A Facile Perfluoroallylation of Olefins

Article abstract of DOI:10.1021/jo9719766

The addition of F-allyl iodide to terminal alkenes is induced by a catalytic amount of copper powder in the absence of solvent at room temperature to 50°C to give the corresponding 1:1 adducts in good yields. A variety of functional groups such as trimethylsilyl, alkyl, epoxy, ester, hydroxyl, bromo, ether, and phosphonate are tolerated in the addition reaction. This reaction also worked well with internal olefins such as cyclohexene, cyclopentene, and 4-octene. Reaction with dienes gives the corresponding linear adduct and cyclization adduct depending on the chain length of the dienes. With 1,7-octadiene, a bis(perfluoroallyl) product is formed, while a tetrahydrofuran derivative is obtained with diallyl ether. Reduction of the adducts with zinc in the presence of nickel dichloride in moist THF or zinc in moist DMF affords the perfluoroallyl derivatives. The adduct reacts with zinc in DMF to form a zinc reagent which couples with organic electrophiles in the presence of CuBr.

Full text of DOI:10.1021/jo9719766

J . Org. Chem. 1998, 63, 2887-2891
2887
A F a cile P er flu or oa llyla tion of Olefin s
Ba V. Nguyen, Zhen-Yu Yang, and Donald J . Burton*
Department of Chemistry, University of Iowa, Iowa City, Iowa 52242
Received October 28, 1997
The addition of F-allyl iodide to terminal alkenes is induced by a catalytic amount of copper powder
in the absence of solvent at room temperature to 50 °C to give the corresponding 1:1 adducts in
good yields. A variety of functional groups such as trimethylsilyl, alkyl, epoxy, ester, hydroxyl,
bromo, ether, and phosphonate are tolerated in the addition reaction. This reaction also worked
well with internal olefins such as cyclohexene, cyclopentene, and 4-octene. Reaction with dienes
gives the corresponding linear adduct and cyclization adduct depending on the chain length of the
dienes. With 1,7-octadiene, a bis(perfluoroallyl) product is formed, while a tetrahydrofuran
derivative is obtained with diallyl ether. Reduction of the adducts with zinc in the presence of
nickel dichloride in moist THF or zinc in moist DMF affords the perfluoroallyl derivatives. The
adduct reacts with zinc in DMF to form a zinc reagent which couples with organic electrophiles in
the presence of CuBr.
In tr od u ction
Organofluorine compounds and their synthesis have
attracted much attention in the fields of biologically
active compounds and materials science.1 Although
perfluoroalkylation of organic molecules has been exten-
sively investigated with perfluoroalkyl iodides,2 few
reports of perfluoroallylation have been documented.
Recently, Burton and co-workers generated perfluoroal-
lylcadmium reagents from F-allyl iodide and cadmium.3
Metathesis of this cadmium reagent with cuprous halide
at low temperature gave the perfluoroallylcopper reagent.
These cadmium or copper reagents reacted readily with
allyl halides to form fluorinated dienes, but they did not
react with less reactive organic halides due to low
thermal stability. More recently, success achieved in the
addition of iododifluoroacetates4 and iododifluorometh-
ylphosphonate5 to functionalized alkenes initiated by
metals prompted us to examine the metal-initiated
addition of F-allyl iodide to alkenes as a general route to
perfluoroallylated products.
copper and the reduction of the adduct products with Zn/
NiCl2‚6H2O. This methodology provides a convenient
approach to perfluoroallyl compounds in good yields. We
now report the detailed methodology as well as a new
method for iodide reduction. We also report the forma-
tion of a zinc reagent from the addition product and its
reaction with electrophiles.
