A Vitamin B12 derivative catalyzed electrochemical trifluoromethylation and perfluoroalkylation of arenes and heteroarenes in organic media

Article abstract of DOI:10.1039/c7cc06221d

The electrochemical trifluoromethylation and perfluoroalkylation of aromatic compounds mediated by a vitamin B₁₂ derivative as a cobalt-based catalyst has been developed. The Co(i) species of a vitamin B₁₂ derivative, prepared by con

Full text of DOI:10.1039/c7cc06221d

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Md. J. Hossain, T.
Ono, K. Wakiya and Y. Hisaeda, Chem. Commun., 2017, DOI: 10.1039/C7CC06221D.
Volume 52 Number
1
4
January 2016 Pages 1–216
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
www.rsc.org/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
author guidelines.
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, outlined
in our author and reviewer resource centre, 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
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
N@D5h-C80
rsc.li/chemcomm

Please do not adjust margins
ChemComm
Page 1 of 5
View Article Online
DOI: 10.1039/C7CC06221D
Journal Name
COMMUNICATION
A Vitamin B Derivative Catalyzed Electrochemical
1
2
Trifluoromethylation and Perfluoroalkylation of Arenes and
Heteroarenes in Organic Media
Received 00th January 20xx,
Accepted 00th January 20xx
a
a,b,c
a
*a,b
DOI: 10.1039/x0xx00000x
Md. Jakir Hossain, Toshikazu Ono,*
Kosuke Wakiya, and Yoshio Hisaeda
www.rsc.org/
The electrochemical trifluoromethylation and perfluoroalkylation a wide range of organic solvents and recognized as a powerful
of aromatic compounds mediated by a vitamin B12 derivative as a catalyst for isomerization with carbon-skeleton
cobalt-based catalyst has been developed. The Co(I) species of a rearrangement, methyl transfer reactions, dehalogenation,
vitamin 12 derivative, prepared by controlled-potential halide coupling reactions, and C=C and C=X bond
electrolysis at –0.8 V vs. Ag/AgCl in methanol, reacted with R
CF n-C n-C n-C 21) to form a Co–R
complex. This complex released an R
irradiation, which then reacted directly with non-activated functionalization mediated by vitamin B12 derivative (
B
5
f
I (R
f
f
hydrogenation, among others. In this study, we report the
first catalytic trifluoromethylation and perfluoroalkylation
=
3
,
F
3 7
,
4
F
9
,
8
F17, and n-C10F
f
radical under visible light reaction of aromatic compounds through direct C–H
) in
1
(
hetero)arenes to form the desired fluoroalkylated molecules organic media.
through direct C–H functionalization. To our knowledge, this
Fluoroalkylated molecules are widely used in many areas,
as organic materials, agrochemicals, and
is the first report of a naturally-derived vitamin B12 catalyzed such
6
trifluoromethylation and perfluoroalkylation of aromatic pharmaceuticals. Among these organofluorine compounds,
compounds as a cobalt-mediated catalyst.
3 f
those bearing trifluoromethyl (CF ) and perfluoroalkyl (R )
groups have received significant interest because of their
metabolic stability, lipophilicity, and electron-withdrawing
7
properties. To introduce CF3 or Rf groups into organic
The redox chemistry of the central cobalt ion in the Co(I)
species of cobalamin (B ) derivatives is widely known, with it
1
2
acting as a supernucleophile to form alkylated complexes
1
when reacted with alkyl halides. This alkylated complex is a
compounds, major improvements have been made via copper-
or palladium-catalyzed couplings of various prefunctionalized
starting materials, such as arenes containing halides, boronic
acids, or directing groups, with either nucleophilic,
useful reagent for forming radical species because the Co–C
bond is readily cleaved homolytically by photolysis,
thermolysis, and electrolysis. Research interest has been
focused on the application of this compound in various
8
,9
electrophilic, or radical CF3 or R reagents.
Several free
radical approaches are available for arene trifluoromethylation
f
2
1
0
molecular transformations. Therefore, catalytic systems using
and fluoroalkylation through direct C–H functionalization.
