The first nucleophilic C-H perfluoroalkylation of aromatic compounds via (arene)tricarbonylchromium complexes

Article abstract of DOI:10.1039/c6cc09905j

The first nucleophilic perfluoroalkylation of arenes is based on the arene π-system activation via (η⁶-arene)tricarbonylchromium complexes. Perfluoroalkyl anions generated from Me₃SiR_F and a fluoride ion source [Me₄N]F exclusively attack the arene ligand under mild conditions. The formed negatively charged analogs of Meisenheimer adducts readily undergo a one-pot oxidation to perfluoroalkyl arenes.

Full text of DOI:10.1039/c6cc09905j

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The first nucleophilic C–H perfluoroalkylation of
aromatic compounds via (arene)tricarbonylchromium
complexes†
Cite this:DOI: 10.1039/c6cc09905j
Received 13th December 2016,
Accepted 24th January 2017
Natalia V. Kirij, Andrey A. Filatov, Gleb Yu. Khrapach and Yurii L. Yagupolskii*
DOI: 10.1039/c6cc09905j
rsc.li/chemcomm
The first nucleophilic perfluoroalkylation of arenes is based on the arene perfluoroalkylation of complex biologically active compounds.
p-system activation via (g6-arene)tricarbonylchromium complexes. Two complementary approaches of direct C–H perfluoroalkylation
Perfluoroalkyl anions generated from Me3SiRF and a fluoride ion have been carried out. The first main trend consists in reactions that
source [Me4N]F exclusively attack the arene ligand under mild conditions. are catalyzed/mediated by transition metals or organocatalysts,11
The formed negatively charged analogs of Meisenheimer adducts or require perfluoroalkyl metal reagents, which are in turn prepared
readily undergo a one-pot oxidation to perfluoroalkyl arenes.
from silicon precursors.2f,6f,11e,12
The second transition metal-free approach consists in per-
The introduction of fluorinated moieties into organic molecules to fluoroalkylation in the positions of the substrate that are inherently
change their properties by design has been a major focus of metho- reactive. Previously, we realized this approach for the aromatic ring
dology development in recent years. Perfluoroalkyl-containing arenes activation by three strong electron-withdrawing substituents, such
are of particular interest in the field of pharmaceuticals, agrochemicals as –NO2, –SO2F and –SO2OCH2CF3 (Scheme 1).13
and materials science due to the unique properties of perfluoroalkyl
The limit of our previous approach is imposed by the activating
(RF) groups.1 Consequently, the development of efficient methods substituents which do not act as protecting groups that can be
to construct an aryl–RF bond has received considerable attention.2,3 introduced and removed easily. Thus, the main purpose of our work
The use of the highly corrosive HF, SbF5 or SF4 reagents has been was to find the appropriate ring activation suitable for the arene C–H
the traditional method towards the preparation of trifluoromethyl perfluoroalkylation. Stable arene-transition metal complexes can
aromatics,4 buttheseareineffectiveforthelate-stagefunctionalization offer such attractive possibility. Among the extensive range of known
of complex molecules. They also cannot be applied to the synthesis of arene-transition metal complexes,14 (Z6-arene)tricarbonylchromium
longer-chain perfluoroalkyl moieties, e.g. a pentafluoroethyl group.5 complexes have drawn our attention as relatively air-stable,
The radical6 and electrophilic7 trifluoromethylations of arenes have crystalline and easily weighable materials.
also been intensively explored, but these methods are often limited to
the substrates bearing electron-donating substituents, and by the cost nitro groups in the well-known anionic s complexes (Meisenheimer
of the crystalline electrophilic trifluoromethylating agents in bulk. adducts), as it serves as a stabilizing substituent for the negative
The Cr(CO)3 group in the arene complexes can be compared to
Many methods of nucleophilic perfluoroalkylation utilizing charge.15 The reactions of (Z6-arene)Cr(CO)3 complexes with carbon
various agents and activation systems have been developed over nucleophiles have been studied intensively, however, to the best of
the last thirty years.8 However, nucleophilic trifluoromethylation is our knowledge, there is no precedent for a direct incorporation of
still challenging due to the low thermal stability of CF3 anion species, perfluorinated carbanions or their equivalents into these compounds.
which can undergo either defluorination to difluorocarbene or Here we report a new strategy for direct C–H perfluoroalkyl-
protonation to fluoroform (CHF3).9 Moreover, the existing methods ation of arenes as ligands of (Z6-arene)Cr(CO)3 complexes.
of nucleophilic trifluoromethylation generally require a catalyst or
the presence of a leaving group in a trifluoromethylating substrate.
The most promising way to obtain perfluoroalkyl-containing
aromatics is direct C–H perfluoroalkylation. It helps evade
the necessity of pre-functionalization10 and allows a late-stage
Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
Scheme 1 Stable gem-trifluoromethyl anionic s complexes based on
5 Murmanskaya Street, 02660, Kiev, Ukraine. E-mail: yagupolskii@ioch.kiev.ua
1,3,5-tris(nitro/sulfonyl)benzene derivatives.