Resu lts a n d Discu ssion
Ad d ition of F-Allyl Iod id e to Olefin s. Addition of
perfluoroalkyl iodide to olefins can be readily achieved
by initiation with a variety of metals or metal com-
plexes.2e-k Among the metals, copper has been the most
widely used due to its low cost, reasonable reactivity, and
ease of purification of the final products.2m We found that
F-allyl iodide reacted readily with terminal alkenes in
the presence of a catalytic amount of copper powder, at
room temperature to 50 °C to give the corresponding
adducts in good yields as shown in Scheme 1. Although
the reaction could be carried out in solvent, the absence
of solvent greatly simplified isolation and purification of
the products. A variety of functionalized groups includ-
ing bromo, trimethylsilyl, ester, epoxy, phenoxy, hy-
droxyl, and phosphonate are tolerated under the reaction
conditions. For example, the addition of F-allyl iodide
to 1-hexene in the presence of Cu(0) at 50 °C in 4 h
produced 1,1,2,3,3-pentafluoro-5-iodo-1-nonene (1) in 80%
isolated yield. Similarly, reaction of F-allyl iodide with
4-penten-1-yl acetate, 1,2-epoxy-5-hexene, and diethyl
allylphosphonate gives 6,6,7,8,8-pentafluoro-4-iodo-7-
octen-1-yl acetate (13), 7,7,8,9,9-pentafluoro-1,2-epoxy-
5-iodo-8-nonene (15), and diethyl 4,4,5,6,6-pentafluoro-
2-iodo-5-hexenylphosphonate (14) in 82%, 79%, and 79%
yield, respectively. All examples of the addition reactions
In a preliminary report,6 we briefly described the
addition of F-allyl iodide to alkenes in the presence of
(1) (a) Hudlicky, M. Chemistry of Organofluorine Compounds, 2nd
ed.; Ellis, Horwood: Chichester, England, 1976. (b) Welch, J . T.
Tetrahedron 1987, 43, 3123.
(2) Addition of perfluoroalkyl iodides to alkenes initiated by heating,
photolysis, radical initiators, and metals: (a) Low, H. C.; Tedder, J .
M.; Walton, J . C. J . Chem. Soc. Faraday Trans. 1 1976, 72, 1300. (b)
Brace, N. O.; Van Elswyk, J . E. J . Org Chem. 1976, 41, 766. (c)
Tordeux, M.; Wakselman, C. Tetrahedron 1981, 37, 315. (d) Baum,
K.; Bedford, C. D.; Hunadi, R. J . J . Org. Chem. 1982, 47, 2251. (e)
Chen, Q. Y.; Yang, Z. Y. J . Chem. Soc., Chem. Commun. 1986, 498. (f)
Chen, Q. Y.; Yang, Z. Y. J . Fluorine Chem. 1985, 28, 399. (g) Chen, Q.
Y.; Yang, Z. Y. Acta Chim. Sin. 1986, 44, 265. (h) Von Werner, K. J .
Fluorine Chem. 1985, 28, 299. (i) Fuchikami, T.; Ojima, I. Tetrahedron
Lett. 1984, 25, 303. (j) Chen, Q. Y.; Yang, Z. Y.; Zhao, C. X.; Qiu, Z. M.
J . Chem. Soc. Perkin Trans. 1 1988, 563. (k) Chen, Q. Y.; Yang, Z. Y.;
Qiu, Z. M. Kexue Tongbao 1987, 593. (l) Lu, X.; Ma, S.; Zhu, J .
Tetrahedron Lett. 1988, 29, 5129. (m) Chen, Q. Y.; Yang, Z. Y. J .
Fluorine Chem. 1985, 28, 399.
(3) Burton, D. J .; Tarumi, Y.; Heinze, P. L. J . Fluorine Chem. 1990,
50, 257.
(4) (a) Yang, Z. Y.; Burton, D. J . J . Fluorine Chem. 1989, 45, 435.
(b) Yang, Z. Y.; Burton, D. J . J . Org. Chem. 1991, 56, 5125.
(5) Yang, Z. Y.; Burton, D. J . Tetrahedron Lett. 1991, 32, 1019.
(6) Yang, Z. Y.; Nguyen, B. V.; Burton, D. J . Synlett 1992, 2, 141.
S0022-3263(97)01976-2 CCC: $15.00 © 1998 American Chemical Society
Published on Web 04/17/1998

2888 J . Org. Chem., Vol. 63, No. 9, 1998
Nguyen et al.
Ta ble 1. P er flu or oa llyla tion of Alk en es
2.1 equiv of F-allyl iodide and copper powder at 50 °C,
the bis-adduct was isolated in 70% yield. On the other
hand, reaction of F-allyl iodide with diallyl ether and
copper under the same conditions afforded the cyclization
product 10 in 55% yield, which indicated that radical
intermediates are most likely involved in the addition
reaction. With divinyl ether, the reaction occurs rapidly
and exothermically at room temperature and produces
polymers which were not structurally characterized.
