Phosphovanadomolybdic acid catalyzed direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 as the CF3 source and O2 as the terminal oxidant

Article abstract of DOI:10.1039/c6nj03654f

A direct C-H trifluoromethylation of (hetero)arenes using NaSO₂CF₃ (Langlois' reagent) as the CF₃ source and O₂ as the terminal oxidant has been developed. In the presence of catalytic amounts of phosphovanadomolybdic acids, such as H₆PV₃Mo₉O₄₀, various kinds of substituted benzenes and heteroaromatic compounds could be converted into the corresponding trifluoromethylated products.

Full text of DOI:10.1039/c6nj03654f

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The role of atropisomers on the photo-reactivity and fatigue of
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LETTERꢀ
ꢀ
Phosphovanadomolybdic acid catalyzed direct C–H
trifluoromethylation of (hetero)arenes using NaSO CF as
2
3
Received 00th January 20xx,ꢀ
Accepted 00th January 20xx
the CF source and O as the terminal oxidant
3
2
Chifeng Li, Kosuke Suzuki, Kazuya Yamaguchi* and Noritaka Mizuno*
DOI: 10.1039/x0xx00000x
www.rsc.org/chemcomm
A direct C–H trifluoromethylation of (hetero)arenes using
NaSO CF (Langlois’ reagent) as the CF source and O as
2
3
3
2
R
2
NaSO CF3
R
the terminal oxidant has been developed. In the presence
H PV Mo O
40
6
3
9
of catalytic amounts of phosphovanadomolybdic acids,
CF3
O (1 atm)
2
such as
H
6
PV
3
Mo
9
O
40
,
various kinds of substituted
X
X
benzenes and heteroaromatic compounds could be
converted into the corresponding trifluoromethylated
products.
(X = CH, N)
ꢀ
Scheme 1 A direct C–H trifluoromethylation of (hetero)arenes using NaSO
as the CF radical source and O as the terminal oxidant.
2 3
CF
3
2
The trifluoromethyl (CF3) group is becoming of increasing
importance in pharmaceuticals, agrochemicals, polymers, and liquid
crystals because the physical and chemical properties of molecules,
such as metabolic stability, membrane permeability, and bioactivity,
the terminal oxidant, which is regarded as the “greenest” oxidant,
has been remained unexplored until now, to the best of our
knowledge.
Herein, we report for the first time that phosphovanadomolybdic
acids can act as efficient catalysts for oxidative direct C–H
trifluoromethylation of (hetero)arenes using NaSO2CF3 as the CF3
source and O2 as the terminal oxidant (Scheme 1). In the presence of
catalytic amounts of phosphovanadomolybdic acids, such as
H6PV3Mo9O40, various kinds of substituted benzenes and
heteroaromatic compounds could be converted into the
corresponding trifluoromethylated products. Although various
aerobic oxidation reactions have been reported using
1
can be remarkably modified by installation of CF3 group(s).
Therefore, the development of efficient trifluoromethylation
methods has attracted considerable attention and become one of the
2
most important subjects in extensive research fields. In particular,
catalytic direct C–H trifluoromethylation of (hetero)arenes is quite
2d,3
important.
Recently, significant progress has been achieved in
radical-based C–H trifluoromethylation using various kinds of CF3
4
sources. Sodium trifluoromethanesulfinate (NaSO2CF3, Langlois’
reagent) is one of the most preferable trifluoromethylation reagents
8,9
phosphovanadomolybdic acids, the trifluoromethylation systems
which utilize heteropoly acid catalysts (HPAs) have never been
reported to date, to the best of our knowledge.
