Fluoride anion-initiated bis-trifluoromethylation of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane

Article abstract of DOI:10.1039/d0cc04826g

The fluoride anion-initiated reaction of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane (Me3SiCF3) that results in the formation of O-silyl-protected 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols is reported. A phenoxide anion, generated during the trifluoromethylation of the phenyl carboxylate, also activates the Me3SiCF3, which permits a catalytic amount of the fluoride anion source to be used. Various functional groups, which can be used for further elaboration, are tolerated in the reaction.

Full text of DOI:10.1039/d0cc04826g

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: K. Takahashi, Y.
Ano and N. Chatani, Chem. Commun., 2020, DOI: 10.1039/D0CC04826G.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/D0CC04826G
COMMUNICATION
Fluoride anion-initiated bis-trifluoromethylation of phenyl
aromatic carboxylates with (trifluoromethyl)trimethylsilane†
Kenjiro Takahashi,a Yusuke Anoa,b and Naoto Chatani*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The fluoride anion-initiated reaction of phenyl aromatic hydroxyhexafluoroisopropyl groups into aromatic compounds
carboxylates with (trifluoromethyl)trimethylsilane (Me3SiCF3) with has been accomplished by employing nucleophilic
the formation of O-silyl-protected
2-aryl-1,1,1,3,3,3- trifluoromethylation protocol.10 The trifluoromethylation of
hexafluoroisopropanols is reported. A phenoxide anion, generated trifluoroacetophenones is a typical method for the synthesis of
during the trifluoromethylation of the phenyl carboxylate, 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols, reaction that
a
a
functions to activate the Me3SiCF3, which permits a catalytic usually involves the use of the Ruppert–Prakash reagent,
amount of the fluoride anion source to be used. Various functional Me3SiCF3,11 or the less reactive Bu3SnCF3 in the presence of a
groups, which can be used for further elaboration, are tolerated in catalytic amount of a Lewis base activator.12 However, the
the reaction.
synthesis of trifluoroacetophenone derivatives are not so
straightforward compared with carboxylic acid derivatives. The
trifluoromethylation of aroyl chlorides is a convenient method
for the synthesis of 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols,
The intrinsic nature of fluorine atoms enables fluorine-
substituted organic compounds to acquire unique properties
that differ from their hydrocarbon analogues.1 Among these,
increased attention has been directed to 1,1,1,3,3,3-
hexafluoroisopropanol (HFIP) and derivatives thereof.2 With the
in which trifluoromethylating reagents derived from
a
trifluoroacetate salt or a fluoroform are usually employed.13
Me3SiCF3 can also be used for the trifluoromethylation of acid
anhydrides as well as acid chlorides.14 Skrydstrup reported on a
practical example that proceeds via the Pd-catalyzed
fluorocarbonylation of aryl bromides or fluorosulfates followed
by trifluoromethylation using Me3SiCF3.15 In these methods,
more than a stoichiometric amount of the fluoride anion (F–)
source is generally required for the efficient activation of
Me3SiCF3.
aid
of
two
trifluoromethyl
groups,
the
hydroxyhexafluoroisopropyl moiety is sufficiently bulky to
confer highly acidic properties on the proton, thus contributing
to the formation of strong hydrogen bonding. The introduction
of the hydroxyhexafluoroisopropyl group can, therefore be
used in the design of catalysts and ligands3 as well as in chemical
sensing
hexafluoroisopropanol
pharmaceutically potent products5 and polymeric materials.6
The conventional synthesis of 2-aryl-1,1,1,3,3,3-
hexafluoroisopropanols typically involves the electrophilic
substitution of arenes or the nucleophilic addition of aryl metal
reagents, using hexafluoroacetone as the electrophile.7
Dehydrogenative coupling of HFIP with electron-rich arenes,
including anilines and indoles, has recently been achieved by
utilizing Co8 or Cu9 catalysis. Alternatively, the introduction of
materials.4
Moreover,
derivatives
2-aryl-1,1,1,3,3,3-
are found in
To the best of our knowledge, reports on the synthesis of 2-
aryl-1,1,1,3,3,3-hexafluoroisopropanols from aromatic esters
using Me3SiCF3 have been limited despite their availability and
synthetic utility. Pentafluorophenyl benzoates can also serve as
a
substrate for the synthesis of 2-aryl-1,1,1,3,3,3-
hexafluoroisopropanols, however the use of a stoichiometric
amount of tetramethylammonium fluoride (Me4NF) is required
(Scheme 1a),14 or alternatively a large excess of Me3SiCF3 was
used when the amount of Me4NF was reduced.16 The
trifluoromethylation of methyl benzoates can proceed in the
presence of a catalytic amount of the F– source to give
trifluoromethyl ketones (Scheme 1b).17 However, the synthesis
of 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols from methyl
benzoates has not been fully explored except for the bis-
trifluoromethylation of an electronically deficient methyl
benzoate.5a
a. Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita,
Osaka 565-0871, Japan. E-mail: chatani@chem.eng.osaka-u.ac.jp
b. Center for Atomic and Molecular Technologies, Graduate School of Engineering,
Osaka University, Suita, Osaka 565-0871, Japan.
