Halofluorination of alkenes mediated by 1,1,3,3,3-pentafluoropropene- diethylamine adduct

Article abstract of DOI:10.1016/j.jfluchem.2012.07.012

1,1,3,3,3-Pentafluoropropene-diethylamine complex (PFPDEA) has been found useful as a fluoride source in halofluorination reactions of various olefins. Reactions proceeded with PFPDEA and N-halosuccinimide (NXS, X = Br, I) or 1,3-dibromo-5,5-dimethylhydan

Full text of DOI:10.1016/j.jfluchem.2012.07.012

Journal of Fluorine Chemistry 143 (2012) 287–291
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Halofluorination of alkenes mediated by 1,1,3,3,3-pentafluoropropene-
diethylamine adduct
Justyna Walkowiak *, Bartosz Marciniak, Henryk Koroniak
Adam Mickiewicz University, Faculty of Chemistry, Grunwaldzka 6, 60-780 Pozna n´ , Poland
A R T I C L E I N F O
A B S T R A C T
Article history:
1,1,3,3,3-Pentafluoropropene-diethylamine complex (PFPDEA) has been found useful as a fluoride
source in halofluorination reactions of various olefins. Reactions proceeded with PFPDEA and
N-halosuccinimide (NXS, X = Br, I) or 1,3-dibromo-5,5-dimethylhydantoin (DBH), as sources of
electrophilic halogens, in a regioselective manner.
Received 30 April 2012
Received in revised form 19 July 2012
Accepted 24 July 2012
Available online 7 August 2012
ß 2012 Elsevier B.V. All rights reserved.
Dedicated to Professor David O’Hagan on
the occasion of receiving ACS Award for
Creative Work in Fluorine Chemistry.
Keywords:
Iodofluorination
Bromofluorination
Fluoroamino reagents (FAR)
1
,1,3,3,3-Pentafluoropropene-diethylamine
complex
1
. Introduction
hexafluoropropene–diethylamine complex (Ishikawa reagent)
[
9], combined with N-halosuccinamides, has been successfully
Fluoroorganic compounds show unique chemical and physical
used to prepare halofluorinated derivatives.
properties in the field of biological and material science [1].
Preparation of fluoroorganic derivatives has risen considerable
interest in development of selective and convenient methods of
introducing fluorine atom(s) into molecules. One of the most
straightforward ways is halofluorination of unsaturated hydro-
carbons, allowing introduction of fluoride ion under conditions
much milder than direct hydrofluorination. Halofluoroalkanes, i.e.
the resultant products, are useful synthetic intermediates of
numerous fluoroorganic compounds [2].
In our previous studies, aimed at synthesis of a new selective
nucleophilic reagent suitable for introduction of fluorine atom(s)
into organic molecules, we developed a convenient route of
obtaining an adduct of 1,1,3,3,3-pentafluoropropene with diethy-
lamine (PFPDEA) [10]. Now we have found that use of PFPDEA and
positive halogen sources (NXS, DBH) supports efficient conversion
of various olefins into corresponding halofluorides under mild
conditions.
In general, halofluorination of the carbon-carbon double bond
is performed by formal addition of halogen fluorides (ClF, BrF, IF),
generated in situ. It can be achieved in reaction of positive halogen
sources and appropriate fluorination reagent. A 70% HFÁpyridine
2. Results and discussion
2.1. 1,1,3,3,3-Pentafluoropropene-diethylamine adduct (PFPDEA)
complex (Olah’s reagent) [3] or Et
3
NÁHF [4] are most commonly
used as fluoride sources, and N-halosuccinimide (NXS) [3,4], N-
halosaccharin (NXSac) [5] or trihaloisocyanuric acids (TXCA) [6]
as sources of electrophilic halogen. Likewise, tetrabutylammo-
nium bifluoride (TBABF) [7], ionic liquid, 1-ethyl-3-methylimi-
1,1,3,3,3-Pentafluoropropene-diethylamine adduct (PFPDEA)
was synthesized by formal nucleophilic substitution of fluoride
with diethylamine (DEA) at the double bond of pentafluoropro-
pene (PFP), similarly to the procedure described previously by
Ishikawa [11]. This reaction gave a mixture of two products,
namely 1-diethylamino-1,3,3,3-tetrafluoropropene (1) and only
traces of the desired N,N-diethyl-1,1,3,3,3-pentafluoropropyla-
mine (2) (Fig. 1). The presented fluorinating mixture readily
hydrolyzes when exposed to moist air, and vigorously reacts with
dazolium oligo hydrogen fluoride (EMIMF(HF)2.3
) [8] or
*
Corresponding author. Tel.: +48 61 8291225; fax: +48 61 8291505.