because it is relatively stable, easy-to-handle, and inexpensive in
5
comparison with other reagents. Although efforts have been devoted
to develop the catalytic direct C–H trifluoromethylation of
(
To begin with, we optimized the reaction conditions for the
trifluoromethylation of 1,4-dimethoxybenzene (1a, model substrate)
in the presence of a catalytic amount of H5PV2Mo10O40 using
NaSO2CF3 as the CF3 source in 1 atm of O2. The solvent screening
revealed that acetonitrile gave better yields of the
trifluoromethylated products than other organic solvents examined,
such as dimethyl sulfoxide, N,N-dimethylformamide, N-
methylpyrrolidone, 1,2-dichloroethane, and ethanol (Table S1, entry
6
hetero)arenes using NaSO2CF3 as the source of CF3 radical, the
previously reported C–H trifluoromethylation systems typically
require superstoichiometric amounts of organic or inorganic
oxidants, such as tert-butylhydroperoxide, hypervalent iodine, and
6
sodium persulfate. With regard to the photocatalytic C–H
trifluoromethylation of arenes using NaSO2CF3 as the CF3 source,
7a
two methods with the use of acetone as the oxidant or under
7b
oxidant-free conditions have been recently reported. The
NaSO2CF3-based trifluoromethylation of (hetero)arenes using O2 as
1
versus entries 6–10, ESI†). Addition of water into the acetonitrile-
based reaction media could significantly improve the yields of the
products, which is likely because of an increase in the solubility of
NaSO2CF3 in the reaction media (Table S1, entries 2–5, ESI†). In
particular, the trifluoromethylation in the 8/2 (v/v) mixture of
acetonitrile and water gave the best result (Table S1, entry 3, ESI†).
However, the further increase in the water contents
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a
Table 1 Effect of catalysts on the oxidative trifluoromethylation of 1a
(acetonitrile/water = 6/4 and 4/6 v/v) resulted in a decrease in the
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yields of the trifluoromethylated products likely because of the poor
solubility of la in these water-rich media (Table S1, entries 4 and 5,
ESI†). The yields of the trifluoromethylated products increased with
an increase in the reaction temperature (bath temperature) up to
OMe
OMe
OMe
CF3
CF3
+
CF3
OMe
3a
OMe
OMe
2a
120 °C (Table S2, ESI†). The effect of amounts of NaSO2CF3 on the
1
a
total yield and the 2a/3a ratio is summarized in Table S3 (ESI†).
Next, we investigated the catalytic activities of various HPAs for
the trifluoromethylation of 1a using NaSO2CF3 in the mixture of
acetonitrile/water (8/2 v/v) at 120 °C (bath temperature). The
reaction hardly proceeded in the absence of catalysts (Table 1, entry
Total yield (%)
Entry
Catalyst
Atmosphere
(
2a/3a)
1
2
3
4
5
6
7
8
w/o
O
2
6 (6/<1)
8 (8/<1)
H
3
PMo12
O
40
O
2
1). Although the trifluoromethylation also significantly proceeded in
3
H PW12O40
O2
<1
air (1 atm), the reaction was slower than that in O2 (Table 1, entry 8
versus entry 9). When using vanadium-free HPAs, such as
H3PMo12O40, H3PW12O40, H4SiMo12O40, and H4SiW12O40, the
reactions were not efficient and gave the trifluoromethylated
products 2a and 3a in quite low yields (Table 1, entries 2–5). The
catalytic activities increased with an increase in the vanadium
H
H
H
H
H
H
H
H
H
H
4
4
4
5
6
6
6
SiMo12
SiW12
O
40
O
O
O
O
O
2
2
2
2
2
4 (4/<1)
O
40
3 (3/<1)
PV
PV
PV
PV
PV
1
2
3
3
3
Mo11
O
40
40
40
69 (57/12)
79 (62/17)
90 (61/29)
65 (59/6)
20 (19/1)
2 (2/<1)
Mo10
O
9
Mo O
content (H3PMo12O40 << H4PV1Mo11O40 < H5PV2Mo10O40
H6PV3Mo9O40 ≈ H7PV4Mo8O40 for phosphomolybdic acids, Table 1,
entries 2, 6–8, and 12; H3PW12O40 << H4PV1W11O40
<
b
9
Mo
9
O
40
Air
c
1
0
Mo
9
O
40
Ar
<
d
11
6
PV
3
Mo
9
O
40 + TEMPO
O
O
O
2
2
2
H5PV2W10O40 < H6PV3W9O40 ≈ H7PV4W8O40 for phosphotungstic
acids, Table 1, entries 3 and 13–16). These results show that
vanadium is an indispensable component for this reaction. Regarding
the polyatoms of vanadium-containing HPAs, molybdenum
exhibited better catalytic activities than tungsten (Table 1, entries 6–
1
2
7
PV
4
Mo
8
O
40
89 (61/28)
15 (15/<1)
49 (46/3)
70 (58/12)
74 (60/14)
19 (19/<1)
24 (24/<1)
27 (26/1)
60 (55/5)
69 (60/9)
74 (63/11)
13
4
1 11
PV W O
40
14
H PV W10O40
5
6
7
2
3
4
O2
1
1
1
1
5
6
7
8
H
PV
W
9
O
40
O
O
O
O
O
O
O
O
2
2
2
2
2
2
2
2
8
the higher oxidation potentials than tungstic acids.