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6cc09905j
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Scheme 2 The general strategy for arene perfluoroalkylation.
Our strategy, shown in Scheme 2, starts from the conversion
of widely available aromatic reactants into (Z6-arene)Cr(CO)3
complexes.18 The Cr(CO)3 unit activates a p-complexed arene
ligand towards nucleophilic exo-addition of a perfluoroalkyl anion,
generated in situ from a trimethyl(perfluoroalkyl)silane16,17
(Me3SiRF, RF = CF3, C2F5) in the presence of the fluoride ion
source tetramethylammonium fluoride ([Me4N]F). The exo-attack
leads to the negatively charged (Z5-cyclohexadienyl)Cr(CO)3 adducts,
which are analogs of Meisenheimer adducts. The oxidation of
these adducts yields perfluoroalkyl-substituted arenes, as a
result of a formal hydride ion substitution.
Fig. 1 Monitoring of the reaction of (Z6-methylbenzene)tricarbonylchromium
(1a) with the system Me3SiCF3/FÀ in THF using 19F NMR spectroscopy.
The first studies to determine the capability of the system of
trimethyl(trifluoromethyl)silane (Me3SiCF3) and [Me4N]F to transfer
the CF3 group to (Z6-arene)Cr(CO)3 were conducted in tetrahydro-
furan (THF) with (Z6-methylbenzene)Cr(CO)3 (1a) as a model sub-
strate (Table 1). The substrate 1a reacted with one CF3 anion
equivalent generated from Me3SiCF3 and [Me4N]F. The methyl group
showed ortho- (2a, 55%) and meta- (3a, 45%) directing effects, but
only minor quantities of intermediates 2a and 3a were formed upon
adding the reagents to the complex solution at À50 1C (Fig. 1).
According to 19F NMR spectra, the silicates [Me4N][Me3Si(CF3)F] and
[Me4N][Me3Si(CF3)2] together with CF3H were the main products
of Me3SiCF3 and [Me4N]F transformations at this temperature.19
A notable increase in yield of the desired adducts 2a and 3a was
observed in the temperature range from À10 1C to 0 1C, in which the
total yield of the adducts reached 62%.
that the trifluoromethyl anion selectively attacks the arene
ligand, forming the negatively charged Z5-cyclohexadienyl
adduct (Fig. 1).13 There were no signals in the range for a Fischer
carbene complex20 due to a nucleophilic attack at the CO ligand
of the Cr(CO)3 unit even at À50 1C.
We screened a range of solvents and revealed dimethoxyethane
(DME) as the solvent of choice (Table 1). A critical improvement of
the trifluoromethylation was achieved by the use of a double excess
of Me3SiCF3 and [Me4N]F, as well as by the portioned addition of
Me3SiCF3 to a mixture of the substrate and the fluoride ion source
at À10 1C. Under these reaction conditions, full conversion of the
starting complex 1a was achieved within 30 min after the addition
of Me3SiCF3 to give 2a and 3a in excellent yields as determined by
19F NMR spectroscopy (Table 1, entry 7). The utilization of other
fluoride ion sources, such as KF or CsF in combination with crown
ethers, was inefficient. The anionic adducts 2a and 3a are stable in
solutions under an inert atmosphere for a long period even at room
temperature, being highly sensitive towards oxidation. They react
smoothly with iodine as the oxidant to form corresponding benzo-
trifluorides (Fig. 1).
Intermediates 2a and 3a resulting from the CF3 anion
exo-attack at the arene ligand were transition-metal analogs of
Meisenheimer adducts. The chemical shifts and F–H coupling
constants of the 19F NMR spectral data provide strong evidence
Table 1 Selected optimization experiments for the trifluoromethylation of
(Z6-methylbenzene)tricarbonylchromium (1a)a
With the optimized procedure at hand, we turned our attention
to the scope and limitations of the reaction. We examined the effect
of varying the number and location of methyl groups in the arene
ligand (Table 2). The reactions of dimethyl- and tetramethyl-
substituted substrates 1b and 1d furnished the expected trifluoro-
methylated intermediates 2b and 2d in high yields (Table 2,
entries 1 and 3). The trifluoromethylation of complexes 1c and
1e having a methyl group in the para-position towards the
reactive center of the arene ligand resulted in a poorer conversion
and a lower yield (Table 2, entries 2 and 4). The unsubstituted
(Z6-benzene)Cr(CO)3 1f participated efficiently in the CF3 anion
transfer to give the desired adduct 2f in a very high yield (Table 3,
entry 1).