1
0a
10b
10c
10d
Recently, MacMillan , Baran , Blackmond , Ritter , and
natural vitamin B12 and their derivatives have been well
investigated in aqueous and organic media. The catalytic
1
0e
Itoh , reported individual radical trifluoromethylation and
fluoroalkylation of aromatic and heteroaromatic compounds
by direct C–H activation through elegant photoredox or
electrochemistry. Despite this remarkable progress, current
trifluoromethylation and perfluoroalkylation methods have
significant limitations. Some systems require expensive
trifluoromethylating and fluoroalkylating reagents (such as S-
chemistry of vitamin B has been reviewed by Gryko and co-
1
2
3
a
workers.
Among them, cobalamin derivative (B ),
2
1
heptamethyl cobyrinate perchlorate [Cob(II)7C ester]ClO (
1
1
),
4
which has ester groups in place of the peripheral amide
4
moieties of naturally occurring cobalamin, is readily soluble in
9
d
9b, 9f, 9j
(
trifluoromethyl)thiophenium salts , Togni’s reagent
8
, or
b, 9a
TES-CF3
), stoichiometric reagents, potentially explosive
8a, 10i
, or harsh reaction conditions.
1
0f, 10g, 10h
reagents
Therefore, a non-toxic, cost-effective, safe, eco-friendly, and
highly effective catalytic trifluoromethylation and
fluoroalkylation method under ambient condition is needed in
industry and academia.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
View Article Online
DOI: 10.1039/C7CC06221D
COMMUNICATION
Journal Name
Table 2. Substrate scope of electrochemical perfluoroalkylation of
a, b
various arenes
Herein, we report an efficient method for introducing
trifluoromethyl and perfluoroalkyl groups onto aromatic
compounds that proceeds via the formation of radical
intermediates in the presence of a catalytic amount of
electrocatalytic reaction. Simple and costꢀeffective
fluoroalkylating reagents (R I), such as trifluoroiodomethane
CF I), heptafluoropropyl iodide (n-C I), nonafluorobutyl
iodide (n-C I), heptadecafluorooctyl iodide (n-C 17I), and
21I), were used in this
1 in an
f
(
3
3 7
F
4
F
9
8
F
henicosafluorodecyl iodide (n-C10
F
reaction.
We initiated our study with the reaction of 1,3,5ꢀ
trimethoxybenzene ( ) with n-C I as the model reaction
2
3 7
F
a
ꢀ4
ꢀ2
using an electrochemical method (Figure S1). The results are
summarized in Table 1. Cyclic voltammetry showed that the
reduction potential of the central cobalt ion (Co(II)/Co(I)) in
Reaction conditions: [1] = 5.0×10 M; [Substrate] = 5.0×10 M; [n-
2n+1I] = 1 eq. to substrate per 1.0 hour; [n-Bu NClO ] = 0.1 M;
Internal standard C12 10; under visible light (>420 nm). Isolated yield
determined by GCꢀMS. [n-C10
C
n
F
4
4
b
F
c
4
b
F21I] = 0.33 eq. to substrate per 1.0
the
1 was –0.61 V vs. Ag/AgCl in methanol. Therefore, –0.6
d
19
hour. Yield determined by FꢀNMR.
V vs. Ag/AgCl was used as the initial setup for the controlledꢀ
potential electrolysis of 1,3,5ꢀtrimethoxybenzene using 9
make the catalytic reaction faster, but, to our disappointment,
the reaction yield was lower for both (Table 1, Entries 3 and
3 7
equiv. of n-C F I in the presence of 1 mol% 1 catalyst in
methanol at room temperature under visible light irradiation.
These conditions afforded the heptafluoropropylated arene
8
). These reductions in yield were attributed to byꢀproduct
formation (Figure S2). After a series of tests using various
solvent, we found that methanol (Table 1, Entry 2) gave the
better performance than others (Table 1, Entries 4–7). When
the visible light source was removed, very little reaction took
place, which suggested that visible light irradiation was
essential for the reaction to proceed (Table 1, Entry 9).
3 7
product 2•C F in 20% yield (Table 1, Entry 1). As a large
amount of 1,3,5ꢀtrimethoxybenzene was found to remain
unreacted, the reaction conditions were optimized to obtain a
better yield. We set the potential to –0.8 V vs. Ag/AgCl, and
obtained 100% conversion of the substrate after 9 h, which
afforded desired product 2•C
). We also tested more negative potentials of –0.9 V vs.
Ag/AgCl in methanol and –1.3 V vs. Ag/AgCl in acetonitrile to
3 7