versus entries 13–16). It is well known that molybdic acids possess
H
PV
W
8
O
40
10
e
e
e
f
2 5
V O
As above-mentioned, vanadium plays important role on the
present trifluoromethylation. However, simple vanadium
compounds, such as V2O5, NaVO3, and VO(acac)2 (acac =
acetylacetonate), gave much lower yields of the trifluoromethylated
products (Table 1, entries 17–19). Although the performance of these
vanadium compounds was significantly improved by addition of
H3PMo12O40, H6PV3Mo9O40 exhibited higher catalytic activity in
comparison with the mixtures of V2O5 + H3PMo12O40, NaVO3 +
NaVO
3
19
VO(acac)
+ H
NaVO + H
2
2
2
2
0
1
2
V
2
O
5
3
PMo12
O
40
f
3
3
PMo12
O
40
f
VO(acac)
2
3 40
+ H PMo12O
a
Reaction conditions: 1a (0.2 mmol), NaSO
2
CF
3
(0.6 mmol), catalyst (10 mol%
H3PMo12O40, and VO(acac)2 + H3PMo12O40 (Table 1, entry 8 versus with respect to 1a), acetonitrile/water (2 mL, 4/1 v/v), 120 °C (bath temp.), O
2
(
1 atm), 6 h. Yields were determined by GC using biphenyl as an internal
entries 20–22). Other transition metal compounds, such as MnCl2,
Mn(acac)2, Mn(acac)3, Co(acac)2, Ni(acac)2, Pd(OAc)2 (OAc =
acetate), and Ag(acac) generally exhibited lower catalytic activities
than vanadium compounds (Table S4, ESI†). Notably, the catalytic
performance of these transition metal compounds was unchanged
even when the reaction was performed in the presence of
H3PMo12O40 (Table S4, ESI†). The aforementioned results support
the synergetic effect of vanadium and HPAs. In particular, the
substitution of vanadium into HPA frameworks can improve the
intrinsic catalytic performance of vanadium for the present C–H
b
c
d
standard. Air (1 atm). Ar (1 atm). TEMPO (0.6 mmol, 1 equiv with respect to
e
f
NaSO
2 3 3 40
CF ), 23 h. Vanadium (30 mol%). Vanadium (30 mol%) + H PMo12O
(
10 mol%).
stage of the present trifluoromethylation, the color of the reaction
solution also changed from orange to dark green, suggesting the
reduction of H6PV3Mo9O40 during the reaction. At the end of the
reaction, the color of the reaction solution again became close to the
original color, and the IVCT band almost disappeared (Fig. S1c,
ESI†). When the reaction was carried out under an Ar atmosphere,
the yields of the products significantly decreased (Table 1, entry 10),
and the color of the reaction solution remained dark green even
when prolonging the reaction time, thus indicating that O2 acts as the
terminal oxidant for the present trifluoromethylation. Consequently,
H6PV3Mo9O40 oxidizes NaSO2CF3, resulting in the formation of the
reduced H6PV3Mo9O40, and then the reduced H6PV3Mo9O40 is
8,9
trifluoromethylation.
