Efficient access to perfluoroalkylated aryl compounds by Heck reaction

Article abstract of DOI:10.1002/1099-0690(200103)2001:6<1121::AID-EJOC1121>3.0.CO;2-3

Efficient introduction of perfluorinated tails onto aromatic rings has been achieved by Heck reaction between perfluoroalkenes and arenediazonium salts, catalysed by palladium acetate. Subsequent transition metal catalysed hydrogenation of the double bond afforded a large variety of aromatic compounds bearing an affinity for fluorous solvents. Formation of perfluoroalkylated phosphane ligands and their use in palladium-catalysed coupling between potassium trifluoro(vinyl)borates and diazonium salts is also described, allowing an easy separation and recycling of the catalytic system.

Full text of DOI:10.1002/1099-0690(200103)2001:6<1121::AID-EJOC1121>3.0.CO;2-3

FULL PAPER
Efficient Access to Perfluoroalkylated Aryl Compounds by Heck Reaction
[a]
[a]
[a]
ˆ
Sylvain Darses, Mathieu Pucheault, and Jean-Pierre Genet*
Keywords: Arenes / Fluorine / Diazo compounds / Palladium / Phosphanes
Efficient introduction of perfluorinated tails onto aromatic
Formation of perfluoroalkylated phosphane ligands and their
rings has been achieved by Heck reaction between per- use in palladium-catalysed coupling between potassium tri-
fluoroalkenes and arenediazonium salts, catalysed by palla- fluoro(vinyl)borates and diazonium salts is also described, al-
dium acetate. Subsequent transition metal catalysed hydro- lowing an easy separation and recycling of the catalytic sys-
genation of the double bond afforded a large variety of aro- tem.
matic compounds bearing an affinity for fluorous solvents.
We decided to explore a new approach to access per-
fluoroalkyl-substituted aromatic compounds based on a
Heck reaction between perfluoroalkenes and arenediazon-
ium salts, followed by hydrogenation of the double bond
Introduction
(Scheme 1).
Perfluoroalkylated compounds have attracted great inter-
est in recent years, not only in the field of catalysis with the
concept of Fluorous Biphase Catalysis (FBC) introduced
by Horvath and Gladysz,[1] but also in the field of combin-
atorial organic synthesis.[2] This attractiveness is closely re-
Scheme 1
lated with their unique properties compared with conven-
tional organic compounds: they are thermally stable, show
This approach would also allow the introduction of the
high chemical inertness and, very particularly, are not sol-
ethylene spacer. To the best of our knowledge, only one
uble in a large range of common organic solvents because
reaction sequence of this type has yet been described in Pro-
of low van der Waals interactions.[3]
sulfuron synthesis,[8] where the palladium-catalysed Heck
There is an increasing need for highly efficient methods
reaction with 1,1,1-trifluoropropene and a diazonium salt,
of introducing perfluoroalkyl chains, in order to access a
followed by in situ reduction of the double bond allowed
large variety of perfluoroalkyl-substituted building blocks.
the introduction of 1,1,1-trifluoroprop-3-yl substituent on
However, only few reports have dealt with the selective pre-
paration of aromatic compounds bearing perfluorinated
the aromatic ring.
tails, whereas these building blocks are of great interest for
preparing most of the ligands used in homogeneous cata-
lysis.[4] The copper-catalysed coupling of 1,1,2,2-tetrahydro-
genoperfluoroalkyl iodides with arylmagnesium bromides
Results and Discussion
generally suffers from limited yields because of the forma-
tion of fluorous by-products that are difficult to remove.[5]
Heck Reaction
Ullmann-type coupling between aryl bromides or iodides
and perfluoroalkyl iodides is used very often,[6] but excess
We first studied the introduction of the perfluoroalkyl
copper and harsh conditions are needed, and do not allow
chain applying classical conditions generally used for the
the introduction of an ethylene spacer between the aromatic
palladium-catalysed reaction of arenediazonium tetra-
ring and the perfluorinated chain. This spacer is often
fluoroborates with alkenes[9] or organoboron com-
necessary to decrease the electron-withdrawing strength of
pounds.[10] Thus, we found that the reaction between 4-
the fluorous tail.[1d] Finally, O-alkylation of phenol derivat-
methylbenzenediazonium tetrafluoroborate and perfluoro-
dec-1-ene (5) in methanol at room temperature was effici-
ently catalysed by palladium acetate (5%) and afforded the
ives with perfluoroalkyl sulfonates is efficient, but suffers
from the use of expensive reagents.[7]
coupling product 1a in 80% yield. However, due to limited
miscibility of the perfluoroalkene in methanol, the reaction
was slow and formation of some by-products was observed.
[a]
Increasing the temperature to 40 °C allowed the coupling
product 1a to be obtained in quantitative yield with high
purity (over 99%, Table 1, Entry 1) in the presence of 0.5
mol-% of catalyst.
`
´
Laboratoire de Synthese Selective Organique (UMR 7573,
´
CNRS), Ecole Nationale Superieure de Chimie de Paris,
11 rue P&M Curie, 75231 Paris cedex 05, France
Fax: (internat.) ϩ 33-1/44071062
E-mail: genet@ext.jussieu.fr
Eur. J. Org. Chem. 2001, 1121Ϫ1128
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ193X/01/0306Ϫ1121 $ 17.50ϩ.50/0
1121

ˆ
S. Darses, M. Pucheault, J.-P. Genet
FULL PAPER
Table 1. Heck coupling between perfluoroalkenes and diazonium
salts
Scheme 2
coupling product 1a was obtained with 4-iodotoluene, and
the reaction was accompanied by the formation of black
palladium. In the same way, coupling of aryl iodides in the
presence of Pd(PPh3)4 and triethylamine in toluene[12] did
not result in any reaction. However, under Jeffery condi-
tions[13] [Pd(OAc)2, DMF, NaHCO3, nBu4NHSO4], coup-
ling of 4-iodotoluene with perfluorodec-1-ene afforded 1a
in 80% yield (Scheme 3).
Scheme 3
Under these conditions, 4-bromotoluene was quite unre-
active, even after 2 d at 90 °C. Thus, this Heck reaction
with perfluoroalkenes could be easily applied to aryl iod-
ides, extending the scope of the present procedure to the
introduction of perfluoroalkyl chains on an aromatic ring.
Thanks to the difference in reactivity of those various
electrophiles in the Heck reaction, we have studied the
chemoselectivity of the reaction, using bifunctional aro-
matic electrophiles. We have shown that coupling of arene-
diazonium tetrafluoroborates bearing a bromide substituent
yielded coupling product 1b exclusively from the diazonium
substituent (Scheme 4, i).
[a] Rf: perfluoroalkyl chain, Rf6 ϭ C6F13, Rf8 ϭ C8F17. Ϫ [b] Deter-
mined by GC.