Copper powder also initiated the addition of F-allyl
iodide to internal olefins such as 4-octene, cyclohexene,
and cyclopentene. Upon reaction of F-allyl iodide with
1 equiv of cyclohexene in the presence of 33 mol % of
copper powder at 50 °C, the addition adduct 7 was
obtained in 73% yield as a 1:2 mixture of cis and trans
isomers as characterized by 19F NMR and GC-MS
analysis.
a
* The entry number is the product number. Isolated yields are
based on alkenes.
Red u ction of th e Ad d u cts. Organic iodides have
been reduced by numerous methods including transition-
metal catalysts7 and mixtures of metal hydrides and
Sch em e 1
metal salts, such as CoCl2, NiCl2, CuCl,10 CeCl3,11
RhCl3,12 TiCl3,13 and Zn/acid.14 These reagents not only
reduce the carbon-halogen bond, they are also capable
of reducing other functionalities. Radical dehalogenation
with tributyltin hydrides15 gives high yields and excellent
selectivity. However, traces of tributyltin iodide are often
difficult to remove from the reduced product.16 Recently
we reported that NiCl2‚6H2O/Zn could reduce R,R-diflu-
oro-γ-iodo esters4 and 1,1-difluoro-3-iodoalkylphospho-
nates5 to the corresponding R,R-difluoro esters and 1,1-
difluoro phosphonates in good yields.
8
9
are summarized in Table 1. However, with styrene,
F-allyl iodide only gave polymers under similar condi-
tions. In all cases no 1,5-perfluorohexadiene, via Wurtz
coupling, was detected. Copper powder, freshly prepared
via reaction of copper(II) sulfate and zinc in water,
exhibits higher reactivity than aged copper powder. The
reaction of F-allyl iodide and terminal alkenes occurs at
room temperature with freshly prepared copper (entries
4 and 18). However, the reaction required heating to 50
°C to initiate the reaction with aged copper powder.
Alcohols usually react with perfluoroolefins, particu-
larly in the presence of base. However, F-allyl iodide
smoothly added to olefins containing hydroxy groups in
the presence of copper. No side reactions, such as
reaction of the hydroxy group with F-allyl iodide or the
addition product, were observed. For example, when
neat 5-hexen-1,2-diol was treated with F-allyl iodide in
the presence of copper at room temperature, the addition
adduct (18) was isolated in 90% yield by silica gel
chromatography. 19F NMR spectroscopy indicated that
the adduct was a mixture of diastereomers. Similarly,
7-octen-1,2-diol gave the addition adduct (19) in 87%
isolated yield.
When the adducts were treated with Zn/NiCl2‚6H2O
in moist THF, reaction occurs rapidly and exothermically
(7) Pinder, A. R. Synthesis 1980, 425.
(8) (a) Satoh, T.; Suzuki, S.; Suzuki, Y.; Miyaji, Y.; Imai, Z.
Tetrahedron Lett. 1969, 4555. (b) Chung, S. K.; Han, G. Synth.
Commun. 1982, 12, 903.
(9) (a) Lin, S. T.; Roth, J . A. J . Org. Chem. 1979, 44, 309. (b) Back,
T. G.; Birass, V. I.; Edwards, V. I.; Krishna, M. V. J . Org. Chem. 1988,
53, 3815.
(10) Narisada, M.; Horibe, I.; Watanabe, F.; Takeda, K. J . Org.
Chem. 1989, 54, 5308.
(11) (a) Luche, J . L. J . Am. Chem. Soc. 1978, 100, 2226. (b) Rucker,
G.; Horster, H.; Gajewski, W. Synth. Commun. 1980, 10, 623.
(12) Nishiki, M.; Miyataka, H.; Niino, Y.; Mitsuo, N.; Satoh, T.
Tetrahedron Lett. 1982, 23, 193.
(13) Ashby, E. C.; Lin, J . J . J . Org. Chem. 1978, 43, 1263.
(14) Levene, P. A. Organic Syntheses; Wiley: New York, 1943;
Collect. Vol. 2, p 320.
(15) Newmam, W. P. Synthesis 1987, 665.
(16) Yang, Z. Y.; Burton, D. J . J . Org. Chem. 1992, 57, 4676.