When the mixture of H6PV3Mo9O40 and NaSO2CF3 in
acetonitrile was heated at 120 °C (bath temperature), the color of the
solution immediately (within 5 min) changed from orange (the color
of the fully oxidized form of H6PV3Mo9O40, Fig. S1a, ESI†) to dark
green, and a new broad absorption band around 780 nm likely due to
4+
6+
5+
5+
the intervalence charge-transfer (IVCT) of V /Mo , V /Mo ,
6+
reoxidized by O2. When
a radical scavenger of 2,2,6,6-
5+
11
and/or Mo /Mo appeared (Fig. S1b, ESI†). These results
indicate that H6PV3Mo9O40 is reduced by NaSO2CF3. At the initial
tetramethylpiperidine 1-oxyl (TEMPO, 1 equiv with respect to
NaSO2CF3) was added to the reaction solution, the reaction was
2
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OMe
OMe
OMe
OMe
CF3
CF3
N
N
CF3
N
CF3
CF3
CF3
+
+
+
N
N
N
CF3
CF3
<1%
CF3
OMe
29%
Entry 1a,c
65%
Entry 9
29%
3%
OMe
61%
d
Entry 5
1
CF3
CF3
4
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
2
+
CF3
CF3
CF3
CF3
+
2
CF3
+
N
N
N
CF3
Entry 2b,c
55%
<1%
Entry 10
26%
C2:C4 = 5.3:1.0)
5%
CF3
(
C1:C2 = 4.8:1.0)
(
Cl
Cl
Cl
Entry 6
31%
12%
Me
2
Me
CF3
CF3
CF3
Me
Cl
Cl
Cl
+
CF3
CF3
CF3
Cl
Cl
3
Cl
+
+
N
N
N
3
CF3
CF3
4
Entry 11
55%
1%
4
Entry 3a,c
92%
<1%
CF3
Entry 7
41%
C3:C4 = 1:1)
6%
(
C2:C3:C4 = 2.8:1.4:1.0)
1
2
3
(
OMe
OMe
2
OMe
CN
CN
2
CN
CF3
4
S
54%
S
b,c
CF3
CF3
CF3
CF3
3
+
CF3
CF3
Entry 12
+
3
4
(C1:C2:C3:C4 = 4.2:1.0:1.6:2.1)
4
Entry 4
61%
4%
Entry 8
33%
2%
(
C2:C3:C4 = 2.7:1.0:1.2)
(C2:C3:C4 = 2.6:1.0:1.7)
Fig. 1 Substrate scope for the H
6
PV
3
Mo
9
O
40-catalyzed C–H trifluoromethylation. Reaction conditions: substrate (0.2 mmol), NaSO
(1 atm), 23 h. Yields were determined by GC with biphenyl as an
internal standard. Ratios of regioisomers were determined by GC and F NMR. Substrate (4 mmol), NaSO CF (0.2 mmol), H PV Mo 40 (10 mol% with respect to
2 3 6 3 9 40
CF (0.6 mmol), H PV Mo O
(
10 mol% with respect to substrate), acetonitrile/water (2 mL, 4/1 v/v), 120 °C (bath temp.), O
2
1
9
a
2
3
6
3
9
O
b
c
d
NaSO
2
CF
3
). Naphthalene (1 mmol), NaSO
2
CF
3
(0.2 mmol), H
6
PV
3
Mo
9
O
40 (10 mol% with respect to NaSO
2
CF
3
2 3
). Yields were calculated based on NaSO CF . 6 h.
