Copper-Catalyzed Direct Trifluoro- and Perfluoroalkylselenolations of Boronic Acids with a Shelf-Stable Family of Reagents

Article abstract of DOI:10.1002/adsc.201700904

Herein the copper-catalyzed direct perfluoroalkylselenolation of aryl- and vinylboronic acids is described for the first time. The key to success is the design of new shelf-stable perfluoroalkylselenolating reagents, namely perfluoroalkyl tolueneselenosulfonates. The reaction occurs at room temperature in the presence of commercially available catalyst and ligand in catalytic quantities. (Figure presented.).

Full text of DOI:10.1002/adsc.201700904

Title: Copper-Catalyzed Direct Trifluoro- and
Perfluoroalkylselenolations of Boronic Acids with a Shelf-Stable
Family of Reagents.
Authors: quentin Glenadel, Clément Ghiazza, Anis Tlili, and Thierry
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10.1002/adsc.201700904
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Copper-Catalyzed Direct Trifluoro- and
Perfluoroalkylselenolations of Boronic Acids with a Shelf-Stable
Family of Reagents
Quentin Glenadel#a, Clément Ghiazza#a, Anis Tlili a*, Thierry Billard a,b*
a
Institute of Chemistry and Biochemistry (ICBMS-UMR CNRS 5246), Univ Lyon, Universitꢀ Lyon 1, CNRS, 43 Bd du
11 Novembre 1918, 69622 Villeurbanne, France
e-mail: thierry.billard@univ-lyon1.fr, anis.tlili@univ-lyon1.fr
CERMEP – in vivo imaging, Groupement Hospitalier Est, 59 Bd Pinel, 69003 Lyon, France
These authors contributed equally to this work.
b
#
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract.
Herein
copper-catalyzed
direct
perfluoroalkylselenolation of aryl- and vinylboronic acids is
described for the first time. The key of success is the design
of new shelf-stable perfluoroalkylselenolating reagents,
namely perfluoroalkyl tolueneselenosulfonates. The reaction
occurs at room temperature in the presence of commercially
available catalyst and ligand in catalytic quantities.
Keywords: Copper catalysis, Trifluoromethylselenolation,
Boronic acids, Fluorine, Selenium
trifluoromethylselenyl group could represent an
interesting alternative to modulate properties of
molecules and then to obtain valuable compounds for
various applications.
Introduction
Due to their specific properties, fluorinated
compounds have played, these last years, a growing
role in various applications to become “essential”
compounds.[1] Consequently, a wide variety of
fluorinated substituents has been developed these last
decades.[2] More recently, new concepts have emerged
from the association of fluorinated moieties and
heteroatoms.[3] These led to the development of new
Despite
the
potential
interests
of
trifluoromethylselenylated compounds, synthetic
strategies to obtain these products are still limited.
Two retrosynthetic approaches have been envisaged.
First, the Se-CF3 bond disconnection which requires
the preliminary synthesis of selenylated starting
material.[8] Second, the C-SeCF3 bond disconnection
molecules with particular physico-chemical properties. which constitutes the most elegant approach from a
Such important property modulations have
particularly been well illustrated with CF3O and CF3S
retrosynthetic point of view. This direct
trifluoromethylselenolation strategy requires the
design of specific reagents. Nucleophilic ones
groups
which
possess
valuable
electronic
characteristics[4] (Hammett constants CF3O: p = 0.38,
m = 0.35, CF3S: p = 0.40, m = 0.50; Swain−Lupton
constants CF3O: F = 0.39, R = -0.04, CF3S: F = 0.36,
R = 0.14) and high lipophilicity parameters[5] (Hansch-
Leo parameters CF3O: R = 1.04, CF3S: R = 1.44). If
these emerging groups have been well studied these
last years the combination with the next chalcogen,
namely the selenium, has been less studied despite
pertinent properties (Hammett constants p = 0.44, m
= 0.45; Swain−Lupton constants F = 0.43, R = 0.02;
Hansch-Leo parameters R = 1.29).[4, 6] Furthermore,
selenylated compounds have shown applications from
including
copper
or
ammonium
trifluoromethylselenolate[9] are the most commonly
used species, but their preparations required the use of
stoichiometric amounts of selenium metal. On the
other hand, trifluoromethylselenyl chloride[10] is the
only
reagent
for
electrophilic
trifluoromethylselenolation. Our group has recently
described an efficient in situ procedure to easily handle
this volatile reagent.[6, 11]
The direct formation of C(sp2)-SeCF3 being
challenging, the direct trifluoromethylselenolation of
aromatic compounds has previously been investigated
(Scheme 1). In particular, metal-catalyzed coupling
material
to
life
sciences.[7]
Consequently,
1
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10.1002/adsc.201700904
Advanced Synthesis & Catalysis
O
O
reactions have been performed starting from aryl
iodides[9a, 9h, 12] or aryl diazoniums[9l] substrates. Very
1) SO2Cl2 (1 equiv.)