Addition of F-allyl iodide to dienes affords linear bis-
adducts or cyclized adducts, depending on the chain
length of the dienes. When 1,7-octadiene reacted with

A Facile Perfluoroallylation of Olefins
J . Org. Chem., Vol. 63, No. 9, 1998 2889
Ta ble 2. Red u ction of Ad d ition P r od u cts
Sch em e 2
Sch em e 3
to produce reduced products with a significant amount
of dehydroiodination products (10-20%), as shown in
Scheme 2. Separation of these two products by simple
distillation was difficult. The formation of the dehydro-
iodination product is probably due to â-hydride elimina-
tion from an intermediate nickel complex, particularly
at elevated temperature. Fortunately, the elimination
side reaction could be minimized by addition of Et2O to
the reaction mixture and careful control of the reaction
temperature at 25 °C. When the adduct was treated with
Zn/NiCl2‚6H2O in moist THF/ether at 25 °C, the reduction
product was isolated in 92% yield without detectable
amounts of the elimination product. Although the exact
mechanism of the effect of ether is not clear, the ether
probably plays two roles in the nickel-catalyzed reaction.
First, ether may reduce the rate of oxidative addition of
the adducts to nickel due to its lower polarity than THF.
Second, ether may also inhibit reductive elimination of
the nickel complex intermediate. In fact, the reduction
reaction in THF/ether proceeded much more smoothly
than that in THF, and no exothermic reaction occurred
in THF/ether.
Since group VIII metals usually cause â-hydride elimi-
nation from alkyl halides, the formation of the elimina-
tion product could be avoided if the adducts were reacted
with zinc in the absence of nickel under appropriate
conditions. In fact, Knochel investigated the reaction of
alkyl halides with zinc to make the corresponding zinc
reagents without formation of the elimination product.17
We found that the adduct was readily reduced by
treatment with zinc in moist DMF at room temperature
as illustrated in Scheme 3. The reaction was conve-
niently monitored by 19F NMR. The AB quartet of
multiplets around -100.5 ppm (J F-F ) 275.0 Hz), the 19F
signal for the CF2 adjacent to the CH2, became a
multiplet at ca. -102.0 ppm when the reaction was
complete. Although the reduction of an adduct with zinc
in moist DMF occurs slower than with Zn/NiCl2‚6H2O
in THF, no elimination product was detected. Various
functional groups were tolerated under the reduction
conditions as shown in Table 2.
a
* The entry number is the product number. Isolated yields are
b
based on the 1:1 addition product. Zn/NiCl2‚6H2O in moist THF/
ether was used as the reducing reagent. c Zn/DMF/H2O was used
as the reducing reagent.
Sch em e 4
Zin c Rea gen ts fr om th e Ad d u cts. Reduction of an
adduct with zinc in moist DMF involves hydrolysis of an
organozinc intermediate. Knochel reported that alkyl
zinc reagents underwent metathesis with CuCN to form
intermediate copper-zinc reagents which react with
organic electrophiles to produce cross-coupled products.
If the zinc reagent was formed when the adduct reacted
with zinc in DMF, it would react with electrophiles in
the presence of CuBr. We found that the adduct could
couple with electrophiles on treatment with zinc and
CuBr. For example, upon reaction of the adduct with
acid-washed Zn in dry DMF at room temperature for 15
min, the adduct was completely consumed, as determined
by 19F NMR analysis. After addition of CuBr and
electrophiles, such as benzoyl chloride or allyl halide, the
resulting mixture was stirred at room temperature for 2
h to give high yields of the coupled products as illustrated
in Scheme 4.
Con clu sion
The addition of F-allyl iodide to alkenes is initiated by
copper metal under mild conditions to give high yields
of the corresponding addition products. Reaction with
dienes give the corresponding linear adduct or cyclization
adduct depending on the chain length of the diene. With
1,7-octadiene, a bis(perfluoroallyl) product is formed,
while a tetrahydrofuran derivative is obtained with
diallyl ether. Reduction of the adducts with zinc in the
presence of nickel dichloride in moist THF or with zinc
in moist DMF affords the perfluoroallyl derivatives. We
also found that the adduct reacts with zinc in DMF to
form a zinc reagent which couples with organic electro-
philes in the presence of CuBr. The mild reaction
conditions, readily available starting materials and cata-
lysts, and simple procedure provides a convenient and
However, â-elimination occurred upon reduction of an
adduct containing a leaving group in the â-position of the
iodide. For example, adduct 16 gave a 37% yield of the
reduction product 26a and a 23% yield of the elimination
product 26b.
(17) (a) Knochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J . J . Org.