O2
H PV Mo O
40
6
3
9
CF3
NaSO CF
2
3
HPA HPAred
NaSO CF3
CF SO
3 2
2
72% yield
step 1
ꢀ
O2
step 2
SO2
Scheme 3 A larger-scale trifluoromethylation of benzene. Reaction conditions:
benzene (40 mmol), NaSO CF (2.0 mmol), H PV Mo 40 (10 mol% with
respect to NaSO CF ), acetonitrile/water (20 mL, 4/1 v/v), 120 °C (bath temp.),
(1 atm), 44 h. Yields were calculated based on NaSO CF
CF3 HPA HPAred
2
3
6
3
9
O
H
CF3
CF3
2
3
H
R
R
R
O
2
2
3
.
step 3
step 4
A
ꢀ
Scheme 2 A possible reaction mechanism for the present HPA-catalyzed product (step 4). The reduced HPA formed in step 1 and step 4 is
9
trifluoromethylation. The reduced HPA (HPAred) formed in step 1 and step 4 is reoxidized by O2.
reoxidized by O .
2
Finally, we turned our attention to the examination of the
substrate scope for the present aerobic C–H trifluoromethylation
using H6PV3Mo9O40 under the optimized reaction conditions. As
summarized in Fig. 1, various kinds of (hetero)arenes could be
converted into the corresponding trifluoromethylated products. As
mentioned above, the trifluoromethylation of 1a gave the
corresponding trifluoromethylated products in high yields (Fig. 1,
entry 5; 90% total yield; 61% yield of 2a; 29% yield of 3a). Notably,
benzene and naphthalene could be efficiently converted into
trifluoromethylbenzene (65% yield based on NaSO2CF3) and
trifluoromethylnaphthalenes (55% total yield based on NaSO2CF3),
significantly suppressed, and the total yield of the
trifluoromethylated products was only 2% (Table 1, entry 11).
Therefore, we consider that the involvement of radical intermediates
12,13
is most likely in the present trifluoromethylation.
of SO2 during the reaction was also confirmed by the gas phase GC-
The formation
+
MS analysis (m/z 64 [M] and 48).
Based on the above-mentioned experimental results, we here
propose a possible reaction mechanism for the present HPA-
catalyzed trifluoromethylation (Scheme 2). Firstly, the single-
electron transfer from NaSO2CF3 to HPA proceeds to give the
reduced HPA and CF3SO2• intermediate (step 1), immediately
followed by its disproportion into CF3• and SO2 (step 2). Then, CF3•
reacts with an arene to afford the radical intermediate A (step 3), and
subsequently, HPA accepts the electron and proton from the
intermediate A to afford the corresponding trifluoromethylated
respectively (Fig. 1, entries
1
and 2).
A larger-scale
trifluoromethylation of benzene (ten-fold scale up) was also
effective and gave trifluoromethylbenzene in 72% yield (based on
NaSO2CF3, Scheme 3). The trifluoromethylation of benzenes
possessing electron-donating as well as electron-withdrawing
substituents on the phenyl rings efficiently proceeded to give the
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8
(a) C. L. Hill and C. M. Prosser-McCartha, CoorVdie.wCAhreticmle.ORnelinv.e,
995, 143, 407; (b) T. Okuhara, N. Mizu
Catal., 1996, 41, 113; (c) R. Neumann, Prog. Inorg. Chem.,
998, 47, 317; (d) Thematic issue on “Polyoxometalates”, ed.,
C. L. Hill, Chem. Rev., 1998, 98, 1−390; (e) I. V. Kozhevnikov,
Catalysts for Fine Chemical Synthesis, Volume 2, Catalysis by
Polyoxometalates, John Wiley & Sons, Chichester, 2002; (f) C.
L. Hill in Comprehensive Coordination Chemistry II, Vol. 4, eds.,
J. A. McCleverty and T. J. Meyer, Elsevier Pergamon,
Amsterdam, 2004, pp. 679–759; (g) N. Mizuno, K. Kamata, S.