E-mail address: Justyna.A.Walkowiak@amu.edu.pl (J. Walkowiak).
0022-1139/$ – see front matter ß 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2012.07.012

2
88
J. Walkowiak et al. / Journal of Fluorine Chemistry 143 (2012) 287–291
proceeds stereospecifically in an anti-sense, as evidenced by the
formation, in good yield, of trans-1-bromo-2-fluorocyclohexane
a, or trans-1-iodo-2-fluorocyclohexane 6b from cis-cyclohexene
Table 2, Entry 7–8). These results prove that halofluorinations of
6
(
Fig. 1. PFPDEA.
olefins proceed via an intermediate halonium ion. However, the
bromofluorination of trans-stilbene yield a mixture of erythro- and
threo-1-bromo-2-fluoro-1,2-diphenylethane in 95:5 ratio, respec-
tively. These observations indicate that both bridged (bromonium
ion) and nonbridged (benzylic cation) intermediates can be
involved in the reaction mechanism.
water, forming the N,N-diethyl-3,3,3-trifluoropropionamide and
hydrogen fluoride [10a].
2.2. Halofluorination of alkenes with PFPDEA
In an unsaturated hydrocarbon system such as 2,5-norborn-
diene, where transannular
p-participations is possible, halofluor-
Our initial survey focused on optimizing conditions for
ination did occur and led to forming a mixture of halofluorides 7
and 8 (Table 2, Entry 9–10).
halofluorination of styrene with PFPDEA as a hydrogen fluoride
source (Table 1). Applying the same literature protocol as the one
used in halofluorination of olefins with Ishikawa reagent (HFP-DA)
The addition is regioselective and the regiochemistry is in line
with the Markovnikov rule. For example, the bromo- and
iodofluorinations of styrene give the 2-bromo-1-fluoro-1-pheny-
lethane with complete regioselectivity (Table 1), and not even
[
9] led to formation of the desired product but these transforma-
tions were very low-yielding. Increasing the amount of PFPDEA
added did not influence significantly the yields of 1-fluoro-2-
haloethylbenzenes. However, changing the reagents addition
sequence led to successful halofluorination of styrene and
considerably improved the yields of the formed products. As
shown in Table 1, the best results were achieved when the
19
traces of the regioisomeric adduct were detected by F NMR
spectroscopy of the crude reaction mixtures. Similarly, in the case
of 2-vinylpyridine, fluorine atom was introduced in more
substituted carbon, forming only one bromofluorinated product
9 (Table 2, Entry 11). In halofluorinations of other simple
unsymmetrical olefins such as 1-alkenes (Table 2, entry 1–6),
the Markovnikov products 4a–f also predominate (9:1) over the
corresponding anti-Markovnikov 5a–f compounds.
reactions were carried out with PFPDEA (5.0 equiv.),
2
H O
(
5
5.0 equiv.), N-iodosuccinimide (NIS, 2.5 equiv.) or 1,3-dibromo-
,5-dimethylohydantoin (DBH, 2.5 equiv.) and hexamethylpho-
sphoric triamide (HMPA, 2.0 equiv.) in CH
temperature for 24 h.
2
Cl
2
at À30 8C to room
Concluding, we demonstrated that 1,1,3,3,3-pentafluoropro-
pene-diethylamine adduct PFPDEA can be a good source of
hydrogen fluoride in halofluorination reactions. The reactions
provide a ready procedure for introducing fluorine into alkenes
under mild conditions with high regioselectivity and stereospe-
cifity. Our competitive studies revealed that in halofluorination
reactions PFPDEA is an efficient fluorinating agent, comparable to
the Ishikawa reagent.
In further works we decided to test various olefins that could be
suitable for halofluorination. It should give us a range of
halofluorinated derivatives. The procedure we developed for
forming the products, was applied in reactions of aromatic,
aliphatic and alicyclic unsaturated hydrocarbons. In the optimized
reaction conditions, various olefins were converted into corre-
sponding halofluorides in good to very good yields, as shown in
Table 2.