THF, 25°C
S
SeRF
Ph
SeRF
recently,
a
nickel-catalyzed
2) TsNa (1.1 equiv.)
CH2Cl2, -78°C
trifluoromethylselenolation of aryl halides (X = Cl, Br,
I) has also been described.[13]
I: RF = CF3 (58 %)
Aryl boronic acids constitute attractive starting
materials because a wide range of substrates is
available and they usually allow performing reactions
under mild conditions.[14] However, to this day, only
two trifluoromethylselenolations of boronic acids have
II: RF = CF2CF3 (44 %)
III: RF = (CF2)5CF3 (40 %)
Scheme
tolueneselenosulfonate reagents.
2.
Synthesis
of
perfluoroalkyl
been
described,
using
ammonium
trifluoromethylselenolate[9j] or trifluoromethylselenyl
chloride.[15] Nevertheless, both approaches required a
stoichiometric amount of copper catalyst. In order to
improve this cross-coupling reaction, the design of a
new shelf-stable reagent, isolable and easy to handle,
has then been investigated.
The in situ formed trifluoromethylselenyl chloride
reacted with sodium toluenesulfinate yielding the
expected compound I with a satisfactory yield. Higher
homolog reagents (II and III) have also been obtained,
following a similar strategy. Single-crystal X-ray
diffraction analysis of III has unambiguously
confirmed the formation of the sulfur-selenium bond
(Figure 1).
This work
Previous work
X
Me4NSeCF3
O O
S
X = I: [Cu]cat.
SeCF3
R
X = Cl, Br, I: [Ni]cat.
Me4NSeCF3
[Cu]stoich. / O2
SeCF3
B(OH)2
B(OH)2
[CF3Se]
[Cu]cat.
[CF3SeCl]
[Cu]stoich.
R
R
R
N2
Figure 1. Single-crystal X-ray structure of the air-stable
reagent III. Ellipsoids shown at 50% probability.
Me4NSeCF3 / [Pd]cat.
or
R
[(bpy)Cu(SeCF3)]2
With the reagents I-III in hand, their applicability
under copper catalysis was studied with 4-
biphenylboronic acid as a model substrate (Table 1).
The formation of the desired product was observed in
63% yield when copper (II) acetate in conjunction with
2,2′-bipyridine (L1) were used in catalytic amount (20
mol %) and the reaction was carried out in CH3CN at
room temperature, in the presence of cesium carbonate
as a base (entry 1). A screening of different solvents
demonstrated that 1,4-dioxane and THF led to the
highest yields (entries 1-6). The nature of base
appeared to have a moderate impact on the reaction,
with an optimal result obtained with cesium carbonate
(entries 6-9). By evaluating different copper salts
(entries 10-12), copper (II) acetate turned to be the
most efficient copper pre-catalyst for this cross-
coupling reaction. It is noteworthy that excellent
reactivity was still obtained when the catalyst loading
(Cu/L) was reduced to 10 mol% (entry 13). Finally,
different other ligands have also been evaluated
(Figure 2) and the 2,2′-bipyridine (L1) was confirmed
as the best choice (entries 14-18).
Scheme 1. State of the art for the direct cross-coupling
trifluoromethylselenolation.
Results and Discussion
These last years, fluorinated derivatives of sulfonates
demonstrated
their
efficiency
illustrated
in
fluoroalkylchalcogenation
as
by
trifluoromethyl triflate[16] and trifluoromethyl
arylsulfonates[17] for trifluoromethoxylation and
difluoromethyl
difluoromethylthiolation.[18]
Inspired by these
benzenethiosulfonate
for
works,
trifluoromethyl
tolueneselenosulfonate (I) has been designed (Scheme
2).
2
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10.1002/adsc.201700904
Advanced Synthesis & Catalysis
Heterocyclic compounds were also evaluated. The
desired products were obtained in low to excellent
yields including pyrimidine derivative (2h), quinoline
(2i) as well as benzothiophene (2j). Finally,
vinylboronic acids were successfully employed in low
to moderate yields. For example, the presence of an
electron-donating group (MeO) on the phenyl ring was
beneficial for the reaction outcome since the product
2l was obtained in 55% yield.