†
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
In this report, we disclose that the reaction of phenyl aromatic
carboxylates with Me3SiCF3 provides O-silyl-protected 2-aryl-
1,1,1,3,3,3-hexafluoroisopropanols, even in the presence of a
Table 1 Optimization of reaction conditions.
View Article Online
DOI: 10.1039/D0CC04826G
O
OSiMe3
Me3SiCF3 3 equiv
catalytic amount of the F– source (Scheme 1c)
.
CF3
CF3
additive
OPh
1,4-dioxane 1 mL
rt, 6 h
1a 0.3 mmol
2a
(a) Bis-trifluoromethylation of pentafluorophenyl benzoates using a stoichiometric amount of R4NF
or a large excess amount of Me3SiCF3 in the presence of a catalytic amount of R4NF.
Entry
Additive (mol%)
CsF (10)
Yield of 2a (%)a
O
OH
1) Me3SiCF3
R4NF
1
81
98
4
CF3
CF3
OC6F5
2
CsF (1)
2) H3O+
3
KF (1)
4
KF (1) + 18-crown-6 (2)
CsOPh (1)
98
70
11
0
(b) Trifluoromethylation of methyl benzoates using a catalytic amount of F– sources.
5
O
O
6
NaOPh (1) + 15-crown-5 (5)
PPh3 (1)
1) Me3SiCF3
cat. Bu4NF or CsF
OMe
CF3
7
2) H3O+
8
Et3N (3)
trace
0
9
10b
none
(c) This work: Bis-trifluoromethylation of phenyl benzoates using a catalytic amount of CsF.
CsF (1)
69
O
OSiMe3
Me3SiCF3
a Isolated yield. b Me3SiCF3 (2.2 equiv) was used.
CF3
CF3
cat. CsF (1 mol%)
OPh
With the optimized conditions in hand, we investigated the
scope of the reaction with respect to phenyl aromatic
carboxylates (Scheme 2). Phenyl 1-naphthoate (1b), 4-
phenylbenzoate (1c), and 3,4-dimethylbenzoate (1d) could be
converted into the corresponding silyl ethers in good yields (2b–
d). Steric hindrance of ortho-substituents affected the progress
of the reaction, resulting in only modest yields of 2e and 2f even
when the reaction run for 24 h. The trifluoromethylation of
halogenated aryl esters (1g and 1h) proceeded smoothly to give
2g and 2h, which would serve as valuable intermediates in
cross-coupling reactions. Both of the ester groups in the
diphenyl naphthalene-1,4-dicarboxylate (1i) could be converted
into siloxyhexafluoroisopropyl groups. When 1j, bearing a
terminal alkyne functionality, was reacted with 5 equivalents of
Me3SiCF3, the silylation of the terminal alkyne took place along
with the formation of the desired trifluoromethylation of ester,
affording 2j in 90% yield.19 Phenyl cinnamate (1k) as well as
phenyl heteroaromatic carboxylates, including quinoline (1l,
1m), benzofuran (1n), indole (1o), and pyridine (1p), were also
applicable for use in this protocol, giving the corresponding
trifluoromethylation products 2k–p in good yields.
Unfortunately, the reaction of phenyl aromatic carboxylates
with other (perfluoroalkyl)trialkylsilanes, such as Et3SiCF3,
Me3SiC2F5, and Me3SiCF2H, was unsuccessful under the
optimized conditions.20
Scheme 1 Trifluoromethylation of aromatic esters with Me3SiCF3.
