n ow led gm en t. This work was supported in part
by the J apan Securities Scholarship Foundation, Shi-
madzu Foundation, and J apan Bioindustry Association.
C
48H45F39: C, 42.30; H, 3.33. Found: C, 42.16; H, 3.27.
1,2,4-Tr is(2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-p en t a d eca flu or o-
(1Z)-n on en yl)ben zen e (2e): pale yellow powder, mp 73-
1
74 °C; H NMR (300 MHz, CDCl3) 7.80 (s, 1H), 7.73 (d, J )
J O0056242