N
N
N
N
L1
L2
O
O
N
N
Ph
Ph
N
N
L4
L5
L3
Figure 2. Ligands used during optimization.
O
Cu(OAc)2 (10 mol%)
O
L1 (10 mol%)
S
R
B(OH)2
Tol
SeCF3
+
R
SeCF3
2
Cs2CO3 (1 equiv.)
THF, RT, 16h
I
Table 1. Trifluoromethylselenolation of 4-biphenylboronic
acid with I.
1
(R = Ar, HetAr, vinyl)
B(OH)2
O
O
SeCF3
[Cu] (x mol%)
L (x mol%)
SeCF3
S
SeCF3
SeCF3
SeCF3
+
Ph
Base (1 equiv.)
Solvent, RT, 16h
NC
2b
21% (50%)
MeO2C
2a
Ph
1a
I
2c
61% (70%)
Ph
74% (85%)
2a
SeCF3
SeCF3
SeCF3
SeCF3
HO
Entry [Cu]
La) xb)
Base
Solvent 2a
(%)c)
Br
MeO
2d
2e
47% (66%)
2f
68%
1
2
3
4
5
6
7
8
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OTf)2
CuBr2
20
20
20
20
20
20
20
20
20
20
20
20
10
10
10
10
10
10
Cs2CO3 CH3CN 63
Cs2CO3 DMF <1
Cs2CO3 DMSO 19
Cs2CO3 diglyme 20
Cs2CO3 dioxane 86
Cs2CO3 THF
K2CO3 THF
K3PO4
Et3N
Cs2CO3 THF
Cs2CO3 THF
Cs2CO3 THF
Cs2CO3 THF
Cs2CO3 THF
Cs2CO3 THF
Cs2CO3 THF
Cs2CO3 THF
Cs2CO3 THF
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
-
70% (80%)
SeCF3
OMe
SeCF3
O
O
N
MeO
N
N
88
71
59
80
70
59
59
85
7
2g
49% (65%)
2h
2i
27% (34%)
55% (66%)
THF
THF
9
SeCF3
SeCF3
10
11
12
13
14
15
16
17
18
SeCF3
Ph
S
MeO
CuI
2k
2l
2j
76% (96%)
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
(26%)
47% (55%)
64
68
21
15
L2
L3
L4
L5
Scheme 3. Trifluoromethylselenolation of boronic acids.
Yields shown are those of isolated products; yields
determined by 19F NMR spectroscopy with PhOCF3 as an
internal standard are shown in parentheses.
a) See Figure 2. b) mol %. c) Yields determined by 19F NMR
spectroscopy with PhOCF3 as an internal standard.
Afterwards, higher homologs of I were also been
evaluated. Reagents II and III were engaged under the
same reaction conditions (Scheme 4).
With the best conditions in hand (entry 13), the
scope
and
limitation
of
the
direct
Moderate to good yields were observed either with
perfluoroethyl (II) or perfluorohexyl (III) reagents
under catalytic conditions. Indeed, the reaction
conditions tolerated bromine substituted arenes (3d) as
well as the presence of heterocyclic compounds. For
instance, the benzothiophene derivatives (3j, 4j) could
be obtained with a good yield of 66% starting from
reagent II and with an excellent yield of 87% when
reagent III was used. These perfluoroalkylselenolated
compounds have never been obtained by cross-
coupling reactions.
trifluoromethylselenolation of aryl- and vinylboronic
acid derivatives has been studied (Scheme 3).
Arenes substituted with electron-withdrawing
groups underwent trifluoromethylselenolation in
moderate to good yield (2a-c). The reaction conditions
were compatible with nitrile as well as ester
substituents. The bromine was also tolerated under the
reaction conditions and the corresponding product
(2d) was obtained in 80% yield. Arenes substituted
with electron-donating groups were also tolerated.
Interestingly,
starting
from
3-
(hydroxymethyl)phenylboronic acid (1e), the selective
C-SeCF3 bond formation occurred in 66% yield.
3
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10.1002/adsc.201700904
Advanced Synthesis & Catalysis
O
Cu(OAc)2 (10 mol%)
O
a)
Ph
L1 (10 mol%)
S
Ar B(OH)2
Tol
SeRF
+
Ar SeRF
OH
H
B(OH)2
Cs2CO3 (1 equiv.)