3. Experimental
The present halofluorination reaction most probably proceeds
via controlled generation of limited amounts of hydrogen fluoride
3.1. General methods
2
from PFPDEA and H O, followed by in situ formation of iodine
fluoride or bromine fluoride species with NIS or DBH, respectively.
The formal electrophilic addition of ‘‘XF’’ to the double bond
NMR spectra were recorded in deuterated solvents at 300 MHz
( H), 75 MHz ( C) and at 282 MHz ( F), calibrated using an
1
13
19
Table 1
a
Halofluorination of styrene.
À
+
b
Entry
F
source (equiv.)
X
source (equiv.)
H
2
O (equiv.)
Yield
1
2
3
HFP-DA (2.5)
PFPDEA (2.5)
PFPDEA (5.0)
PFPDEA (5.0)
HFP-DA (2.5)
PFPDEA (2.5)
PFPDEA (5.0)
PFPDEA (5.0)
HFP-DA (2.5)
PFPDEA (2.5)
PFPDEA (5.0)
PFPDEA (5.0)
NIS (2.5)
NIS (2.5)
NIS (2.5)
NIS (2.5)
NBS (2.5)
NBS (2.5)
NBS (2.5)
NBS (2.5)
DBH (2.5)
DBH (2.5)
DBH (2.5)
DBH (2.5)
2.5
2.5
5.0
5.0
2.5
2.5
5.0
5.0
2.5
2.5
5.0
5.0
81%
19%
47%
74%
46%
10%
18%
50%
71%
17%
38%
77%
c
4
5
6
7
c
8
9
1
1
0
1
c
1
2
a
b
c
Literature protocol: HFP-DA or PFPDEA, NXS or DBH, H
2
O and HMPA [9].
Yields determined by F NMR analysis, using m-fluorotoluene as an internal standard ( F NMR (282 MHz, CDCl
Alternative addition sequence: PFPDEA + H O, NXS or DBH and HMPA.
19
19
3
)
d
= À114.1 (m, 1 F)).
2

J. Walkowiak et al. / Journal of Fluorine Chemistry 143 (2012) 287–291
289
Table 2
Products distribution in halofluorination of various olefins with PFPDEA.
+
a
Entry
1
Olefin
X
source
Products
Yields
.
( )7
DBH
F
Br
68% (4a:5a, 90:10)
76% (4b:5b, 86:14)
52% (4c:5c, 87:13)
Br
I
F
.
.
.
( )
7
( )
7
4
a
5a
2
3
4
5
NIS
F
I
F
( )
7
( )
7
4
b
5b
.
( )13
DHB
F
Br
Br
I
F
( )13
( )13
4
c
5c
NIS
F
I
74% (4d:5d, 88:12)
64% (4e:5e, 88:12)
F
.
.
( )13
( )13
4
d
5d
DBH
F
Br
( )15
.
( )15
Br
F
( )15
4
e
5e
6
7
NIS
F
I
64% (4f:5f, 88:12)
I
F
.
.
( )15
( )15
4
f
5f
DBH
F
59%
.
Br
6
a
8
9
NIS
F
I
46%
.
.
6
b
7
DBH
39% (7a:8a, 44:56)
.
Br
F
Br
F
a
8a
1
1
1
a
0
1
2
NIS
32% (7b:8b, 42:58)
I
F
I
.
.
F
7
b
8a
DBH
DBH
51%
.
N
N
Br
F
9
59% (erythro:threo, 95:5)
F
.
.
Br
1
0
19
19
Yields determined by F NMR analysis using m-fluorotoluene as an internal standard ( F NMR (282 MHz, CDCl
3
)
d
=À114.1 (m, 1F)).