Uchida and K. Yamaguchi in Modern Heterogeneous Oxidation
Catalysis, ed., N. Mizuno, Wiley-VCH, Weinheim, 2009,
pp. 185−216; (h) S. Wang and G. Yang, Chem. Rev., 2015, 115,
corresponding trifluoromethylated products (Fig. 1, entries 3–8). In
the case of 1,4-dichlorobenzene and 1,2-dichlorobenzene, the
reaction proceeded without any dechlorination (Fig. 1, entries 6 and
1
D : 10.1039/C6N 3654F
n oO Ia nd M. Miso nJ 0o , Adv.
1
7). No hydration and hydrolytic decomposition proceeded for
benzonitrile (Fig. 1, entry 8). Heteroarenes, such as pyrazine, 3,5-
dichloropyridine, quinoline, and dibenzothiophene, could be also
converted into the corresponding trifluoromethylated products (Fig.
1, entries 9–12).
In conclusion, we have successfully developed for the first time
the efficient direct C–H trifluoromethylation of (hetero)arenes
catalyzed by vanadium-containing heteropoly acids using NaSO2CF3
as the CF3 source and O2 as the terminal oxidant. The reaction
proceeds via radical pathway. Various kinds of structurally diverse
4893.
9
(a) A. M. Khenkin, G. Leitus and R. Neumann, J. Am. Chem.
Soc., 2010, 132, 11446; (b) K. Yamaguchi, N. Xu, X. Jin, K.
Suzuki and N. Mizuno, Chem. Commun., 2015, 51, 10034; (c)
N. Xu, X. Jin, K. Suzuki, K. Yamaguchi and N. Mizuno, New
J. Chem., 2016, 40, 4865.
(hetero)arenes, such as substituted benzenes, naphthalene, pyrazine,
pyridine, quinoline, and thiophene, could be converted into the
corresponding trifluoromethylated products.
This work was supported in part by JSPS KAKENHI Grant No.
1
1
0 (a) M. Sadakene and E. Steckhan, Chem. Rev., 1998, 98, 219;
(b) I. V. Kozhevnikov, Chem. Rev., 1998, 98, 171.
26708009 and Grant No. 15H05797 in “Precisely Designed
Catalysts with Customized Scaffolding”.
1 (a) J. K. Lee, J. Melsheimer, S. Berndt, G. Mestl, R. Schlögl and
K. Köhler, Appl. Catal., A, 2001, 214, 125; (b) A. Rudnitskaya,
J. A. F. Gamelas, D. V. Evtuguin and A. Legin, New J. Chem.,
2
012, 36, 1036.
12 (a) X. Wu, L. Chu and F. L. Qing, Angew. Chem., Int. Ed., 2013,
2, 2198; (b) F. Yang, P. Klumphu, Y. M. Liang and B. H.
Notes and references
5
1
(a) J. T. Welch, Tetrahedron, 1987, 43, 3123; (b) Thematic issue
on ‘Fluorine in the Life Sciences’, ChemBioChem, 2004, 5, 557;
Lipshutz, Chem. Commun., 2014, 50, 936; (c) Y. Lu, Y. Li, R.
Zhang, K. Jin and C. Duan. J. Fluor. Chem., 2014, 161, 128; (d)
J. Jacquet, S. Blanchard, E. Derat, M. D.-E. Murr and L.
Fensterbank, Chem. Sci., 2016, 7, 2030.
(c) S. Purser, P. R. Moore, S. Swallow and V. Gouverneur, Chem.
Soc. Rev., 2008, 37, 320.
2
(a) T. Furuya, A. S. Kamlet and T. Ritter, Nature, 2011, 473, 470;
(b) O. A. Tomashenko and V. V. Grushin, Chem. Rev., 2011, 111,
1
3 We attempted to detect the adduct of TEMPO–CF by means of
GC, GC-MS, and F NMR analyses. However, the detection
was not successful. In the following reported radical
3
19
4475; (c) E. Merino and C. Nevado, Chem. Soc. Rev., 2014, 43,
6598; (d) C. Alonso, E. M. Marigorta, G. Rubiales and F.
Palacios, Chem. Rev., 2015, 115, 1847.
trifluoromethylation systems, the detection of the TEMPO–CF
3
adduct is also unsuccessful: (a) W. Kong, M. Casimiro, E.