Entry Solvent Me3SiCF3 (mmol) [Me4N]F (mmol) T (1C) Yieldb (%)
1
2
3
4
5
6
7
8
9
THF
THF
THF
THF
THF
DME
DME
1.3
1.3
1.3
1.3
1.3
1.3
2.2
1.2
1.2
1.2
1.2
1.2
1.2
2.0
1.2
1.2
À50
À35
À20
À10
0
À10
À10
À10
À10
9
15
20
41
62
69
92
0
CH3CN 1.3
Et2O 1.3
To our delight, the same mild reaction conditions allowed the
selective meta-trifluoromethylation of complexes 1 with strong
electron-donating substituents (Table 3). Very high and nearly
quantitative conversion was observed for complexes with methoxy
0
a
b
Reaction conditions: 1a (1 mmol), solvent (5 mL). The total yield of
regioisomers 2a and 3a determined by 19F NMR spectroscopy using
fluorobenzene as the internal standard.
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Table 2 Effect of varying the number and location of methyl groups on
the arene ligand trifluoromethylationa
Table 4 Scope of the trifluoromethylation via (Z6-arene)tricarbonyl-
chromium complexesa
Entry
Substrate
R
Product
Yieldb [%]
1
2
3
4
1b
1c
1d
1e
1,4-Dimethyl
1,3,5-Trimethyl
1,2,4,5-Tetramethyl
1,2,3,4,5-Pentamethyl
2b
2c
2d
2e
93
54
89
12
a
Reaction conditions: 1 (1 mmol), Me3SiCF3 (2 mmol), [Me4N]F (2 mmol),
DME (5 mL). Determined by 19F NMR spectroscopy using fluorobenzene
b
as the internal standard.
Table 3 Scope of trifluoromethylation of monosubstituted (Z6-arene)-
tricarbonylchromium complexesa
Entry Substrate R
Solvent Product
Yieldb [%]
a
Yields given for the oxidative decomplexation determined by 19F NMR
spectroscopy using fluorobenzene as the internal standard. The oxida-
1
2
3
4
5
6
7
1f
H
OCH3
OCH3
N(Me)2 DME
N(Me)2 DMF
CF3
DME
DME
DMF
2f
95c
87
68
97
70
53
b
c
tion conditions: 1 (1 equiv.). Iodine (2.5 equiv.), À60 1C – rt, 4 h. 1,4-
1g
1g
1h
1h
1i
3g
3g
3h
3h
2i
d
Benzoquinone (4 equiv.), À60 1C – rt, 4 h. CAN (5.5 equiv.), À60 1C – rt,
e
4 h. Yields of isolated products. For the isomer mixture, the minor
regioisomeric position is labeled with *.
DME
1j
C(O)OEt DME
Addition at the ester CO 89
Like a trifluoromethyl moiety, the pentafluoroethyl group is
valuable for modulating the properties of molecules of interest to
the pharmaceutical and agrochemical industries.1d Trimethyl-
(pentafluoroethyl)silane (Me3SiC2F5) reacted with the complexes
1b, 1f and 1h in a fashion identical to that of Me3SiCF3, giving
Z5-cyclohexadienyl adducts that were successfully oxidized to
a
Reaction conditions: 1 (1 mmol), Me3SiCF3 (2.2 mmol), [Me4N]F
(2 mmol), solvent (5 mL). Determined by 19F NMR spectroscopy using
fluorobenzene as the internal standard. The total yield of exo- and
endo-adducts (exo : endo = 10 : 1).
b
c
and dimethylamino groups in the arene ligand, respectively corresponding pentafluoroethyl arenes 5b, 5f and 5h (Table 4).
(Table 3, entries 3 and 5). The intermediates 3g and 3h were In conclusion, we have developed the first nucleophilic C–H
also generated in good yields in dimethylformamide (DMF) perfluoroalkylation of arenes as ligands of stable and easy to handle
(Table 3, entries 3 and 5).
(Z6-arene)tricarbonylchromium complexes. The complexed arene
Unexpectedly, the electron-withdrawing trifluoromethyl group selectively reacts with a trifluoromethyl or pentafluoroethyl anion
induced only ortho-trifluoromethylation at the aromatic ring under mild conditions, forming cyclohexadienyl adducts. The
(Table 3, entry 6). (Z6-Ethylbenzoate)Cr(CO)3 (1j) also reacted adducts are sensitive towards oxidation, which allows an efficient
smoothly with the CF3 anion, giving, however, a product of the release of a metal-free perfluoroalkyl arene. We expect that this
nucleophilic attack on the ester carbonyl site. According to 19F method will complement the existing approaches towards perfluoro-
NMR spectra, the ester carbonyl solely underwent nucleophilic alkyl aromatics, as well as help to look at the selective reactivity of
addition, since no signals in the range for intermediates 2 and 3 the trifluoromethyl and pentafluoroethyl anion from a new angle.
were observed, as well as any traces of the corresponding
benzotrifluoride after oxidation (Table 3, entry 7).
Notes and references
The reactivity of the anionic adducts was also consistent with
the Z5-cyclohexadienyl structure.21 Thus, the oxidation of adducts 2
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