1
13
19
internal reference: TMS ( H), CDCl
3
(
C) or CFCl
3
(
F). Chemical
using a AMD-402 spectrometer. Thin-layer chromatography (TLC)
was performed on coated silica gel plate Merck 60
shifts ( ) are quoted in parts per million (ppm) and coupling
d
254
F .
constants (J) are measured in Hertz (Hz). The following abbrevia-
tions are used to describe multiplicities s = singlet, d = doublet,
t = triplet, q = quartet, b = broad, m = multiplet. Mass spectra were
recorded by GC/MS coupling (EI, 70 eV). HRMS (EI) were recorded
Visualization of the reaction components was achieved using
U.V. fluorescence (254 nm) and cerium(IV) ammonium nitrate or
4
KMnO solution stain. For purification of products column
chromatography was carried out over Merck silica gel

2
90
J. Walkowiak et al. / Journal of Fluorine Chemistry 143 (2012) 287–291
6
0 (0.063–0.2 mm). All reagents purchased from suppliers were
used without further purification. CH Cl was dried and distilled
over CaH . Solvents for chromatography were distilled prior to use.
3.2.1.5. Bromofluorination of 1-hexadecene. According to the gen-
eral procedure, in the reaction of fluorinating agent PFPDEA
(0.926 g, 5.0 mmol), H O (0.009 g, 9.0 L, 5.0 mmol), DBH (0.715 g,
.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and 1-hexadecene
(0.224 g, 0.289 mL, 1.0 mmol) in dry CH Cl a mixture of 4c and 5c
2
2
2
2
m
2
3.2. General procedures
2
2
was obtained. The NMR data were in a good agreement with those
already reported [12].
3.2.1. Halofluorination of alkenes; general procedure
In an ordinary glassware round-bottom flask to a solution of
PFP-DA (5 equiv.) in dry CH
2
Cl
2
(1.5 mL) at room temperature,
3.2.1.6. Iodofluorination of 1-hexadecene. According to the general
water (5 equiv.) was added. Forthwith the hydrolysis occurred, the
resulting mixture was placed in cooling bath (acetonitrile/dry ice).
To the cooled reaction mixture (À30 8C) NXS or DBH (2.5 equiv.)
and HMPA (2.0 equiv.) were added, and the whole was stirred at
the temperature for next 30 min. A solution of alkene (1 equiv.) in
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
5.0 mmol),
2
H O (0.009 g, 9.0 mL, 5.0 mmol), NIS (0.563 g,
2.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and 1-hexadecene
(0.224 g, 0.289 mL, 1.0 mmol) in dry CH Cl a mixture of 4d and 5d
2 2
was obtained.
1
CH
2
Cl
2
(1.5 mL) was added dropwise, cooling bath was removed
4d: H NMR (300 MHz, CDCl
3
):
d
4.48 (dddt, 1H, J = 48.0, 11.1,
I), 3.28
a b
H I), 1.91–1.56 (m, 2H), 1.46–
and the reaction mixture was allowed to stand at room
temperature for 24 h. When the reaction was complete the
appropriate amount of NMR internal standard, m-fluorotoluene
5.8, 5.0 Hz, CHF), 3.33 (ddd, 1H, J = 19.5, 11.1, 5.0 Hz, CH
(ddd, 1H, J = 19.5, 11.1, 5.8 Hz, CH
1.15 (m, 24H), 0.88 (t, 3H J = 6.7, Hz). C NMR (100 MHz, CDCl
92.2 (d, J = 174.5 Hz), 34.8 (d, J = 20.5 Hz), 31.9, 29.69, 29.67, 29.65,
9.6, 29.4, 29.3, 29.2, 24.7 (d, J = 4.2 Hz), 22.7, 14.1. F NMR
(282 MHz, CDCl
a b
H
1
3
3
): d
(1 equiv.), was added and a sample analyzed by NMR.
19
2
+
3.2.1.1. Bromofluorination of styrene. According to the general
3
):
d
À171.4 (m, 1F, CHF). HRMS (EI): m/z [M ] calcd
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
for C16 32FI: 370.1533; found: 370.1537.
H
1
5
2
.0 mmol),
.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and styrene
Cl 3a was obtained.
H
2
O
(0.009 g, 9.0
m
L, 5.0 mmol), DBH (0.715 g,
5d: H NMR (300 MHz, CDCl ): 4.65 (ddd, 1H, J = 48.2, 9.5,
3
d
5.3 Hz, CH F), 4.49 (ddd, 1H, J = 48.2, 9.5, 8.1 Hz, CH F), 4.21
a
H
b
a b
H
(0.104 g, 0.115 mL, 1.0 mmol) in dry CH
2
2
(dddt, 1H, J = 13.3, 8.1, 5.3, 5.3, Hz, CHI), 1.96–1.65 (m, 2H), 1.48–
1
3
The NMR data were in a good agreement with those already
reported [7–9].