THF, RT, 16h
1
II or III
3-4
Cu(OAc)2 / L1
+
+
Cs2CO3
THF, RT, 16h
SeCF2CF3
SeCF2CF3
Ph
Ph
Ph
1a
Ph
Br
Ph
3a
3d
74% (85%)
39% (41%)
b)
SeCF2CF3
SeCF3
SeCF2CF3
O
O
Cu(OAc)2 / L1
1a
Cs2CO3
S
CF3SeSeCF3
Tol
SeCF3
THF, RT, 16h
S
N
I
3j
57% (66%)
3i
Ph
28% (32%)
3a
AcO-
or NEt3
or Cs2CO3
c)
SeCF2CF2CF2CF2CF2CF3
O
O
S
CF3SeSeCF3
Ph
Tol
SeCF3
SeCF2CF2CF2CF2CF2CF3
4a
39%
I
4j
S
Scheme 5. Investigations for mechanism determination.
63% (87%)
Scheme 4. Perfluoroalkylselenolation of boronic acids.
Yields shown are those of isolated products; yields
determined by 19F NMR spectroscopy with PhOCF3 as an
internal standard are shown in parentheses.
Based on these observations, the mechanism
outlined in Scheme 6 could be proposed. The complex
A, formed in situ, would be the active catalytic species.
Complex A would then react with the aryl boronic acid,
as documented in the literature,[20] yielding a new
complex B. Finally, this complex would react with the
trifluoromethylselenolated species affording the
desired product 2. Further investigations of the
reaction mechanism are currently in progress in our
laboratory.
In order to shed some light on the reaction
mechanism, some NMR and mass spectroscopy
investigations were performed. Similar results were
observed when the reaction was performed under inert
conditions, excluding a Chan-Lam type mechanism.
Furthermore, the complete conversion of aryl boronic
acid 1a was observed in presence of catalyst and in
absence of reagent I. The protodeborylated starting
material was formed as major product, with trace
amounts of the corresponding phenol as well as the
homocoupling products (Scheme 5a), supposing the
formation of an aryl-copper species. In absence of aryl
boronic acid, reagent I was entirely degraded into the
diselenide CF3SeSeCF3 (singlet at -37.70 ppm in 19F
NMR[10e, 19]). Noteworthy, adding the aryl boronic acid
1a after the full consumption of the reagent I furnished
the desired product (3a) (Scheme 5b). Moreover, the
degradation of the reagent I was also effective in the
presence of NEt3, Cs2CO3 or acetate anion (Scheme
5c). These observations, led to suppose the
intermediate formation of more electrophilic transient
active species from I by nucleophilic attack of acetate
anion or bases. Finally, the formation of a 16 electrons
copper complex A (X = OAc) could be detected by
mass spectroscopy during the reaction.
Cu(OAc)2
L1
AcO-
N
Cu
X
Ar SeCF3
Ar B(OH)2
N
A
1
2
X = Ts, SeCF3, OAc
OH
X B
X SeCF3
N
OH
Cu Ar
N
B
Scheme 6. Proposition of mechanism.
Conclusion
In summary, we reported herein the synthesis of a new
stable reagent for trifluoromethylselenolation. The
design of such reagent allowed the direct
trifluoromethylselenolations of aryl- and vinylboronic
acids under catalytic conditions for the first time. The
catalytic system used of Cu(OAc)2 in conjunction with
4
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10.1002/adsc.201700904
Advanced Synthesis & Catalysis
Crystallographic
Data
Centre
a commercially available ligand. Furthermore, we
demonstrated for the first time that the procedure could
be extended to perfluoroalkyl derivatives. Further
investigations regarding the reactivity of this new
family of reagents are under evaluation in our
laboratory.
via www.ccdc.cam.ac.uk/data_request/cif.
Typical procedure for the fluoroalkylselenolation of
boronic acids
To a flask equipped with a magnetic stir bar are added I, II
or III (0.3 mmol, 1.0 equiv.), the boronic acid 1 (0.3 mmol,
1.0 equiv.), Cu(OAc)2 (0.03 mmol, 10 mol%), the
bipyridine L1 (0.03 mmol, 10 mol%), Cs2CO3 (0.3 mmol,
1.0 equiv.) and anhydrous THF (1.5 mL). The reaction is
stirred at 25°C for 15-18 hours (conversion is checked by
19F NMR with PhOCF3 as internal standard). The reaction
mixture is then partitioned between water and EtOAc and
the aqueous layer is extracted with EtOAc. The combined
organic layers are washed with brine, dried over MgSO4,
filtered, and concentrated to dryness. The crude residue is
purified by chromatography to afford the desired product 2,
3 or 4.