We began our studies by conducting the reaction of phenyl
2-naphthoate (1a, 0.3 mmol) with Me3SiCF3 (3 equiv) in the
presence of 10 mol% of CsF in 1,4-dioxane at room temperature,
giving the 1,1,1,3,3,3-hexafluoro-2-naphthylisopropyl silyl ether
(2a) in 81% isolated yield (Table 1, entry 1). PhOSiMe3 was also
present in the crude reaction mixture, as evidenced by 1H NMR
and GC analysis. Reducing the amount of CsF to 1 mol%
improved the yield of 2a to 98% (entry 2). When 1 mol% of KF
was used in place of CsF as an additive, the yield of 2a was
significantly decreased (entry 3), due, in part, to the low
solubility of KF in 1,4-dioxane. In fact, the addition of KF with
18-crown-6 provided the desired trifluoromethylation product
without loss of the yield of 2a (entry 4). It should be noted that
this reaction also proceeded when 1 mol% of CsOPh was added,
leading to the formation of 2a in 70% yield (entry 5). However,
other additives including NaOPh/15-crown-5, PPh3, and Et3N
were ineffective (entries 6-8), and no reaction occurred in the
absence of an additive (entry 9). Lowering the amount of
Me3SiCF3 (2.2 equiv) decreased the yield of 2a. (entry 10). After
the screening of solvents and leaving groups, 1,4-dioxane and a
phenoxy group, respectively, were suitable for achieving an
efficient transformation.18
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
View Article Online
O
OSiMe3
O
OSiMe3
DOI: 10.1039/D0CC04826G
Me3SiCF3 3 equiv
CsF 1 mol%
Me3SiCF3 3 equiv
CsF 1 mol%
CF3
CF3
CF3
OPh
OPh
CF3
R
R
1,4-dioxane, rt, 6 h
1,4-dioxane 1 mL
rt, 6 h
1a 3.2 mmol
2a 96% (1.14 g)
1 0.3 mmol
2
OH
OSiMe3
OSiMe3
CF3
CF3
OSiMe3
CF3
CF3
CF3
CF3
1 M aq. NaOH
1,4-dioxane, rt, 30 min
CF3
CF3
3a 92% (0.84 g)
Ph
2d 89%a
Scheme 3 Large-scale synthesis of 2-naphthylhexafluoroisopropanol 3a.
2b 82%
2c 98%
OSiMe3
CF3
CF3
Ph
OSiMe3
OSiMe3
Recently, Lloyd-Jones reported on a detailed mechanistic
investigation of anion-initiated trifluoromethylation using
Me3SiCF3.21 They concluded that the pentacoordinate silicon
intermediates such as Me3SiF(CF3)– or Me3Si(CF3)2– are unable
to transfer a CF3 group directly, while CF3– can serve as an active
nucleophile. It should also be noted that metal phenoxides such
as CsOPh and KOPh are effective initiators for the anion-
initiated trifluoromethylations using Me3SiCF3. On the basis of
this report and our results, a proposed reaction mechanism for
this transformation is illustrated in Scheme 4. The reaction of
Me3SiCF3 with CsF initially gives CsCF3, which then reacts with
CF3
CF3
I
CF3
CF3
MeO
Cl
2e 71%a
2f 45%a
2g 78%
Me3SiO
F3C
F3C
OSiMe3
CF3
CF3
OSiMe3
CF3
CF3
Br
2h 86%
2i 90%a,b
Me3SiCF3 to produce an equilibrium mixture of
a
O
OSiMe3
pentacoordinate silicon intermediate (Scheme 4a). The
CF3
CF3
nucleophilic attack of CF3– to the carbonyl group in 1 then gives
OPh
the trifluoroacetophenone 4 along with the elimination of PhO–.
–
The subsequent addition of CF3 to
4 results in the
Me3Si
1j
2j 90%c
deprotonation of the 2-aryl-1,1,1,3,3,3-hexafluoroisopropanol
–
(2’), which then reacts with Me3SiCF3 to afford CF3 and 2
(Scheme 4b). The reaction of PhO– with Me3SiCF3 can also
provide CF3– along with the formation of PhOSiMe3 (Scheme 4c).
Owing to this process, the use of a catalytic amount of CsF
initiator is sufficient to allow the transformation of 1 into 2.
OSiMe3
OSiMe3
CF3
CF3
CF3
CF3
CF3
CF3
N
N
OSiMe3
2k 85%
2l 83%
2m 89%
(a)
CF3
OSiMe3
Me3SiCF3
CsF
OSiMe3
OSiMe3
Me
Me
–
Me3SiCF3
Cs+ CF3
Cs+
Me Si
CF3
CF3
CF3
CF3
– Me3SiF
CF3
CF3
CF3
N
Me
O
Br
N
(b)
O
O
O
–
–
2p 81%a
CF3
CF3
2n 86%
2o 67%
CF3
– PhO–
Scheme 2 Scope of phenyl carboxylates. Reaction conditions: phenyl carboxylate (0.3
mmol), Me3SiCF3 (0.9 mmol), CsF (0.003 mmol), 1,4-dioxane (1 mL), rt, 6 h unless
otherwise noted. a Run for 24 h. b Me3SiCF3 (6 equiv) was used. c Me3SiCF3 (5 equiv) was
used.