1.14 (m, 24H), 0.88 (t, 3H J = 6.7, Hz). C NMR (100 MHz, CDCl
3
): d
86.6 (d, J = 177.4 Hz), 31.9, 31.2 (d, J = 19.2 Hz), 29.68, 29.67, 29.65,
1
9
2
9.6, 29.5, 29.4, 29.3, 29.1, 28.7, 24.1, 14.1. F NMR (282 MHz,
CDCl ): F). HRMS (EI): m/z
À198.5 (td, 1F, J = 48.2, 13.3 Hz, CH
[M ] calcd for C16 32FI: 370.1533; found: 370.1537.
3.2.1.2. Iodofluorination of styrene. According to the general
3
d
2
+
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
H
5
2
.0 mmol),
.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and styrene
Cl 3b was obtained.
2
H O (0.009 g, 9.0 mL, 5.0 mmol), NIS (0.563 g,
3.2.1.7. Bromofluorination of 1-octadecene. According to the gen-
eral procedure, in the reaction of fluorinating agent PFPDEA
(0.104 g, 0.115 mL, 1.0 mmol) in dry CH
2
2
The NMR data were in a good agreement with those already
reported [3d,6–9].
(0.926 g, 5.0 mmol), H
2.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and 1-octadecene
0.253 g, 0.320 mL, 1.0 mmol) in dry CH Cl a mixture of 4e and 5e
2
O (0.009 g, 9.0 mL, 5.0 mmol), DBH (0.715 g,
(
2
2
3
.2.1.3. Bromofluorination of 1-decene. According to the general
was obtained.
1
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
4e: H NMR (300 MHz, CDCl
3
):
d
4.62 (dddt, 1H, J = 47.0, 11.1,
Br),
Br), 1.87–1.55 (m, 2H),
5
2
.0 mmol),
.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and 1-decene
Cl a mixture of 4a and 5a
H
2
O
(0.009 g, 9.0
m
L, 5.0 mmol), DBH (0.715 g,
6.2, 5.7 Hz, CHF), 3.48 (ddd, 1H, J = 19.7, 10.8, 5.7 Hz, CH
3.42 (ddd, 1H, J = 19.7, 10.8, 6.2 Hz, CH
1.52–1.13 (m, 28H), 0.88 (t, 3H, J = 6.8 Hz). C NMR (75 MHz,
CDCl ): 91.1 (d, J = 174.7 Hz), 32.7 (d, J = 25.5 Hz), 32.4 (d,
J = 20.5 Hz), 30.9 (s, C-6), 28.7–28.6 (7C), 28.6, 28.5, 28.4, 28.3 (d,
a b
H
a b
H
1
3
(0.140 g, 0.189 mL, 1.0 mmol) in dry CH
2
2
was obtained. The NMR data were in a good agreement with those
already reported [12].
3
d
1
9
J = 6.5 Hz), 23.7 (d, J = 4.3 Hz), 21.7, 13.1. F NMR (282 MHz,
+
3.2.1.4. Iodofluorination of 1-decene (4b). According to the general
CDCl
3
):
d
À178.3 (m, 1F, CHF). HRMS (EI): m/z [M ] calcd for
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
C H36BrF: 350.1954; found: 350.1963.
18
1
5
2
.0 mmol),
.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and 1-decene
Cl a mixture of 4b and 5b
H
2
O
(0.009 g, 9.0
m
L, 5.0 mmol), NIS (0.563 g,
5e: H NMR (300 MHz, CDCl ): 4.61 (ddd, 1H, J = 47.1, 9.3,
3
d
5.4 Hz, CH F), 4.45 (ddd, 1H, J = 47.1, 9.3, 8.1 Hz, CH F), 4.19
a
H
b
a b
H
(0.140 g, 0.189 mL, 1.0 mmol) in dry CH
2
2
(dddt, 1H, J = 13.8, 8.1, 5.4, 5.4, Hz, CHBr), 1.93–1.66 (m, 2H), 1.47–
1
3
was obtained.