These conditions were applied to different diazonium
salts and two different commercially available perfluoroal-
kenes[11] [CH2ϭCHC6F13 (4) and CH2ϭCHC8F17 (5)]. As
is shown in Table 1, quantitative yields were generally ob-
tained with reaction times ranging from 2 to 15 min. All
the perfluoroalkenyl-substituted aromatic compounds were
easily purified by simple filtration through silica gel to af-
ford, exclusively, (E)-alkenes of very high GC purities (from
96 to over 99%). Moreover, this reaction is compatible with
bromo substituents (Entries 2Ϫ8), as no coupling products
originating from the insertion of palladium(0) into the
CϪBr bond were obtained. Lower yields observed with per-
fluorooct-1-ene (1cЈ) could be explained by the volatility of
the coupled product (Entry 5). Thus, it was possible to ac-
cess, very efficiently, various aryl bromides bearing a per-
fluoroalkyl chain. These compounds are important pre-
cursors in triarylphosphane synthesis.
Scheme 4
This Heck reaction could be conducted at lower catalytic
rates (Scheme 2). The reaction of benzenediazonium tetra-
Under identical conditions (MeOH, 40 °C), coupling of
fluoroborate in the presence of 0.01 mol-% of catalyst gave 4-iodobenzenediazonium tetrafluoroborate afforded the
the coupling product 1i with a TOF (Turn Over Frequency) perfluoroalkyl-substituted 1j in moderate yield (70%), ac-
of around 7000. In the same way, coupling of 4-bromoben- companied by the bis-coupling product (Scheme 4, ii). By
zenediazonium tetrafluoroborate afforded the expected conducting the reaction at room temperature, however, and
compound 1b with a TON (Turn Over Number) of 65000 using a 1:3 mixture of MeOH/THF in order to improve the
and a TOF of 260000.
solubility of the perfluoroalkene, the selectivity is increased
We then studied the extension of this coupling to other up to 90:10 in favour of the monocoupling product 1j
electrophiles, mainly aryl iodides and bromides. Under pre- (Scheme 4, ii). Finally, Heck reaction of 3-bromoiodoben-
viously described conditions [cat. Pd(OAc)2, methanol], no zene under Jeffery conditions[13] afforded exclusively the
1122
Eur. J. Org. Chem. 2001, 1121Ϫ1128

Efficient Access to Perfluoroalkylated Aryl Compounds by Heck Reaction
FULL PAPER
product 1c, from the coupling of the iodide substituent, in Table 2. Reduction of the double bond of perfluoroalkylated aryl
bromides
good yield (Scheme 4, iii). Hence, concerning the reactivity
of the tested electrophiles for the present reaction, we can
classify the halides or pseudohalides in the order
N2ϩ Ͼ I ϾϾ Br.
Entry[a]
[MT] 1%
Solvent
Conversion[b]
(Purity[c])
Reduction of the Double Bond
We then decided to study the reduction of the double
bond of the different perfluoroalkenyl-substituted aromatic
compounds. In situ experiments, consisting of a Heck reac-
tion, followed by hydrogenation under hydrogen (1 atm) us-
ing the same palladium catalyst, were not conclusive be-
cause of low conversions and the formation of by-products.
However, hydrogenation performed on isolated perfluoroal-
kenyl-substituted aromatic compounds under standard con-
ditions (1 mol-% of Pd/C, 1 atm of H2) allowed quantitative
reduction of the double bond in high yields (Scheme 5).
1
PtO2
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
CH2Cl2
CH2Cl2
CH2Cl2
20
2
RhCl(PPh3)3
RuCl3
0
3
0
4
RuCl(PPh3)3
Ru(Met)2(cod)
RuCl2(PPh3)2
Rh/C
Ͻ 1
5
6
6
23
7
95 (76)
31 (97)
95 (Ͼ 98)
100 (Ͼ 99)
8
Rh/C
9[d]
Rh/C
10[d][e]
Rh/C
[a]
Reactions conducted under 1 atm of H2 at room temp. for 18 h
[b]
using 1 mol-% of catalyst (Rf ϭ C8F17). Ϫ
Conversion deter-
[c]
[d]
mined by GC. Ϫ Determined by GC. Ϫ Reaction conducted
[e]
under 50 bar of H2. Ϫ
catalyst for 24 h at 20 °C.
Reaction conducted using 2 mol-% of
tion using Rh/C as catalyst. In nonprotic solvents (THF,
1,4-dioxane, AcOEt, CH2Cl2), hydrogenation was very slow
at room temperature under 1 atm of hydrogen, but it af-
forded the expected products with good purities (over 90%
in dichloromethane, Entry 8). Increasing the pressure to 50
bar allowed for almost quantitative hydrogenation after 18
h, the purity being unchanged (Entry 9). Particularly, in
dichloromethane, purities over 99% could be achieved using
2 mol-% of Rh/C at 50 bar of H2 for 24 h (Table 2, Entry
10 and Scheme 6).
Scheme 5
In the case of the nitro-substituted compound 1h, we ob-
serve a concomitant complete reduction of the nitro group,
affording the perfluoroalkylated aniline 2k in high yield. In
any case, reduced products of high purity were easily ob-
tained by simple filtration through silica gel. The notable
exception was the reduction of the aryl bromide derivative
2b, where cleavage of the bromo substituent predominated.
Thus, we looked for other conditions to perform the re-
duction of such compounds. Our first idea was to use non-
transition metal catalysed reductions, and more particu-
larly, diimide reductions. Several conditions for generating
the diimide were investigated[14] (H2O2, KO2CNϭNCO2K/
AcOH, H2O2/Cu cat.), but each time the reaction stopped
before completion, with yields not exceeding 30%, even in
the presence of excess reagent. We then turned to transition
metal catalysed reduction methods that could be compat-
ible with the presence of bromo substituents. PtO2 under
hydrogen has already been used for the hydrogenation of
aryl bromides bearing a long alkene chain with good select-
ivities.[15] Applied to our substrate (Table 2, Entry 1), we
observed the formation of large amounts of debrominated
compounds accompanied by low conversions.
Scheme 6
Under these optimised conditions (cat. Rh/C, dichloro-
methane, 50 bar of H2), conversions and purities of the
compounds are very dependent on catalyst loading, temper-
ature and reaction time. Reproducible results were generally
achieved at 20 °C during 24 h using 2 mol-% of catalyst
(Scheme 6). For all of the tested substrates, quantitative
yields and purities were obtained. As in the case of the
Heck reaction, simple filtration through silica gel allowed
the isolation of very pure compounds.