Chem. 1988, 53, 2390. (b) Berk, S. C.; Knochel, P.; Yeh, M. C. P. J .
Org. Chem. 1988, 53, 5789.

2890 J . Org. Chem., Vol. 63, No. 9, 1998
Nguyen et al.
35.9 Hz, 1F), -101.9 (m, 2F), -110.2 (ddt, J ) 114.9, 65.3,
practical method for the preparation of interesting and
important compounds.
1
27.2 Hz, 1F), -187.6 (ddt, J ) 114.9, 36.0, 14.1 Hz, 1F); H
NMR (δ) 2.0 (m, 2H), 1.5-1.3 (m, 24H), 0.9 (t, J ) 6.7 Hz,
3H); 13C NMR (δ) 154.3 (tdm, J ) 290.0, 42.7 Hz), 125.4 (ddtd,
J ) 238.1, 43.9, 36.6, 19.5 Hz), 118.5 (tdt, J ) 241.5, 28.9, 4.2
Hz), 35.2 (t, J ) 24.5 Hz), 32.4 (s), 30.1 (s), 30.0 (s), 29.8 (s),
29.7 (s), 29.6 (s), 29.5 (s), 23.1 (s), 21.0 (t, J ) 3.6 Hz), 14.2 (s);
FT-IR (cm-1) 1785.7 (m); GC-MS (m/z) 258 (M+ - C5H10, 0.4),
257 (0.6), 244 (1.0), 243 (1.4), 229 (1.8), 228 (2.5), 216 (2.8),
21.5 (3.9), 202 (4.1), 131 (5.7), 111 (4.7), 97 (12.8), 84 (23.0),
70 (45.6), 57 (100.0).
P r ep a r a tion of 1,1,2,3,3-P en ta flu or o-6-p h en yl-1-h ex-
en e (23). Similarly, 23 was prepared from 3.8 g (10 mmol) of
5, 0.6 g (10 mmol) of zinc, 0.1 g (0.4 mmol) of NiCl2‚6H2O, in
10 mL THF, 10 mL of Et2O, and 0.5 mL of water at room
temperature. Usual workup gave 2.3 g (92%) of 23: GLPC
purity >99%; 19F NMR (δ) -96.0 (ddm, J ) 64.2, 36.0 Hz, 1F),
-101.9 (m, 2F), -109.8 (ddt, J ) 115.2, 64.0, 26.8 Hz, 1F),
-187.7 (ddt, J ) 115.0, 36.0, 14.2 Hz, 1F); 1H NMR (δ) 7.3 (m,
2H), 7.2 (m, 3H), 2.7 (t, J ) 7.6 Hz, 2H), 2.0-2.2 (m, 2H), 1.8-
1.9 (m, 2H); 13C NMR (δ) 154.6 (tdm, J ) 291.1, 42.1 Hz), 141.5
(s), 129.1 (s), 128.9 (s), 126.8 (s), 125.7 (ddtd, J ) 238.6, 44.0,
36.4, 19.5 Hz), 118.8 (tdt, J ) 214.6, 29.0, 4.2 Hz), 35.5 (s),
34.7 (t, J ) 24.6 Hz), 23.8 (t, J ) 3.8 Hz); FT-IR (cm-1) 1785.5
(s); GC-MS (m/z) 251 (M+ + 1, 1.5), 250 (12.4), 230 (0.2), 199
(0.2), 131 (2.5), 117 (35.7), 103 (3.0), 91 (100.0), 77 (5.7); HRMS
calcd for C12H11F5 250.0781, obsd 250.0778.
Exp er im en ta l Section
Gen er a l Ma ter ia ls. F-allyl iodide19 and copper20 were
prepared according to literature methods. All alkenes were
purchased from Aldrich Chemical Co. All reactions were
monitored by 19F NMR analysis of the reaction mixtures on a
90-MHz spectrometer. The 1H, 19F, and 13C NMR spectra of
final products were obtained on a 300-MHz spectrometer
(CDCl3, CFCl3, or TMS internal references). FT-IR were
recorded as CCl4 solutions in a 0.1 cm path length cell. Low-
resolution mass spectra analyses were performed at 70 eV in
the electron-impact mode on a single quadrapole instrument
interfaced to a gas chromatograph fitted with an OV-101
column. High-resolution mass spectra analyses were per-
formed by the University of Iowa High Resolution Mass
Spectroscopy Facility at 70 eV in the electron impact mode.