3
1.15 (m, 28H), 0.88 (t, 3H J = 6.8, Hz). C NMR (100 MHz, CDCl ): d
1
4
b: H NMR (300 MHz, CDCl
3
):
d
4.45 (dddt, 1H, J = 47.2, 11.0,
I), 3.29
I), 1.86–1.61 (m, 2H), 1.52–
85.2 (d, J = 176.4 Hz), 56.0 (d, J = 51.9 Hz), 36.2 (d, J = 34.0 Hz), 31.9,
29.7–29.6 (7C), 29.6, 29.5, 29.4 (d, J = 2.1 Hz), 28.8, 26.8, 22.7,
5
.8, 5.0 Hz, CHF), 3.33 (ddd, 1H, J = 19.9, 10.9, 5.0 Hz, CH
a b
H
1
9
(ddd, 1H, J = 19.9, 10.9, 5.8 Hz, CH
a
H
b
14.13. F NMR (282 MHz, CDCl
3
+
):
d
À210.33 (td, 1F, J = 47.1,
F). HRMS (EI): m/z [M ] calcd for C18 36BrF: 350.1954;
found: 350.1963.
13
1
9
2
.14 (m, 12H), 0,88 (t, 3H J = 6.7 Hz). C NMR (100 MHz, CDCl
3
):
d
13.8 Hz, CH
2
H
7.1 (d, J = 174.6 Hz), 34.8 (d, J = 20.5 Hz), 31.8, 29.3, 29.2, 29.1,
19
4.7 (d, J = 4.2 Hz), 22.6, 14.1. F NMR (282 MHz, CDCl
3
):
d
À171.5
+
(m, 1F, CHF). HRMS (EI): m/z [M ] calcd for C10
H20FI: 286.0594;
3.2.1.8. Iodofluorination of 1-octadecene. According to the general
found: 286.0602.
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
1
5
b: H NMR (300 MHz, CDCl
3
):
d
4.62 (ddd, 1H, J = 47.2, 9.5,
F), 4.18
5.0 mmol),
2
H O (0.009 g, 9.0 mL, 5.0 mmol), NIS (0.563 g,
5
.3 Hz, CH
a
H
b
F), 4.48 (ddd, 1H, J = 47.2, 9.5, 8.1 Hz, CH H
a b
2.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and 1-hexadecene
(
dddt, 1H, J = 13.7, 8.1, 5.3, 5.3 Hz, CHI), 1.94–1.67 (m, 2H), 1.46–
2 2
(0.253 g, 0.320 mL, 1.0 mmol) in dry CH Cl a mixture of 4f and 5f
was obtained.
13
1
8
2
1
.16 (m, 12H), 0.88 (t, 3H J = 6.7 Hz). C NMR (100 MHz, CDCl
3
):
d
1
6.6 (d, J = 177.5 Hz), 31.8, 31.2 (d, J = 19.6 Hz), 29.3, 29.2, 29.1,
4f: H NMR (300 MHz, CDCl
3
):
d
4.45 (dddt, 1H, J = 47.6, 11.0,
I), 3.29
a b
H I), 1.84–1.64 (m, 2H), 1.49–
1
9
2.6, 14.1. F NMR (282 MHz, CDCl
3
):
d
À198.5 (td, 1F, J = 47.2,
20FI: 286.0594;
5.8, 5.1 Hz, CHF), 3.33 (ddd, 1H, J = 19.5, 10.9, 5.1 Hz, CH
(ddd, 1H, J = 19.5, 10.9, 5.8 Hz, CH
3
1.13 (m, 28H), 0.87 (t, 3H J = 6.7, Hz). C NMR (75 MHz, CDCl ): d
a b
H
+
3.7 Hz, CH
2
F). HRMS (EI): m/z [M ] calcd for C10
H
1
3
found: 286.0602.

J. Walkowiak et al. / Journal of Fluorine Chemistry 143 (2012) 287–291
291
1
9
9
2
0.2 (d, J = 172.6 Hz), 32.5 (d, J = 26.4 Hz), 32.2 (d, J = 20.3 Hz), 30.7,
8.8-28.7 (7 C), 28.6, 28.5, 28.4, 28.3 (d, J = 6.6 Hz), 23.7 (d,
(d, J = 23.8 Hz); F NMR (282 MHz, CDCl
3
):
d
À189.43 (ddd, 1F,
+
J = 46.2, 23.6, 22.6 Hz CHF). HRMS (EI): m/z [M ] calcd for
19
J = 4.5 Hz), 21.5, 13.0. F NMR (282 MHz, CDCl
3
):
d
À171.35 (m, 1F,
7 7
C H BrFN: 202.9746; found: 202.9752.