Merino and C. Nevado, J. Am. Chem. Soc., 2013, 135, 14480;
3
4
(a) A. Studer, Angew. Chem., Int. Ed., 2012, 51, 8950; (b) H.
Liu, Z. Gu and X. Jiang, Adv. Synth. Catal., 2013, 355, 617.
(a) T. Kino, Y. Nagase, Y. Ohtsuka, K. Yamamoto, D. Uraguchi,
K. Tokuhisa and T. Yamakawa, J. Fluor. Chem., 2010, 131, 98;
(b) Y. Yang, Y. Liu, Y. Jiang, Y. Zhang and D. A. Vicic, J. Org.
Chem., 2015, 80, 6639; (c) Q. Lefebvre, N. Hoffmann and M.
Rueping, Chem. Commun., 2016, 52, 2493.
(b) R. N. Loy and M. S. Sanford, Org. Lett., 2011, 13, 2548; (c)
D. Nagib and D. MacMillan, Nature, 2011, 480, 224; (d) E.
Mejía and A. Togni, ACS Catal., 2012, 2, 521; (e) S. Seo, J. B.
Taylor and M. F. Greaney, Chem. Commun., 2013, 49, 6385; (f)
A. Sato, J. Han, T. Ono, A. Wzorek, J. L. Aceña and V. A.
Soloshonok, Chem. Commun., 2015, 51, 5967; (g) L. He, K.
Natte, J. Rabeah, C. Taeschler, H. Neumann, A. Brückner and M.
Beller, Angew. Chem., Int. Ed., 2015, 54, 4320; (h) M. Baar and
S. Blechert, Chem. –Eur. J., 2015, 21, 526; (i) F. Sladojevich, E.
McNeill, J. Orgel, S. Zheng and T. Ritter, Angew. Chem., Int.
Ed., 2015, 54, 3712; (j) J. W. Beatty, J. J. Douglas, K. P. Cole
and C. R. J. Stephenson, Nat. Commun., 2015, 6, 7919; (k) K.
Natte, R. V. Jagadeesh, L. He, J. Rabeah, J. Chen, C. Taeschler,
S. Ellinger, F. Zaragoza, H. Neumann, A. Brückner and M.
Beller, Angew. Chem., Int. Ed., 2016, 55, 2782.
5
6
(a) M. Tordeux, B. R. Langlois and C. Wakselman, J. Org.
Chem., 1989, 54, 2452; (b) B. R. Langlois, E. Laurent and N.
Roidot, Tetrahedron Lett., 1991, 32, 7525; (c) C. Zhang, Adv.
Synth. Catal., 2014, 356, 2895.
(a) Y. Ji, T. Brueckl, R. D. Baxter, Y. Fujiwara, I. B. Seiple, S.
Su, D. G. Blackmond and P. S. Baran, Proc. Natl. Acad. Sci.,
2011, 108, 14411; (b) Y. Yang, K. Iwamoto, E. Tokunaga and N.
Shibata, Chem. Commun., 2013, 49, 5510; (c) D. Wang, G.-J.
Deng, S. Chen and H. Gong, Green Chem., 2016, 18, 5967.
(a) L. Li, X. Mu, W. Liu, Y. Wang, Z. Mi and C. Li, J. Am.
Chem. Soc., 2016, 138, 5809; (b) L. Cui, Y. Matusaki, N. Tada,
T. Miura, B. Uno and A. Itoh, Adv. Synth. Catal., 2013, 355,
7
2203.
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New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ03654F
Graphical abstract
R
2
NaSO CF3
R
H PV Mo O
40
6
3
9
CF3
O (1 atm)
2
X
X
(
X = CH, N)
In the presence of phosphovanadomolybdic acids, a direct C–H trifluoromethylation of
(
hetero)arenes efficiently proceeded by utilizing NaSO CF as the CF source and O as the
2 3 3 2
terminal oxidant.