Ar
OPh
Ar
CF3
Ar
CF3
1
4
2'
OSiMe3
CF3
CF3
Me3SiCF3
–
+
CF3
Ar
We next examined a large-scale trifluoromethylation of 1a,
which successfully afforded 2a without any loss of yield
(Scheme 3). The subsequent deprotection of 2a by treatment
2
(c)
PhO–
–
Me3SiCF3
CF3
+ PhOSiMe3
with
a
base
led
to
the
formation
of
2-
Scheme 4 A proposed mechanism.
naphthylhexafluoroisopropanol (3a) in 88% yield in 2 steps.
In conclusion, we report on the development of an efficient
method for the synthesis of 2-(hetero)aryl-1,1,1,3,3,3-
hexafluoroisopropanol
derivatives
from
phenyl
(hetero)aromatic carboxylates by using Me3SiCF3 in
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
Pudzianowski, D.-R. Wu, M. Yarde, D.-R. Shen, V. Borowski, J.
combination with
a catalytic amount of CsF. Various
View Article Online
H. Xie, H. Sun, C. D'Arienzo, M. DabrosD, OMI:.1A0..1G0a39le/Dlla0,CFC.0W48a2n6gG,
C. A. Weigelt, Q. Zhao, W. Foster, J. E. Somerville, L. M. Salter-
Cid, J. C. Barrish, P. H. Carter and T. G. M. Dhar, Bioorg. Med.
Chem. Lett., 2018, 28, 85; (i) J. J.-W. Duan, Z. Lu, B. Jiang, S.
Stachura, C. A. Weigelt, J. S. Sack, J. Khan, M. Ruzanov, M. A.
Galella, D.-R. Wu, M. Yarde, D.-R. Shen, D. J. Shuster, V.
Borowski, J. H. Xie, L. Zhang, S. Vanteru, A. K. Gupta, A.
Mathur, Q. Zhao, W. Foster, L. M. Salter-Cid, P. H. Carter and
T. G. M. Dhar, ACS Med. Chem. Lett., 2019, 10, 367.
(a) D. W. Reynolds, P. E. Cassidy, C. G. Johnson and M. L.
Cameron, J. Org. Chem., 1990, 55, 4448; (b) P. E. Cassidy, T.
M. Aminabhavi, V. S. Reddy and J. W. Fitch III, Eur. Polym. J.,
1995, 31, 353; (c) J. W. Fitch, E. Bucio, L. Martinez, J. Macossay,
S. R. Venumbaka, N. Dean, D. Stoakley and P. E. Cassidy,
Polymer, 2003, 44, 6431; (d) M. Miyasaka, N. Koike, Y.
Fujiwara, H. Kudo and T. Nishikubo, Polym. J., 2011, 43, 325.
(a) B. S. Farah, E. E. Gilbert and J. P. Sibilia, J. Org. Chem., 1965,
30, 998; (b) J. Sepio and R. L. Soulen, J. Fluorine Chem., 1984,
24, 61; (c) L. S. Chen, G. J. Chen and C. Tamborski, J.
Organomet. Chem., 1981, 215, 281; (d) T. J. Barbarich, B. G.
Nolan, S. Tsujioka, S. M. Miller, O. P. Anderson and S. H.
Strauss, J. Fluorine Chem., 2001, 112, 335; (e) B. G. Nolan, S.
Tsujioka and S. H. Strauss, J. Fluorine Chem., 2002, 118, 103.
H. Zhao, S. Zhao, X. Li, Y. Deng, H. Jiang and M. Zhang, Org.
Lett., 2019, 21, 218.
functionalities including metal-malleable halogen groups are
compatible to this protocol. A key to the successful reaction is
the sufficient leaving ability and basicity of the phenoxide anion
that can activate Me3SiCF3 to promote the following
trifluoromethylation.
Conflicts of interest
There are no conflicts to declare.
6
7
Acknowledgements
This work was supported by a Grant in Aid for Specially
Promoted Research by MEXT (No. 17H06091).