GLPC analysis were performed on a 5% OV-101 column and
thermal conductivity detector.
P r ep a r a tion of 1,1,2,3,3-P en ta flu or o-5-iod o-1-n on en e
(1). In a typical experimental procedure, a 50-mL, two-necked,
round-bottomed flask, equipped with a septum, a Teflon-coated
magnetic stir-bar, and a water condenser topped with an argon
inlet, was charged with 8.9 g (30 mmol) of F-allyl iodide, 3.4
g (40 mmol) of 1-hexene, and 0.6 g (10 mmol) of copper. The
reaction mixture was stirred at 50 °C under an argon atmo-
sphere for 4 h. The volatile components were removed under
reduced pressure, and the residue was introduced into a silica
gel column and eluted with hexane to give 9.1 g (80%) of 1:
GLPC purity >99%; 19F NMR (δ) -94.5 (dd, J ) 61.6, 36.2
Hz, 1F), -100.9 (AB qm, J ) 274.5 Hz, 2F), -108.7 (ddt, J )
115.3, 59.5, 28.6 Hz, 1F), -186.7 (ddt, J ) 115.1, 35.9, 14.5
Hz, 1F); 1H NMR (δ) 4.2 (m, 1H), 3.0-2.7 (m, 2H), 1.8-1.7
(m, 2H), 1.6-1.3 (m, 4H), 0.9 (t, J ) 7.1 Hz, 3H); 13C NMR (δ)
153.9 (tdm, J ) 291.0, 42.0 Hz), 124.4 (ddtd, J ) 237.4, 43.4,
36.1, 20.3 Hz), 117.2 (tdm, J ) 244.8, 29.3 Hz), 45.7 (t, J )
24.7 Hz), 40.3 (s), 31.6 (s), 22.1 (s), 21.7 (s), 13.6 (s); FT-IR
(cm-1) 1785.7 (s); GC-MS (m/z) 342 (M+, 1.8), 215 (0.6), 195
(32.5), 175 (26.1), 167 (11.8), 155 (21.3), 153 (18.0), 149 (8.2),
139 (55.3), 131 (100.0), 127 (39.1), 121 (9.4), 113 (9.6), 109
(11.7), 95 (11.5).
P r ep a r a tion of 1,1,2,3,3-P en ta flu or o-6-p h en oxy-1-h ex-
en e (26a ). Similarly, 26 was prepared from 1.9 g (5 mmol) of
16, 0.6 g (10 mmol) of zinc in 10 mL of DMF, and 0.5 mL of
water at room temperature. Usual workup gave 0.5 g (37%)
of 26: GLPC purity 93%; 19F NMR (δ) -95.6 (dd, J ) 63.7,
36.3 Hz, 1F), -102.2 (m, 2F), -109.5 (ddt, J ) 115.7, 63.6,
1
26.1 Hz, 1F), -187.7 (ddt, J ) 115.1, 36.1, 13.7 Hz, 1F); H
NMR (δ) 7.3 (m, 2H), 7.0-6.9 (m, 3H), 4.0 (t, J ) 6.0 Hz, 2H),
2.4-2.2 (m, 2H), 2.1-2.0 (m, 2H). 13C NMR (δ) 158.8 (s), 154.2
(tdm, J ) 290.4, 41.8 Hz), 129.5 (s), 125.0 (ddtd, J ) 238.2,
44.0, 36.7, 19.8 Hz), 120.9 (s), 118.1 (tdt, J ) 241.5, 28.4, 4.6
Hz), 114.1 (s), 66.2 (s), 31.7 (t, J ) 24.9 Hz), 21.7 (t, J ) 4.0
Hz); FT-IR (cm-1) 1772.7 (s); GC-MS (m/z) 266 (M+, 23.9), 267
(M+ + 1, 3.0), 173 (0.2), 153 (1.5), 145 (0.5), 131 (8.9), 94
(100.0), 77 (11.5), 65 (11.2); HRMS calcd for
266.0730, obsd 266.0720.