We next tested ruthenium and rhodium complexes, which
have already been used in the selective reduction of the
double bond of alkene-substituted aryl bromides.[16] Among
the tested catalysts in MeOH at room temperature and un-
Fluorous Biphase Catalysis
Starting from these perfluoroalkylated aryl bromides, ac-
der 1 atm of hydrogen, Rh/C proved to be most efficient, cess to perfluoroalkyl-substituted phosphanes was straight-
affording the expected product 2b with 76% purity and 95% forward by lithium/halogen exchange, followed by con-
conversion (Table 2, Entries 2Ϫ7). The observed by-prod- densation onto a halophosphane.[17] Treatment of per-
ucts originated from debromination. Other solvents were fluoroalkylated aryl bromides 2b and 2e with 1 equiv. of
tested in order to increase the selectivity of the hydrogena- n-butyllithium at Ϫ30 °C afforded aryllithium derivatives,
Eur. J. Org. Chem. 2001, 1121Ϫ1128
1123

ˆ
S. Darses, M. Pucheault, J.-P. Genet
FULL PAPER
which, upon treatment with freshly distilled PCl3, gave al-
most quantitative yields of perfluoroalkyl-substituted phos-
phanes 3b and 3e (Scheme 7). 31P NMR analysis revealed
that these phosphanes had purities of over 95% after simple
filtration through silica gel. For many purposes, these prod-
ucts could be engaged without further purification. Analyt-
ically pure compounds were obtained by recrystallisation
from ether/methanol mixtures with moderate yields.
Scheme 7
This easy treatment avoided classical BH3 protection of
the phosphorus atom. A perfluoroalkylated analogue of the
very useful tri-o-tolylphosphane[18] was prepared efficiently
for the first time by this method.
The concept of FBC was tested on an example: the palla-
dium-catalysed cross-coupling reaction of arenediazonium
tetrafluoroborates with potassium organotrifluorobor-
ates.[10,19] To the best of our knowledge this concept has not
yet been applied to cross-coupling reactions with or-
ganoboron compounds. The catalyst precursor was pre-
pared by mixing 2 equiv. of perfluoroalkyl-substituted pho-
sphane 3b with palladium acetate at room temperature in a
1:1 mixture of methanol/FC-72 for 5 min, followed by re-
moval of methanol. To this perfluorous solution of catalyst
was added a methanol solution of 4-(ethoxycarbonyl)ben-
zenediazonium tetrafluoroborate (6) and potassium trifluo-
ro(vinyl)borate (7). At the end of the coupling, methanol
was removed, the perfluorous phase washed with methanol
and water, and reloaded with substrates.
Figure 1. Fluorous biphase cross-coupling of 6 with 7
ling of the palladium catalyst in the cross-coupling reaction
of arenediazonium salts with organotrifluoroborates.
Experimental Section
1
General Remarks: H NMR and 13C NMR spectra were recorded
with a Bruker AC 200 at 200 or 50 MHz, respectively; chemical
shifts (δ) are reported in ppm units by reference to Me4Si, and
coupling constants (J) are reported in Hz and refer to apparent
peak multiplicities. 31P and 19F NMR spectra were recorded with
a Bruker ARX 400 instrument at 162 and 376 MHz, respectively
using H3PO4 and CFCl3 as an internal reference. Ϫ Mass spectra
were determined with a Ribermag instrument. Ϫ Elementary ana-
lyses were done at the Regional Service of Microanalysis (Univers-
As we can see in Figure 1, good conversions and purities
were obtained up to the 5th cycle, after which a decrease
in conversions was observed. We also noted an increase in
reaction times with the number of cycles: This could origin-
ate from a slight loss of palladium catalyst during the wash-
ings.
´
ite Pierre et Marie Curie). Ϫ Thin layer chromatography was car-
ried out on silica gel plates (Merck F254) and spots were detected
by UV. Ϫ GC analyses were performed with a Hewlett-Packard
5890 instrument equipped with a J&W Scientific DB-1701 capillary
column (15 m, Ø ϭ 0.25 µm), using a flame ionisation detector.
Head pressure was fixed to 50 kPa using the following temperature
program: 70 °C for 1 min, 20 °C/min up to 210 °C. Ϫ Anhydrous
THF and ether were distilled from sodium/benzophenone; CH2Cl2
was distilled from calcium hydride; methanol (Prolabo, Normap-
urԹ) was used as received. Pd(OAc)2 and aromatic amines were pur-
chased from Acros or Aldrich, and were used as received. Per-
fluoroalkenes were bought from Interchim. Phosphorus trichloride
was freshly distilled prior to use. Arenediazonium salts were pre-
pared according to described procedures.[10b,10f,20]
Conclusion
Starting from arenediazonium salts, readily available
from aromatic amines, it was possible by a two step trans-
ition metal catalysed reaction (Heck reaction followed by
hydrogenation) to access a large variety of perfluoroal-
kylated aromatic compounds very efficiently. More particu-
larly, perfluoroalkyl-substituted aryl bromides and anilines
were accessible. This represents one of the most efficient
methods of attaching a perfluoroalkyl chain to an aromatic
ring. Moreover, simple purification (filtration) and the high
purities obtained will allow an easy scale up of this proced-
General Procedure for the Heck Coupling between Arenediazonium
Tetrafluoroborates and Perfluoroalkenes: To a stirred suspension of
arenediazonium salt and Pd(OAc)2 (0.5 mol-%) in MeOH (1 mL/
mmol) was added under argon 1,1,2-trihydrogenoperfluoroalk-1-
ene (1 equiv.). The mixture was heated at 40 °C until gas evolution
ceased. CAUTION: Some reactions were highly exothermic! The
ure. Finally, encouraging results were obtained on the recyc- resulting mixture was stirred for additional 10 min and MeOH was
1124 Eur. J. Org. Chem. 2001, 1121Ϫ1128

Efficient Access to Perfluoroalkylated Aryl Compounds by Heck Reaction
FULL PAPER
removed under reduced pressure. The residue was extracted with
cyclohexane/ether (99:1) for 1f؊k or with cyclohexane for 1a؊e,
filtered through silica gel and the solvent was removed under va-
cuum to afford the expected product.
Ϫ111.8 (m, 2 F, F3), Ϫ81.4 (m, 3 F, F10). Ϫ C16H6BrF13 (601.1):
calcd. C 31.97, H 1.01; found C 31.83, H 1.07.
1-(4Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca-
fluorodecane (2b): White solid (27.19 g, 45.1 mmol), prepared from
1b (46 mmol) in 98% yield according to the general procedure. Ϫ
General Procedure for the Heck Coupling under Jeffery Conditions:
A mixture of iodo- or bromoarene, 1,1,2-trihydrogenoperfluoroalk-
1-ene (1 equiv.), Pd(OAc)2 (1 or 2 mol-%), NaHCO3 (2.5 equiv.),
and nBu4NHSO4 (1 equiv.) in DMF (1.5 mL/mmol) was stirred at
90 °C for 24 h. Cyclohexane (5 mL/mmol) was added, the mixture
was washed with water (5 mL/mmol), brine (5 mL/mmol, four
times), and water (5 mL/mmol), dried with MgSO4 and concen-
trated under reduced pressure. The residue was dissolved in cyclo-
hexane, filtered through silica gel and concentrated under vacuum
to give the expected product.