+
CHF). HRMS (EI): m/z [M ] calcd for C18
98.1851.
H36FI: 398.1846; found:
3
3.2.1.14. Bromofluorination of trans-stilbene. According to the
general procedure, in the reaction of fluorinating agent PFPDEA
1
5
f: HNMR(300 MHz, CDCl
F), 4.46 (ddd, 1H, J = 47.28, 9.2, 8.3 Hz, CH
J = 13.8, 8.3, 5.4, 5.4, Hz, CHI), 1.92–1.65 (m, 2H), 1.42–1.11 (m, 28H),
3
):
d
4.61(ddd, 1H, J = 47.8, 9.2, 5.4 Hz,
CH
H
a b
a b
H F), 4.13 (dddt, 1H,
(0.926 g, 5.0 mmol), H
2.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and trans-stilbene
(0.180 g, 1.0 mmol) in dry CH Cl a mixture of erythro-1-bromo-2-
fluoro-1,2-diphenylethane erythro-10 and threo-1-bromo-2-
fluoro-1,2-diphenylethane threo-10 was obtained. The NMR data
were in a good agreement with those already reported [14].
2
O (0.009 g, 9.0 mL, 5.0 mmol), DBH (0.715 g,
13
0
.87 (t, 3H, J = 6.7 Hz). C NMR (100 MHz, CDCl
J = 175.8 Hz), 55.4 (d, J = 50.7 Hz), 36.0 (d, J = 32.9 Hz), 31.8, 29.7-
9.6 (7 C), 29.5, 29.4, 29.3 (d, J = 2.1 Hz), 28.8, 26.8, 22.7, 14.0.
3
):
d
83.1 (d,
2
2
2
19
FNMR (282 MHz, CDCl
3
):
d
À198.54(td,1F, J = 47.8, 13.8 Hz, CH
2
F).
+
HRMS (EI): m/z [M ] calcd for C18
H
36FI: 398.1846; found: 398.1851.
Acknowledgements
3.2.1.9. Bromofluorination of cyclohexene. According to the general
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
Financial support by the European Union through Human
Capital: National Cohesion Strategy is gratefully acknowledged
5
.0 mmol),
.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and cyclohexene
Cl 6a was obtained. The
NMR data were in a good agreement with those already reported
8].
2
H O (0.009 g, 9.0 mL, 5.0 mmol), DBH (0.715 g,
2
(
POKL.04.01.01-00-019/10 for B.M.). We are indebted to Prof. Dr.
(0.082 g, 0.101 mL, 1.0 mmol) in dry CH
2
2
G u¨ nter Haufe for advice and fruitful discussions. Part of this work
was supported also by Polish Ministry of Science and National Edu-
cation (grant N N204 277240 to J.W.). Pentafluoropropene sample
[
(
PFP) was kindly provided to us by SynQuest Laboratories Ltd.
3
.2.1.10. Iodofluorination of cyclohexene. According to the general
procedure, in the reaction of fluorinating agent PFPDEA (0.926 g,
.0 mmol), H O (0.009 g, 9.0 L, 5.0 mmol), NIS (0.563 g, 2.5 mmol),
HMPA (0.358 g, 0.35 mL, 2.0 mmol) and styrene (0.082 g, 0.101 mL,
.0 mmol) in dry CH Cl 6b was obtained. The NMR data were in a
good agreement with those already reported [8].
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5
2
m
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8
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(
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13
iodonortricyclane 8b was obtained. The H, C NMR data were in a
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(
1
9
7
3
):
):
d
À191.83 (d, 1F, J = 58.5 Hz,
(
[
[
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.5 mmol), HMPA (0.358 g, 0.35 mL, 2.0 mmol) and 2-vinylpyr-
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8.52 (m, 1H, Ar), 7.71 (td, 1H,
1
(
5
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(
2
2
m
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2
1
9
3
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3
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1