C12H11F5O
1,1,2,3,3-P en ta flu or o-1,5-h exa d ien e (26b). The yield of
26b was 0.2 g (23%): GLPC purity >99%, bp 55 °C; 19F NMR
(δ) -96.2 (ddm, J ) 63.8, 36.1 Hz, 1F), -101.7 (m, 2F), -109.9
(ddt, J ) 114.8, 64.2, 27.4 Hz, 1F), -188.0 (ddt, J ) 114.8,
P r ep a r a tion of 1,1,2,3,3-P en ta flu or o-5-iod o-6-p h en oxy-
1-h exen e (16). Similarly, 16 was prepared from 6.5 g (25
mmol) of F-allyl iodide, 2.7 g (20 mmol) of allyl phenyl ether,
and 0.4 g (6 mmol) of Cu at 50 °C. Usual workup gave 6.2 g
(78%) of 16: GLPC purity >99%; 19F NMR (δ) -94.0 (ddm, J
) 60.8, 35.9 Hz, 1F), -101.1 (AB qm, J ) 273.4 Hz, 2F), -108.2
(ddt, J ) 116.9, 59.0, 28.8 Hz, 1F), -186.7 (ddt, J ) 115.2,
1
36.7, 14.0 Hz, 1F); H NMR (δ) 5.8-5.7 (m, 1H), 5.3 (m, 2H),
2.8 (td, J ) 15.7, 7.0 Hz, 2H); 13C NMR (δ) 154.4 (tdm, J )
290.0, 42.6 Hz), 127.2 (t, J ) 5.3 Hz), 125.1 (dm, J ) 250.0
Hz), 122.2 (s), 117.4 (tdm, J ) 242.8, 29.1 Hz), 39.8 (t, J )
25.6 Hz); FT-IR (cm-1) 1786.4 (s); GC-MS (m/z) 172 (M+, 0.6),
157 (0.5), 152 (2.5), 144 (1.1), 139 (1.3), 131 (100.0), 103 (59.4).
P r epar ation of 1,1,2,3,3-pen taflu or o-5-ben zoyl-1-decen e
(28). A dry, 50-mL, two-necked, round-bottomed flask, equipped
with an argon inlet, a Teflon-coated stir-bar, and septum, was
charged with 1.3 g (3.5 mmol) of 2, 0.3 g (5 mmol) of acid-
washed Zn, and 10 mL of dry DMF. After stirring for 15 min
at room temperature, 2 had been completely consumed, as
determined by 19F NMR analysis. To the flask was added 0.7
g (5 mmol) of CuBr and 1.0 g (7 mmol) of benzoyl chloride,
and the reaction mixture was stirred at room temperature for
2 h. The reaction mixture was introduced onto a silica gel
column and eluted with hexane/CH2Cl2 (6/4) to give 0.95 g
(80%) of 28: 19F NMR (δ) -95.4 (ddm, J ) 63.1, 35.9 Hz, 1F),
-100.9 (AB qm, J ) 271.6 Hz, 2F), -108.9 (ddt, J ) 115.1,
62.7, 26.6 Hz, 1F), -187.1 (ddt, J ) 115.7, 36.1, 14.5 Hz, 1F);
1H NMR (δ) 7.9 (m, 2H), 7.6 (m, 1H), 7.5 (m, 2H), 3.8 (m, 1H),
3.0-2.9 (m, 1H), 2.3-2.1 (m, 1H), 1.8-1.5 (m, 2H), 1.3-1.2
(m, 6H), 0.8 (m, 3H); 13C NMR (δ) 201.2 (s), 153.5 (tdm, J )
290.7, 42.4 Hz), 136.5 (s), 133.0 (s), 128.6 (s), 128.1 (s), 124.8
(ddtd, J ) 238.2, 43.9, 36.5, 19.5 Hz), 117.4 (tdt, J ) 242.4,
28.8, 4.5 Hz), 38.9 (s), 36.0 (t, J ) 24.3 Hz), 33.4 (s), 31.5 (s),
26.5 (s), 22.2 (s), 13.5 (s); FT-IR (cm-1) 1766.9 (s); GC-MS (m/
z) 334 (M+, 1.3), 315 (0.1), 294 (1.5), 264 (5.5), 133 (2.7),
1
35.9, 15.5 Hz, 1F); H NMR (δ) 7.3 (m. 2H), 7.0 (m, 1H), 6.9
(m, 2H), 4.4 (m, 1H), 4.2 (dm, J ) 5.1 Hz, 2H), 3.2-2.7 (m,
2H); 13C NMR (δ) 157.7 (s), 153.7 (tdm, J ) 289.8, 41.8 Hz),
129.5 (s), 124.1 (ddtd, J ) 238.0, 43.7, 35.8, 19.8 Hz), 121.6
(s), 116.9 (tdt, J ) 244.4, 29.2, 4.5 Hz), 114.8 (s), 72.6 (s), 41.3
(t, J ) 25.2 Hz), 14.8 (s); FT-IR (cm-1) 1786.2 (s); GC-MS (m/
z) 392 (M+, 11.3), 393 (M+ + 1, 1.4), 299 (1.3), 279 (1.9), 235
(4.0), 220 (33.9), 173 (7.1), 171 (23.5), 152 (15.6), 131 (22.3),
108 (9.5), 94 (100.0), 93 (80.4), 77 (33.4), 65 (57.0); HRMS calcd
for C12H10OF5I 391.9696, obsd 391.9679.