1
M.p. 54 °C. Ϫ H NMR (CDCl3, 200 MHz): δ ؍ 2.23Ϫ2.49 (m, 2
H, H2), 2.85Ϫ2.93 (m, 2 H, H1), 7.11 (d, 2 H, J ϭ 8.4 Hz, H2Ј),
7.46 (dt, 2 H, J ϭ 8.4 and 2.2 Hz, H3Ј). Ϫ 13C NMR (CDCl3,
50 MHz): δ ϭ 25.8 (C1), 32.6 (t, JCF ϭ 22.1 Hz, C2), 120.5 (C4Ј),
129.9 (C2Ј), 131.8 (C3Ј), 137.9 (C1Ј). Ϫ 19F NMR (CDCl3): δ ϭ
Ϫ126.7 (m, 2 F, F9), Ϫ124.0 (m, 2 F, F4), Ϫ123.3 (m, 2 F), Ϫ122.4
(m, 4 F, F6 and F7), Ϫ122.2 (m, 2 F), Ϫ115.1 (m, 2 F, F3), Ϫ81.5
(m, 3 F, F10). Ϫ MS (70 eV); m/z (%): 602 and 604 (11) [Mϩ·], 523
(5), 169 and 171 (100). Ϫ C16H8BrF17 (603.1): calcd. C 31.86, H
1.34; found C 31.88, H 1.21.
General Procedure for the Pd/C Hydrogenation of Perfluoroalkenes:
A suspension of the perfluoroalkene 1 and 5% Pd/C (1 mol-%) in
a degassed methanol/THF (1:1) mixture (2 mL/mmol) was placed
under H2 and stirred at room temp. for 18 h (reduction monitored
by GC). At the end of reaction the solvent was removed. The res-
idue was extracted with cyclohexane/ether (99:1), filtered through
silica gel and the solvent was removed under vacuum to afford the
expected product 2.
1-(4Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene
(1bЈ): White solid (2.305 g, 4.60 mmol), prepared from 4-bromo-
benzenediazonium tetrafluoroborate (5 mmol) and 4 in 92% yield
1
according to the general procedure. Ϫ M.p. Ͻ 30 °C. Ϫ H NMR
(CDCl3): δ ؍ 6.23 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 12.0 Hz,
H2), 7.15 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 2.3 Hz, H1), 7.37 (d,
2 H, J ϭ 8.5 Hz, H2Ј), 7.57 (d, 2 H, J ϭ 8.5 Hz, H3Ј). Ϫ 13C NMR
(CDCl3): δ ϭ 115.1 (t, JCF ϭ 23.1 Hz, C2), 124.5 (C4Ј), 129.1 (C2Ј),
132.2 (C3Ј), 132.5 (C1Ј), 138.6 (t, JCF ϭ 9.5 Hz, C1). Ϫ 19F NMR
(CDCl3): δ ϭ Ϫ127.7 (m, 2 F, F7), Ϫ123.7 (m, 2 F, F4), Ϫ123.4
(m, 2 F), Ϫ122.1 (m, 2 F), Ϫ111.8 (m, 2 F, F3), Ϫ81.4 (m, 3 F,
F10). Ϫ C14H6BrF13 (501.1): calcd. C 33.56, H 1.21; found C 33.52,
H 1.14.
General Procedure for the Rh/C Hydrogenation of Perfluoroalkenes:
A suspension of the perfluoroalkene 1 and 5% of Rh/C (2 mol-%)
in degassed dichloromethane (4 mL/mmol) was placed under 50
bar of H2 and stirred at 20 °C for 24 h (reduction monitored by
GC). At the end of reaction the solvent was removed. The residue
was extracted with cyclohexane/ether (99:1), filtered through silica
gel and the solvent was removed under vacuum to afford the ex-
pected product 2.
1-(4Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane
(2bЈ): White solid (1.892 g, 3.76 mmol), prepared from 1bЈ
(4 mmol) in 94% yield according to the general procedure. Ϫ M.p.
30 °C. Ϫ 1H NMR (CDCl3): δ ؍ 2.25Ϫ2.51 (m, 2 H, H2),
2.87Ϫ2.95 (m, 2 H, H1), 7.12 (d, 2 H, J ϭ 8.4 Hz, H2Ј), 7.48 (dt, 2
H, J ϭ 8.4 and 2.2 Hz, H3Ј). Ϫ 13C NMR (CDCl3): δ ϭ 25.8 (C1),
32.6 (t, JCF ϭ 22.1 Hz, C2), 120.5 (C4Ј), 129.9 (C2Ј), 131.8 (C3Ј),
137.9 (C1Ј). Ϫ MS (70 eV); m/z (%): 502 and 504 (16) [Mϩ·], 423
(7), 169 and 171 (100). Ϫ C14H8BrF13 (503.1): calcd. C 33.42, H
1.60; found C 33.47, H 1.64.
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-1-(4Ј-methyl-
phenyl)dec-1-ene (1a): White solid (2.686 g, 4.95 mmol), prepared
from 4-methylbenzenediazonium tetrafluoroborate (5 mmol) and 5
in 99% yield according to the general procedure. Ϫ M.p. 30 °C. Ϫ
1H NMR (CDCl3): δ ϭ 2.42 (s, 3 H, CH3), 6.18 (dt, 1 H, JHH
ϭ
16.1 Hz and JHF ϭ 12.3 Hz, H2), 7.1Ϫ7.3 (m, 3 H, H1 and H3Ј),
7.41 (d, 2 H, J ϭ 8.1 Hz, H2Ј). Ϫ 13C NMR (CDCl3): δ ϭ 21.1
(CH3), 113.1 (t, JCF ϭ 23.0 Hz, C2), 127.4 (C2Ј), 129.5 (C3Ј), 130.8
(C1Ј), 139.5 (t, JCF ϭ 9.5 Hz, C1), 140.4 (C4Ј). Ϫ C17H9F17 (536.2):
calcd. C 38.08, H 1.69; found C 38.06, H 1.73.
1-(3Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca-
fluorodec-1-ene (1c): Colorless oil (2.975 g, 4.95 mmol), prepared
from 3-bromobenzenediazonium tetrafluoroborate (5 mmol) and 5
in 99% yield according to the general procedure. Ϫ 1H NMR
(CDCl3): δ ؍ 6.25 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 12.0 Hz,
H2), 7.13 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 2.1 Hz, H1), 7.29 (t,
1 H, J ϭ 7.8 Hz, H5Ј), 7.42 (d, 1 H, J ϭ 7.8 Hz, H6Ј), 7.55 (d, 1 H,
J ϭ 7.8 Hz, H4Ј), 7.65 (s, 1 H, H2Ј). Ϫ 13C NMR (CDCl3): δ ϭ
115.9 (t, JCF ϭ 23.3 Hz, C2), 123.0 (C3Ј), 126.0 (C6Ј), 130.2 (C2Ј
and C5Ј), 132.8 (C4Ј), 135.4 (C1Ј), 138.1 (t, JCF ϭ 9.5 Hz, C1). Ϫ
19F NMR (CDCl3): δ ϭ Ϫ126.7 (m, 2 F, F9), Ϫ123.7 (m, 2 F, F4),
Ϫ123.3 (m, 2 F), Ϫ122.5 (m, 4 F, F6 and F7), Ϫ122.0 (m, 2 F),
Ϫ112.0 (m, 2 F, F3), Ϫ81.5 (m, 3 F, F10). Ϫ C16H6BrF13 (601.1):
calcd. C 31.97, H 1.01; found C 31.79, H 1.03.