Experimental Section
Synthesis
of
1-methyl-4-
{[(trifluoromethyl)selanyl]sulfonyl}benzene (I)
To a flask equipped with a magnetic stir bar are added the
benzyl trifluoromethyl selenide (16 mmol, 1.0 equiv.),
sulfuryl chloride (16 mmol, 1.0 equiv.) and anhydrous THF
(5 mL). The reaction is stirred at 25°C for 10 minutes and
then cooled down to -78°C. Anhydrous DCM (27 mL) is
added followed by sodium p-toluenesulfinate (17.7 mmol,
1.1 equiv.). The reaction is stirred until complete conversion
of the active reagent Cl-SeCF3 at -78°C (around 15 minutes,
characterized by a change of color from yellow to colorless).
The reaction mixture is then filtered over a pad of silica
(rinsed with DCM) and the filtrate is concentrated to dryness.
It should be noted that the filtration should be processed
quickly due to the formation of NaCl probably deleterious
to the reagent stability. The crude residue is purified by
chromatography (cyclohexane/toluene: 80/20) to afford the
desired product I (yellow liquid, 2.82 g, 58% yield).
Supporting Information
Spectroscopic characterization and copies of spectra of
compounds I-III, 2, 3, 4 and X-ray crystallographic
information files for compounds III are available in the
Supporting Information.
Acknowledgements
Synthesis
of
1-methyl-4-{[(1,1,2,2,2-
pentafluoroethyl)selanyl]sulfonyl}benzene (II)
Clément Ghiazza holds a doctoral fellowship from la Région
Rhône Alpes. The authors are grateful to the CNRS and the French
Ministry of Research for financial support. The French Fluorine
Network is also acknowledged for its support. We thank Dr.
Erwann Jeanneau (Centre de Diffractométrie Henri
Longchambon) for collecting the crystallographic data and
solving the structure of III.
To a flask equipped with a magnetic stir bar are added the
benzyl pentafluoroethyl selenide (3.4 mmol, 1.0 equiv.),
sulfuryl chloride (3.4 mmol, 1.0 equiv.) and anhydrous THF
(3.5 mL). The reaction is stirred at 25°C for 50 minutes and
then cooled down to -78°C. Anhydrous DCM (7.5 mL) is
added followed by sodium p-toluenesulfinate (3.8 mmol,
1.1 equiv.). The reaction is stirred until complete conversion
of the active reagent Cl-SeCF2CF3 at -78°C (around 15
minutes, characterized by a change of color from yellow to
colorless). The reaction mixture is then filtered over a pad
of silica (rinsed with DCM) and the filtrate is concentrated
to dryness. It should be noted that the filtration should be
processed quickly due to the formation of NaCl probably
deleterious to the reagent stability. The crude residue is
purified by chromatography (cyclohexane/toluene: 80/20
and cyclohexane/EtOAc: 98/2 to 95/5) to afford the desired
product II (yellow liquid, 463 mg, 38% yield).
References
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Synthesis
of
1-methyl-4-{[(1,1,2,2,3,3,4,4,5,5,6,6,6-
tridecafluorohexyl)selanyl]sulfonyl}benzene (III)
To a flask equipped with a magnetic stir bar are added the
benzyl tridecafluorohexyl selenide (2.0 mmol, 1.0 equiv.),
sulfuryl chloride (2.0 mmol, 1.0 equiv.) and anhydrous THF
(2 mL). The reaction is stirred at 25°C for 50 minutes and
then cooled down to 0°C. Anhydrous DCM (7 mL) is added
followed by sodium p-toluenesulfinate (2.2 mmol, 1.1
equiv.). The reaction is stirred until complete conversion of
the active reagent Cl-SeRf at 0°C (around 15-30 minutes,
characterized by a change of color from yellow to colorless).
The reaction mixture is then filtered over a pad of silica
(rinsed with DCM) and the filtrate is concentrated to dryness.
It should be noted that the filtration should be processed
quickly due to the formation of NaCl probably deleterious
to the reagent stability. The crude residue is purified by
chromatography (cyclohexane/toluene: 80/20) to afford the
desired product III (445 mg, 40% yield). Off-white solid
(mp < 50 °C, calibration substance: azobenzol at 68.0 °C).
CCDC-1548880
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge
contains
the
supplementary
5
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10.1002/adsc.201700904
Advanced Synthesis & Catalysis
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Advanced Synthesis & Catalysis
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Advanced Synthesis & Catalysis
FULL PAPER
Copper-Catalyzed Direct Trifluoro- and
Perfluoroalkylselenolations of Boronic Acids with
a Shelf-Stable Family of Reagents
Adv. Synth. Catal. Year, Volume, Page – Page
Quentin Glenadel, Clément Ghiazza, Anis Tlili*,
Thierry Billard*
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