P r ep a r a tion of 1,1,2,3,3-P en ta flu or o-1-h ep ta d ecen e
(20). A two-necked, round-bottom flask, equipped with an
argon inlet, a Teflon-coated stir-bar, and a septum port, was
charged with 0.6 g (10 mmol) of Zn, 10 mL of DMF, 0.5 mL of
water, and 2.3 g (5 mmol) of 3. The reaction mixture was
stirred at room temperature for 1 h. Then the reaction mixture
was introduced onto a silica gel column and eluted with
hexane. After removal of the solvent, 1.2 g (73%) of 20 was
obtained: GLPC purity 95%; 19F NMR (δ) -96.3 (dd, J ) 65.1,
(18) Yang, Z. Y.; Burton, D. J . J . Org. Chem. 1992, 57, 5144.
(19) Miller, W. T., J r.; Fainberg, A. H. J . Am. Chem. Soc. 1957, 79,
4164.
(20) Brewster, R. Q.; Groening, T. Organic Syntheses; Wiley: New
York, 1943; Collect. Vol. II, p 446.

A Facile Perfluoroallylation of Olefins
J . Org. Chem., Vol. 63, No. 9, 1998 2891
131 (1.1), 105 (100.0), 77 (23.9); HRMS calcd for C17H19F5O
334.1356, obsd 334.1351.
GC-MS (m/z) 290 (M+, 1.9), 275 (6.3), 248 (20.6), 209 (2.0),
171 (9.1), 131 (3.6), 117 (25.5), 91 (100.0), 77 (3.8), 65 (9.5);
HRMS calcd for C15H15F5 290.1094, obsd 290.1098.
P r ep a r a tion of 1,1,2,3,3-P en ta flu or o-5-ben zyl-1,7-oc-
ta d ien e (29). Similarly, 29 was prepared from 1.9 g (5 mmol)
of 5, 0.6 g (10 mmol) of Zn, 10 mL of DMF, 1.0 g (7 mmol) of
CuBr, and 0.8 g (10 mmol) of allyl chloride at room temper-
ature for 2 h. Usual workup gave 1.0 g of 29 (69%); 19F NMR
(δ) -96.0 (ddm, J ) 64.6, 36.3 Hz, 1F), -99.9 (m, 2F), -109.6
(ddt, J ) 115.0, 64.1, 27.7 Hz, 1F), -186.6 (ddt, J ) 115.0,
Ack n ow led gm en t. We thank the National Science
Foundation for support of this work.
Su p p or tin g In for m a tion Ava ila ble: 13C NMR spectra for
all compounds and experimental data for compounds 2-15,
17-19, 21, 22, 24, 25, and 27 (38 pages). This material is
contained in libraries on microfiche, immediately follows this
article in the microfilm version of the journal, and can be
ordered from the ACS; see any current masthead page for
ordering information.
1
35.9, 14.3 Hz, 1F); H NMR (δ) 7.3-7.1 (m, 5H), 5.8-5.7 (m,
1H), 5.1-5.0 (m, 2H), 2.7-2.6 (m, 2H), 2.1-2.0 (m, 5H); 13C
NMR (δ) 153.7 (tdm, J ) 311.7, 42.6 Hz), 139.7 (s), 135.3 (s),
129.3 (s), 128.4 (s), 126.3 (s), 125.2 (ddtd, J ) 246.4, 43.8, 36.6,
19.5 Hz), 118.5 (tdm, J ) 242.9, 28.5 Hz), 117.7 (s), 40.3 (s),
37.7 (s), 37.2 (t, J ) 23.7 Hz), 33.9 (s); FT-IR (cm-1) 1298.2(s);
J O9719766