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-1-(4Ј-methyl-
phenyl)decane (2a): White solid (2.110 g, 2.92 mmol), prepared
from 1a (4 mmol) in 98% yield according to the general procedure.
1
Ϫ M.p. 35 °C. Ϫ H NMR (CDCl3): δ ؍ 2.32Ϫ2.52 (m, 2 H, H2),
2.34 (s, 3 H, CH3), 2.88Ϫ2.96 (m, 2 H, H1), 7.11Ϫ7.20 (m, 4 H,
H2Ј and H3Ј). Ϫ 13C NMR (CDCl3): δ ϭ 20.6 (CH3), 25.9 (C1),
33.1 (t, JCF ϭ 22.2 Hz, C2), 128.0 (C2Ј), 129.3 (C3Ј), 136.0 and 136.2
(C2Ј and C4Ј). Ϫ MS (70 eV); m/z (%): 538 (6) [Mϩ·], 105 (100). Ϫ
C17H11F17 (538.2): calcd. C 37.93, H 2.06; found C 38.10, H 1.96.
1-(4Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca-
fluorodec-1-ene (1b): White solid (29.45 g, 49.0 mmol), prepared
from 4-bromobenzenediazonium tetrafluoroborate (50 mmol) and
5 in 98% yield according to the general procedure. Ϫ M.p. 45 °C.
1-(3Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca-
Ϫ 1H NMR (CDCl3): δ ϭ 6.23 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ fluorodecane (2c): White solid (2.340 g, 2.88 mmol), prepared from
12.1 Hz, H2), 7.14 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 2.3 Hz, H1), 1c (4 mmol) in 97% yield according to the general procedure. Ϫ
7.37 (d, 2 H, J ϭ 8.5 Hz, H2Ј), 7.57 (d, 2 H, J ϭ 8.5 Hz, H3Ј). Ϫ M.p. 38 °C. Ϫ 1H NMR (CDCl3): δ ؍ 2.26Ϫ2.53 (m, 2 H, H2),
13C NMR (CDCl3): δ ϭ 115.0 (t, JCF ϭ 23.2 Hz, C2), 124.4 (C4Ј),
2.89Ϫ2.97 (m, 2 H, H1), 7.13Ϫ7.25 (m, 2 H, H5Ј and H6Ј),
128.9 (C2Ј), 132.1 (C3Ј), 132.3 (C1Ј), 138.4 (t, JCF ϭ 9.5 Hz, C1). Ϫ 7.38Ϫ7.44 (m, 2 H, H2Ј and H4Ј). Ϫ 13C NMR (CDCl3): δ ϭ 26.0
19F NMR (CDCl3): δ ϭ Ϫ126.7 (m 2 F, F9), Ϫ123.7 (m, 2 F, F4), (C1), 32.6 (t, JCF ϭ 22.2 Hz, C2), 122.6 (C3Ј), 126.8 (C6Ј), 129.8
Ϫ123.3 (m, 2 F), Ϫ122.4 (m. 4 F, F6 and F7), Ϫ121.9 (m, 2 F),
(C4Ј), 130.2 (C5Ј), 131.3 (C2Ј), 141.3 (C1Ј). Ϫ MS (70 eV); m/z (%):
Eur. J. Org. Chem. 2001, 1121Ϫ1128
1125

ˆ
S. Darses, M. Pucheault, J.-P. Genet
FULL PAPER
602 and 604 (10) [Mϩ], 169 and 171 (100), 109 (39). Ϫ C16H8BrF17 H2 and H6Ј), 7.35 (s, 1 H, H2Ј), 7.58 (d, 1 H, J ϭ 8.2 Hz, H5Ј). Ϫ
(603.1): calcd. C 31.86, H 1.34; found C 31.98, H 1.11.
13C NMR (CDCl3): δ ϭ 22.7 (CH3), 114.7 (t, JCF ϭ 23.3 Hz, C2),
126.1 (C6Ј), 126.8 (C4Ј), 129.7 (C2Ј), 132.6 (C1Ј), 132.8 (C5Ј), 138.6
(t, JCF ϭ 9.6 Hz, C1), 138.7 (C3Ј).
1-(3Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene
(1cЈ): Colorless oil (1.754 g, 3.50 mmol), prepared from 3-bromo-
benzenediazonium tetrafluoroborate (5 mmol) and 4 in 70% yield
according to the general procedure. Ϫ 1H NMR (CDCl3): δ ؍ 6.23
(dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 12.0 Hz, H2), 7.13 (dt, 1 H,
JHH ϭ 16.1 Hz and JHF ϭ 2.2 Hz, H1), 7.29 (t, 1 H, J ϭ 7.8 Hz,
H5Ј), 7.43 (d, 1 H, J ϭ 7.8 Hz, H6Ј), 7.55 (d, 1 H, J ϭ 7.8 Hz, H4Ј),
1-(4Ј-Bromo-3Ј-methylphenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecane (2e): Colorless oil (4.780 g, 7.77 mmol), pre-
pared from 1e (8.0 mmol) in 97% yield according to the general
procedure. Ϫ 1H NMR (CDCl3): δ ؍ 2.24Ϫ2.54 (m, 2 H, H2), 2.45
(s, 3 H, CH3), 2.86Ϫ2.94 (m, 2 H, H1), 6.94 (d, 1 H, J ϭ 8.1 Hz,
H6Ј), 7.15 (s, 1 H, H2Ј), 7.52 (d, 1 H, J ϭ 8.1 Hz, H5Ј). Ϫ 13C NMR
(CDCl3): δ ϭ 22.5 (CH3), 25.7 (C1), 32.7 (t, JCF ϭ 22.2 Hz, C2),
122.9 (C4Ј), 127.0 (C6Ј), 130.6 (C2Ј), 132.5 (C5Ј), 138.17 and 138.25
(C1Ј and C3Ј). Ϫ MS (70 eV); m/z (%): 616 and 618 (12) [Mϩ·], 537
(9), 183 and 185 (100). Ϫ C17H10BrF17 (617.1): calcd. C 33.09, H
1.63; found C 33.19, H 1.84.
7.66 (s, 1 H, H2Ј). Ϫ 13C NMR (CDCl3): δ ϭ 115.8 (t, JCF
ϭ
23.3 Hz, C2), 123.0 (C3Ј), 126.1 (C6Ј), 130.3 (C2Ј and C5Ј), 132.9
(C4Ј), 135.4 (C1Ј ), 138.2 (t, JCF ϭ 9.6 Hz, C1).