Notes and references
1
Selected reviews: (a) B. E. Smart, J. Fluorine Chem., 2001, 109,
3; (b) F. Babudri, G. M. Farinola, F. Naso and R. Ragni, Chem.
Commun., 2007, 1003; (c) S. Purser, P. R. Moore, S. Swallow
and V. Gouverneur, Chem. Soc. Rev., 2008, 37, 320; (d) R.
Berger, G. Resnati, P. Metrangolo, E. Weber and J. Hulliger,
Chem. Soc. Rev., 2011, 40, 3496; (e) L. E. Zimmer, C. Sparr and
R. Gilmour, Angew. Chem. Int. Ed., 2011, 50, 11860; (f) T.
Fujiwara and D. O’Hagan, J. Fluorine Chem., 2014, 167, 16; (g)
E. P. Gillis, K. J. Eastman, M. D. Hill, D. J. Donnelly and N. A.
Meanwell, J. Med. Chem., 2015, 58, 8315; (h) Y. Zhou, J. Wang,
Z. Gu, S. Wang, W. Zhu, J. L. Aceña, V. A. Soloshonok, K. Izawa
and H. Liu, Chem. Rev., 2016, 116, 422; (i) N. A. Meanwell, J.
Med. Chem., 2018, 61, 5822; (j) M. Inoue, Y. Sumii and N.
Shibata, ACS Omega, 2020, 5, 10633.
8
9
(a) Z. Xu, Z. Hang, L. Chai and Z.-Q. Liu, Org. Lett., 2016, 18,
4662; (b) J. Chen, M. Li, J. Zhang, W. Sun and Y. Jiang, Org.
Lett., 2020, 22, 3033.
10 P. Beier, M. Zibinsky and G. K. S. Prakash, Org. React., 2016,
91, 1.
11 (a) I. Ruppert, K. Schlich and W. Volbach, Tetrahedron Lett.,
1984, 25, 2195; (b) G. K. S. Prakash, R. Krishnamurti and G. A.
Olah, J. Am. Chem. Soc., 1989, 111, 393; (c) G. K. S. Prakash
and A. K. Yudin, Chem. Rev., 1997, 97, 757; (d) X. Liu, C. Xu, M.
Wang and Q. Liu, Chem. Rev., 2015, 115, 683.
12 (a) T. Hagiwara, T. Kobayashi and T. Fuchikami, NIPPON
KAGAKU KAISHI, 1997, 869; (b) I. A. Sanhueza, K. J. Bonney, M.
C. Nielsen and F. Schoenebeck, J. Org. Chem., 2013, 78, 7749.
13 (a) Y. Chang and C. Cai, J. Fluorine Chem., 2005, 126, 937; (b)
Y. Zhang, M. Fujiu, H. Serizawa and K. Mikami, J. Fluorine
Chem., 2013, 156, 367; (c) J. B. Geri, M. M. WadeꢀWolfe and
N. K. Szymczak, Angew. Chem. Int. Ed., 2018, 57, 1381.
14 L. A. Babadzhanova, N. V. Kirij, Y. L. Yagupolskii, W. Tyrra and
D. Naumann, Tetrahedron, 2005, 61, 1813.
15 K. Domino, C. Veryser, B. A. Wahlqvist, C. Gaardbo, K. T.
Neumann, K. Daasbjerg, W. M. DeꢀBorggraeve and T.
Skrydstrup, Angew. Chem. Int. Ed., 2018, 57, 6858.
16 H. Lenormand, V. Corcé, G. Sorin, C. Chhun, L.-M. Chamoreau,
L. Krim, E.-L. Zins, J.-P. Goddard and L. Fensterbank, J. Org.
Chem., 2015, 80, 3280.
17 (a) J. Wiedemann, T. Heiner, G. Mloston, G. K. S. Prakash and
G. A. Olah, Angew. Chem. Int. Ed., 1998, 37, 820; (b) R. P. Singh,
G. Cao, R. L. Kirchmeier and J. M. Shreeve, J. Org. Chem., 1999,
64, 2873.
18 See the Electronic Supplementary Information (ESI) for details.
19 (a) M. Ishizaki and O. Hoshino, Tetrahedron, 2000, 56, 8813;
(b) P. Arde, V. Reddy and R. Vijaya Anand, RSC Adv., 2014, 4,
49775; (c) K. Nozawa-Kumada, M. Inagi and Y. Kondo, Asian J.
Org. Chem., 2017, 6, 63.
20 In the reaction using a stoichiometric amount of CsF, the bis-
perfluoroalkylation of 1a with Et3SiCF3 or Me3SiC2F5 took place.