1-(3Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane
(2cЈ): Colorless oil (1.819 g, 3.62 mmol), prepared from 1cЈ
(4 mmol) in 90% yield according to the general procedure. Ϫ 1H
NMR (CDCl3): δ ؍ 2.20Ϫ2.53 (m, 2 H, H2), 2.88Ϫ2.97 (m, 2 H,
H1), 7.15Ϫ7.27 (m, 2 H, H5Ј and H6Ј), 7.40Ϫ7.44 (m, 2 H, H2Ј and
H4Ј). Ϫ 13C NMR (CDCl3): δ ϭ 26.1 (C1), 32.7 (t, JCF ϭ 22.2 Hz,
C2), 122.7 (C3Ј), 126.9 (C6Ј), 129.9 (C4Ј), 130.3 (C5Ј), 131.4 (C2Ј),
141.3 (C1Ј). Ϫ C14H8BrF13 (503.1): calcd. C 33.42, H 1.60; found
C 33.59, H 1.47.
1-(4Ј-Ethoxycarbonylphenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodec-1-ene (1f): White solid (2.937 g, 4.94 mmol),
prepared from ethyl 4-ethoxycarbonylbenzenediazonium tetra-
fluoroborate (5 mmol) and 5 in 99% yield according to the general
1
procedure. Ϫ M.p. 41 °C. Ϫ H NMR (CDCl3): δ ؍ 1.43 (t, 3 H,
J ϭ 7.1 Hz, CH3), 4.42 (q, 2 H, J ϭ 7.1 Hz, OCH2), 6.32 (dt, 1 H,
JHH ϭ 16.1 Hz and JHF ϭ 12.0 Hz, H2), 7.25 (dt, 1 H, JHH
ϭ
16.1 Hz and JHF ϭ 2.2 Hz, H1), 7.56 (d, 2 H, J ϭ 8.4 Hz, H2Ј),
8.10 (d, 2 H, J ϭ 8.4 Hz, H3Ј). Ϫ 13C NMR (CDCl3): δ ϭ 14.1
(CH3), 61.1 (OCH2), 116.6 (t, JCF ϭ 23.3 Hz, C2), 127.3 (C2Ј), 130.0
(C3Ј), 131.7 (C4Ј), 137.4 (C1Ј), 138.6 (t, J ϭ 9.3 Hz, C1), 165.7 (Cϭ
O). Ϫ C19H11F17O2 (594.3): calcd. C 38.40, H 1.87; found C 38.40,
H 1.72.
1-(2Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca-
fluorodec-1-ene (1d): White solid (2.940 g, 4.89 mmol) prepared
from 2-bromobenzenediazonium tetrafluoroborate (5 mmol) and 5
in 98% yield according to the general procedure. Ϫ M.p. 30 °C. Ϫ
1H NMR (CDCl3): δ ؍ 6.22 (dt, 1 H, JHH ϭ 16.0 Hz and JHF
ϭ
12.0 Hz, H2), 7.25 (1 H, td, J ϭ 7.7 and 1.8 Hz, H4Ј), 7.36 (1 H,
td, J ϭ 7.5 and 1.2 Hz, H5Ј), 7.53Ϫ7.69 (m, 3 H, H1, H3Ј and H6Ј).
Ϫ
13C NMR (CDCl3): δ ϭ 117.2 (t, JCF ϭ 23.2 Hz, C2), 124.6
1-(4Ј-Ethoxycarbonylphenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecane (2f): White solid (2.331 g, 3.91 mmol), pre-
pared from 1f (4 mmol) in 98% yield according to the general pro-
cedure. Ϫ M.p. 50 °C. Ϫ 1H NMR (CDCl3): δ ؍ 1.42 (t, 3 H, J ϭ
7.1 Hz, CH3), 2.28Ϫ2.54 (m, 2 H, H2), 2.95Ϫ3.04 (m, 2 H, H1),
4.40 (q, 2 H, J ϭ 7.1 Hz, OCH2), 7.31 (d, 2 H, J ϭ 8.2 Hz, H2Ј),
8.03 (d, 2 H, J ϭ 8.2 Hz, H3Ј). Ϫ 13C NMR (CDCl3): δ ϭ 14.1
(CH3), 26.3 (C1), 32.4 (t, JCF ϭ 22.2 Hz, C2), 60.8 (OCH2), 128.1
(C2Ј), 129.1 (C4Ј), 129.9 (C3Ј), 144.1 (C1Ј), 166.2 (CϭO). Ϫ MS
(70 eV); m/z (%): 596 (14) [Mϩ·], 568 (27), 551 (80), 163 (45), 131
(75), 109 (100). Ϫ C19H13F17O2 (596.3): calcd. C 38.27, H 2.20;
found C 38.26, H 2.29.
(C2Ј), 127.4 (C5Ј or C6Ј), 127.5 (C5Ј or C6Ј), 130.9 (C4Ј), 133.2 (C3Ј),
133.7 (C1Ј ), 138.6 (t, JCF ϭ 9.7 Hz, C1). Ϫ C17H11BrF17 (601.1):
calcd. C 31.97, H 1.01; found C 31.79, H 0.92.
1-(2Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca-
fluorodecane (2d): White solid (2.362 g, 3.92 mmol), prepared from
1d (4 mmol) in 98% yield according to the general procedure. Ϫ
M.p. 31 °C. Ϫ 1H NMR (CDCl3): δ ؍ 2.27Ϫ2.58 (m, 2 H, H2),
3.07Ϫ3.15 (m, 2 H, H1), 7.10Ϫ7.18 (m, 1 H, H6Ј), 7.26Ϫ7.31 (m,
2 H, H4Ј and H5Ј), 7.59 (d, 1 H, J ϭ 7.6 Hz, H3Ј). Ϫ 13C NMR
(CDCl3): δ ϭ 27.0 (C1), 31.0 (t, JCF ϭ 22.2 Hz, C2), 124.0 (C2Ј),
127.6 (C5Ј), 128.3 (C4Ј), 130.2 (C6Ј), 132.9 (C3Ј), 138.3 (C1Ј). Ϫ MS
(70 eV); m/z (%): 602 and 604 (10) [Mϩ·], 523 (7), 169 and 171
(100). Ϫ C16H8BrF17 (603.1): calcd. C 31.86, H 1.34; found C
31.91, H 1.23.
1-(2Ј-Ethoxycarbonylphenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodec-1-ene (1g): Colorless oil (2.661 g, 4.48 mmol),
prepared from 2-ethoxycarbonylbenzenediazonium tetrafluorobor-
ate (5 mmol) and 5 in 90% yield according to the general procedure.
1
1-(2Ј-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene
(1dЈ): Colorless oil (2.435 g, 4.86 mmol), prepared from 2-bromo-
benzenediazonium tetrafluoroborate (5 mmol) and 4 in 97% yield
according to the general procedure. Ϫ 1H NMR (CDCl3): δ ؍ 6.23
(dt, 1 H, JHH ϭ 16.0 Hz and JHF ϭ 12.0 Hz, H2), 7.25 (1 H, td,
J ϭ 7.6 and 1.8 Hz, H4Ј), 7.37 (1 H, td, J ϭ 7.5 and 1.2 Hz, H5Ј),
7.54Ϫ7.70 (m, 3 H, H1, H3Ј and H6Ј). Ϫ 13C NMR (CDCl3): δ ϭ
117.1 (t, JCF ϭ 23.2 Hz, C2), 124.6 (C2Ј), 127.4 (C5Ј or C6Ј), 127.6
Ϫ H NMR (CDCl3): δ ؍ 1.42 (t, 3 H, J ϭ 7.1 Hz, CH3), 4.42 (q,
2 H, J ϭ 7.1 Hz, OCH2), 6.08 (dt, 1 H, JHH ϭ 15.9 and JHF
ϭ
12.1 Hz, H2), 7.44Ϫ7.63 (m, 3 H), 8.03Ϫ8.11 (m, 2 H). Ϫ 13C
NMR (CDCl3): δ ϭ 14.0 (CH3), 61.4 (OCH2), 116.6 (t, JCF
ϭ
22.7 Hz, C2), 127.8 (C6Ј), 129.2 (C4Ј), 129.6 (C2Ј), 130.9 (C3Ј), 132.3
(C4Ј), 135.5 (C1Ј), 139.7 (t, JCF ϭ 9.4 Hz, C1), 166.4 (CϭO).
1-(2Ј-Ethoxycarbonylphenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecane (2g): Colorless oil (2.349 g, 3.94 mmol), pre-
pared from 1g (4 mmol) in 99% yield according to the general pro-
cedure. Ϫ 1H NMR (CDCl3, 200 MHz): δ ؍ 1.42 (t, 3 H, J ϭ
7.1 Hz, CH3), 2.34Ϫ2.61 (m, 2 H, H2), 3.23Ϫ3.31 (m, 2 H, H1),
4.42 (q, 2 H, J ϭ 7.1 Hz, OCH2), 7.28Ϫ7.38 (m, 2 H, H4Ј and H6Ј),
7.49 (2 H, td, J ϭ 7.4 and 1.5 Hz, H5Ј), 8.03 (dd, 2 H, J ϭ 7.7 and
1.2 Hz, H3Ј). Ϫ 13C NMR (CDCl3, 50 MHz): δ ϭ 13.9 (CH3), 25.6
(C5Ј or C6Ј), 130.9 (C4Ј), 133.2 (C3Ј), 133.8 (C1Ј), 138.7 (t, JCF
ϭ
9.8 Hz, C1). Ϫ C14H6BrF13 (501.1): calcd. C 33.56, H 1.21; found
C 33.50, H 1.25.
1-(4Ј-Bromo-3Ј-methylphenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodec-1-ene (1e): Colorless oil (5.320 g, 8.65 mmol),
prepared from 4-bromo-3-methylbenzenediazonium tetrafluoro-
borate (9.3 mmol) and 5 in 93% yield according to the general pro- (C1), 32.6 (t, JCF ϭ 22.0 Hz, C2), 60.9 (OCH2), 126.7 (C4Ј), 129.8
1
cedure. Ϫ H NMR (CDCl3): δ ؍ 2.45 (s, 3 H, CH3), 6.22 (dt, 1
(C2Ј), 131.0 (C3Ј and C6Ј), 132.2 (C5Ј), 140.8 (C1Ј), 167.0 (CϭO). Ϫ
H, JHH ϭ 16.0 Hz and JHF ϭ 12.1 Hz, H2), 7.08Ϫ7.20 (m, 2 H, MS (70 eV); m/z (%): 596 (7) [Mϩ·], 551 (14), 149 (36), 131 (100).
1126 Eur. J. Org. Chem. 2001, 1121Ϫ1128

Efficient Access to Perfluoroalkylated Aryl Compounds by Heck Reaction
FULL PAPER
Ϫ C19H13F17O2 (596.3): calcd. C 38.27, H 2.20; found C 38.27,
H 2.17.
(t, JCF ϭ 22.1 Hz, C2Ј), 128.4 (d, JCP ϭ 7.0 Hz, C3), 134.0 (d, JCP ϭ
19.7 Hz, C2), 135.4 (d, JCP ϭ 10.8 Hz, C1), 139.8 (C4). Ϫ 19F NMR
(CDCl3): δ ϭ Ϫ126.6 (m, 2 F, F9), Ϫ124.0 (m, 2 F, F4), Ϫ123.2
(m, 2 F), Ϫ122.4 (m, 4 F, F6 and F7), Ϫ122.1 (m, 2 F), Ϫ115.1 (m,
2 F, F3), Ϫ81.34 (m, 3 F, F10). Ϫ 31P NMR (CDCl3): δ ϭ Ϫ6.6. Ϫ
C48H18F51P (1600): calcd. C 37.93, H 2.06; found C 38.10, H 1.93.
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-1-(4Ј-nitro-
phenyl)dec-1-ene (1h): Grey solid (2.768 g, 4.88 mmol), prepared
from 4-nitrobenzenediazonium tetrafluoroborate (5 mmol) and 5 in
98% yield according to the general procedure. Ϫ M.p. 92Ϫ97 °C.
Ϫ 1H NMR (CDCl3): δ ؍ 6.39 (dt, 1 H, JHH ϭ 16.0 Hz and JHF ϭ
12.0 Hz, H2), 7.28 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 2.1 Hz, H1),
7.68 (d, 2 H, J ϭ 8.4 Hz, H2Ј), 8.30 (d, 2 H, J ϭ 8.4 Hz, H3Ј). Ϫ
13C NMR (CDCl3): δ ϭ 118.7 (t, JCF ϭ 23.3 Hz, C2), 124.1 (C3Ј),
128.3 (C2Ј), 137.3 (t, JCF ϭ 4.0 Hz, C1), 139.3 (C1Ј), 148.5 (C4Ј). Ϫ
C16H6F17NO2 (567.2): calcd. C 33.88, H 1.07, N 2.47; found C
33.85, H 0.99, N 2.64.
Tris[4-(3Ј,3Ј,4Ј,4Ј,5Ј,5Ј,6Ј,6Ј,7Ј,7Ј,8Ј,8Ј,9Ј,9Ј,10Ј,10Ј,10Ј-heptadeca-
fluorodecyl)-2-methylphenyl]phosphane (3e): This was prepared
from 2e (5.7 mmol) according to the procedure described for 3b,
affording 2.97 g of a light yellow solid (95% yield). The solid could
be recrystallized from Et2O/methanol (1:1) in 64% yield Ϫ M.p. 76
1
°C. Ϫ H NMR (CDCl3): δ ؍ 2.32Ϫ2.51 (m, 6 H, H2Ј), 2.40 (s, 9
H, CH3), 2.87Ϫ2.95 (m, 6 H, H1Ј), 6.67 (dd, 3 H, J ϭ 7.8 and
4.1 Hz, H5), 6.95 (d, 3 H, J ϭ 7.8 Hz, H6), 6.95 (d, 3 H, J ϭ 3.4 Hz,
H3). Ϫ 13C NMR (CDCl3, 50 MHz): δ ϭ 21.0 (d, JCP ϭ 21.2 Hz,
CH3), 26.0 (C1Ј), 32.6 (t, JCF ϭ 22.1 Hz, C2Ј), 125.9 (C5), 130.1
(C3), 132.6 (d, JCP ϭ 10.6 Hz, C1), 133.3 (C6), 139.6 (C4), 143.0 (d,
JCP ϭ 26.6 Hz, C2). Ϫ 19F NMR (CDCl3): δ ϭ Ϫ126.5 (m, 2 F,
F9), Ϫ123.9 (m, 2 F, F4), Ϫ123.1 (m, 2 F), Ϫ122.3 (m, 4 F, F6 and
F7), Ϫ122.1 (m, 2 F), Ϫ115.1 (m, 2 F, F3), Ϫ81.2 (m, 3 F, F10). Ϫ
31P NMR (CDCl3): δ ϭ Ϫ30.5. Ϫ C51H30F51P (1643): calcd. C
37.29, H 1.84; found C 37.43, H 1.76.