However, a mixture of the expected O-silyl-protected alcohols
and the free alcohols was formed. See the Electronic
Supplementary Information (ESI) for details.
21 C. P. Johnston, T. H. West, R. E. Dooley, M. Reid, A. B. Jones,
E. J. King, A. G. Leach and G. C. Lloyd-Jones, J. Am. Chem. Soc.,
2018, 140, 11112 and references cited therein.
2
3
(a) I. Colomer, A. E. R. Chamberlain, M. B. Haughey and T. J.
Donohoe, Nat. Rev. Chem., 2017, 1, 0088; (b) S. K. Sinha, T.
Bhattacharya and D. Maiti, React. Chem. Eng., 2019, 4, 244;
(c) L. Schulz and S. R. Waldvogel, Synlett, 2019, 30, 275.
(a) E. F. Perozzi and J. C. Martin, J. Am. Chem. Soc., 1979, 101,
1591; (b) S. Morikawa, K. Michigami and H. Amii, Org. Lett.,
2010, 12, 2520; (c) M. E. O’Reilly, I. Ghiviriga, K. A. Abboud and
A. S. Veige, J. Am. Chem. Soc., 2012, 134, 11185; (d) L. Ratjen,
M. vanꢀGemmeren, F. Pesciaioli and B. List, Angew. Chem. Int.
Ed., 2014, 53, 8765.
4
5
V. Schroeder, S. Savagatrup, M. He, S. Lin and T. M. Swager,
Chem. Rev., 2019, 119, 599.
(a) L. Li, J. Liu, L. Zhu, S. Cutler, H. Hasegawa, B. Shan and J. C.
Medina, Bioorg. Med. Chem. Lett., 2006, 16, 1638; (b) E. L.
Grimm, C. Brideau, N. Chauret, C.-C. Chan, D. Delorme, Y.
Ducharme, D. Ethier, J.-P. Falgueyret, R. W. Friesen, J. Guay,
P. Hamel, D. Riendeau, C. Soucy-Breau, P. Tagari and Y. Girard,
Bioorg. Med. Chem. Lett., 2006, 16, 2528; (c) N. Kumar, L. A.
Solt, J. J. Conkright, Y. Wang, M. A. Istrate, S. A. Busby, R. D.
Garcia-Ordonez, T. P. Burris and P. R. Griffin, Mol. Pharmacol.,
2010, 77, 228; (d) Y. Wang, N. Kumar, P. Nuhant, M. D.
Cameron, M. A. Istrate, W. R. Roush, P. R. Griffin and T. P.
Burris, ACS Chem. Biol., 2010, 5, 1029; (e) N. Kumar, D. J.
Kojetin, L. A. Solt, K. G. Kumar, P. Nuhant, D. R. Duckett, M. D.
Cameron, A. A. Butler, W. R. Roush, P. R. Griffin and T. P.
Burris, ACS Chem. Biol., 2011, 6, 218; (f) M. P. Bourbeau, K. S.
Ashton, J. Yan and D. J. St. Jean, Jr., J. Org. Chem., 2014, 79,
3684; (g) K. Matsuno, Y. Ueda, M. Fukuda, K. Onoda, M. Waki,
M. Ikeda, N. Kato and H. Miyachi, Bioorg. Med. Chem. Lett.,
2014, 24, 4276; (h) H. Gong, D. S. Weinstein, Z. Lu, J. J.-W.
Duan, S. Stachura, L. Haque, A. Karmakar, H. Hemagiri, D. K.
Raut, A. K. Gupta, J. Khan, D. Camac, J. S. Sack, A.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/D0CC04826G
COMMUNICATION
Fluoride anion-initiated trifluoromethylation of phenyl aromatic
carboxylates with (trifluoromethyl)trimethylsilane leading to the
formation of 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols†
Received 00th January 20xx,
Accepted 00th January 20xx
Kenjiro Takahashi,a Yusuke Anoa,b and Naoto Chatani*a
DOI: 10.1039/x0xx00000x
O
OSiMe3
CF3
Me3SiCF3
CsF (1 mol%)
OPh
CF3
R
R
1,4-dioxane, rt
activation of Me3SiCF3 by F– and leaving PhO–
a. Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita,
Osaka 565-0871, Japan. E-mail: chatani@chem.eng.osaka-u.ac.jp
b. Center for Atomic and Molecular Technologies, Graduate School of Engineering,
Osaka University, Suita, Osaka 565-0871, Japan.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
Please do not adjust margins