1-(4Ј-Aminophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca-
fluorodecane (2k): White solid (1.990 g, 3.69 mmol), prepared from
1h (4 mmol) in 92% yield according to the general procedure. Ϫ
M.p. 68 °C. Ϫ 1H NMR (CDCl3): δ ؍ 2.19Ϫ2.49 (m, 2 H, H2),
2.76Ϫ2.89 (m, 2 H, H1), 3.64 (2 H, br s, NH2), 6.68 (d, 2 H, J ϭ
8.3 Hz, H3Ј), 7.04 (d, 2 H, J ϭ 8.3 Hz, H2Ј). Ϫ 13C NMR (CDCl3):
δ ϭ 25.4 (C1), 33.2 (t, JCF ϭ 22.2 Hz, C2), 115.3 (C3Ј), 129.0 (C1Ј
and C2Ј), 144.9 (C4Ј). Ϫ MS (70 eV); m/z (%): 539 (7) [Mϩ·], 520
(2), 106 (100). Ϫ C18H10F17N (539.2): calcd. C 35.64, H 1.87, N
2.60; found C 35.62, H 1.78, N 2.61.
Cross-Coupling between 6 and 7: A mixture of Pd(OAc)2 (0.5 mg,
0.005 mmol) and perfluorinated triphenylphosphane 3b (16 mg,
0.01 mmol) in degassed FC-72/methanol (1:1) mixture (1 mL) was
stirred at room temperature for 5 min under argon, then methanol
was removed. To this biphasic solution was added a mixture of
potassium trifluoro(vinyl)borate 7 (134 mg, 1 mmol) and 4-ethoxy-
carbonylbenzenediazonium tetrafluoroborate (6, 264 mg, 1 mmol)
in degassed MeOH (2 mL). The resulting mixture was vigorously
stirred until gas evolution ceased. The organic layer was removed
and the fluorous phase was washed under argon with methanol
(1 mL), water (1 mL) and twice with methanol (1 mL). The com-
bined organic layers were concentrated under reduced pressure, dis-
solved in Et2O (10 mL), washed with water (10 mL twice) and brine
(10 mL). The solution was dried with anhydrous MgSO4, concen-
trated under reduced pressure to give 175 mg of 4-ethoxycarbonyl-
styrene (yield 99%). To the fluorous phase was then added the same
mixture as described above to begin a new cycle.
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-1-phenyldec-1-
ene (1i): Colorless oil (2.578 g, 4.94 mmol), prepared from benzene-
diazonium tetrafluoroborate (5 mmol) and 5 in 99% yield accord-
1
ing to the general procedure. Ϫ H NMR (CDCl3): δ ؍ 6.31 (dt,
1 H, JHH ϭ 16.1 Hz and JHF ϭ 12.2 Hz, H2), 7.27 (dt, 1 H, JHH ϭ
16.1 Hz and JHF ϭ 2.2 Hz, H1), 7.45Ϫ7.57 (m, 5 H). Ϫ 13C NMR
(CDCl3): δ ϭ 114.4 (t, JCF ϭ 23.2 Hz, C2), 127.5 (C2Ј), 128.8 (C3Ј),
130.0 (C4Ј), 133.6 (C1Ј), 139.7 (t, JCF ϭ 9.5 Hz, C1). Ϫ C16H7F17
(522.2): calcd. C 36.80, H 1.35; found C 36.80, H 1.43.
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-1-(4Ј-iodo-
phenyl)dec-1-ene (1j): White solid (2.905 g, 4.48 mmol), prepared
from 4-iodobenzenediazonium tetrafluoroborate (5 mmol) and 5 in
90% yield according to the general procedure using THF/methanol
(1:1) as the solvent at room temperature (the crude product con-
1
tained around 10% of bis-coupling product). Ϫ M.p. 67 °C. Ϫ H
NMR (CDCl3): δ ؍ 6.24 (dt, 1 H, JHH ϭ 16.1 Hz and JHF
ϭ
12.0 Hz, H2), 7.12 (dt, 1 H, JHH ϭ 16.1 Hz and JHF ϭ 2.2 Hz, H1),
7.23 (d, 2 H, J ϭ 8.4 Hz, H2Ј), 7.78 (d, 2 H, J ϭ 8.4 Hz, H3Ј). Ϫ
13C NMR (CDCl3): δ ϭ 96.2 (C4Ј), 115.1 (t, JCF ϭ 22.9 Hz, C2),
129.0 (C2Ј), 132.9 (C1Ј), 138.1 (C3Ј), 138.6 (t, JCF ϭ 9.6 Hz, C1). Ϫ
MS (70 eV); m/z (%): 648 (4) [Mϩ·], 279 (14), 152 (100). Ϫ
C16H6F17I (648.1): calcd. C 29.65, H 0.95; found C 29.50, H 0.88.
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fluorodecyl)phenyl]phosphane (3b): To a cooled (Ϫ30 °C) mixture
of 2b (5.428 g; 9 mmol) in anhydrous THF/Et2O (1:1, 60 mL) was
added dropwise nBuLi (3.6 mL, 2.5  in hexane) keeping the in-
ternal temperature below Ϫ30 °C. The solution, which turned a
yellow-green colour, was stirred for 5 min. Freshly distilled PCl3
(260 µL, 3 mmol) was added dropwise at Ϫ30 °C and the mixture,
which turned a purple colour, was stirred at room temperature for
10 min. The solution was filtered through SiO2 under argon, eluting
with anhydrous Et2O (20 mL, twice). Solvents were removed under
reduced pressure to afford 4.5 g of a pale yellow solid (94% yield).
The compound (containing around 5% of the oxide) could be
recrystallized in Et2O/MeOH (1:1) to give the phosphane 3b as a
white powder (3.36 g; 70% yield). Ϫ M.p. 98 °C. Ϫ 1H NMR
(CDCl3): δ ؍ 2.35Ϫ2.53 (m, 6 H, H2Ј), 2.90Ϫ2.99 (m, 6 H, H1Ј),
7.20Ϫ7.32 (12 H, Ar). Ϫ 13C NMR (CDCl3): δ ϭ 26.1 (C1Ј), 32.6
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1128
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