F in 84% yield (Table 1, Entry
Notably, no product was formed in the absence of the
1
2
catalyst (Table 1, Entry 10). Based on these results, we
decided to attempt the reaction of 1,3,5ꢀtrimethoxybenzene
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
Please dCo h ne omt Ca do j um s mt margins
View Article Online
DOI: 10.1039/C7CC06221D
Journal Name
COMMUNICATION
(
100 equiv. to catalyst) with 9 equiv. of n-C
Ag/AgCl in the presence of 1 mol% of
for about under visible light irradiation at room methoxy/methyl groups at various positions (2–7
3
F
7
I at –0.8 V vs. lower yield obtained for 2•C10
F
21 was due to the low solubility
1
catalyst in methanol of n-C10
F
21I in the electrolysis condition. Benzenes bearing
) were well
tolerated, with the corresponding products obtained in good
catalystꢀmediated yields. However, 1,2ꢀdimethoxyꢀ4ꢀmethylbenzene ( ) and
reacted under the optimized
9
h
temperature, as our standard conditions.
Using these optimized conditions, the
1
6
direct C–H trifluoromethylation and perfluoroalkylation 1,3,5ꢀtrimethylbenzene
(7)
conditions, but incomplete conversion led to
low yields of the corresponding products
(
6•C
our
heteroarenes, including 1ꢀphenylpyrrole and
,2ꢀdimethylindole, which were
8
F
17 and 7•C
3
F
7
, Table 2). Interestingly,
method was
also suitable for
1
perfluoroalkylated efficiently, yielding the
desired products in moderate to good yields
(8
–9
, Table 2).
We initially hypothesized that the
1ꢀ
mediated
perfluoroalkylation reactions proceeded via a
radical (R •) intermediate. To justify radical (n-
•) formation, we tested the catalytic
trifluoromethylation
and
f
3 7
C F
reaction in the presence of a radical inhibitor,
PBN (Nꢀtertꢀbutylꢀαꢀphenylnitrone). In the
presence of 1 equiv. PBN to the substrate, a
dramatic reduction of yield (18% vs. 84%) was
observed. (Table 1, Entry 11). This result
suggested that the reaction likely involved a
radical intermediate. Indeed,
a PBN–spin
adduct (PBN•C ) was detected by ESR
3 7
F
experiment and GCꢀMS (Figure S3). These
results suggested that perfluoroalkylation
proceeded via a radical intermediate (n-C
that was mediated by . Notably,
3
F
7
•)
1
1
was
remained substantially in the reaction, and its
high durability was confirmed by UV–Vis and
MALDIꢀTOFꢀMS analysis after the reaction
(
Figure S4). Therefore, half the amount of
catalyst (0.5% to substrate) sufficiently
reacted to produce 2•C in 81% yield (Table
, Entry 12). The turnover number was 162 in
this case.
1
3 7
F
1
3 3 7 4 9 8 3 7,
FIgure 1. (a) Crystal structures of 2•CF , 2•C F , 2•C F , 2•C F17, 2•C10F21, 4•C F
9
•C , and 9•C 17, showing displacement ellipsoids at the 50% probability level.
4
F
7
8
F
Based on the evidence above, a reaction
mechanism was proposed, as shown in
Figure 1(b). First, Co(I) was generated from
Co(II) by controlledꢀpotential electrolysis at –
Hydrogen atoms have been omitted for clarity. (b) Expected catalytic cycles of
electrolysis for radical fluoroalkylation of aromatic compounds mediated by 1. (c)
Chemical structure of 1.
reaction was applicable to a broad range of fluoroalkylating
0
f
.8 V vs. Ag/AgCl and Co(I) quickly reacted with R I to form
reagents (R
f
I) and aromatic substrates. The results for
the Co(III)–R
f
complex. The complex then released an R
f
f
trifluoromethylation and perfluoroalkylation of 1,3,5ꢀ
radical under visible light irradiation. Finally, the generated R
trimethoxybenzene
(
2
), 1,4ꢀdimethoxybenzene
), 1,2ꢀdimethoxybenzene
), 1,3,5ꢀtrimethylbenzene (
), and 1,2ꢀdimethylindole ( ) using this
(
3
), 1,2,4ꢀ
), 1,2ꢀ
),
radical reacted with nonꢀactivated substrates, such as arenes
trimethoxybenzene
(
4
(5
and heteroarenes, followed by a oneꢀelectron oxidation and
dimethoxyꢀ4ꢀmethylbenzene (
6
7
10e
proton loss to give the desired product.
Although
1ꢀphenylpyrrole (
8
9
trifluoromethylꢀ and fluoroalkylꢀcobalamines have been
catalytic reaction are summarized in Table 2. Some major
products were identified by single crystal Xꢀray structure
analyses (Figure 1(a)). For example, trifluoromethylation and
11
synthesized and characterized by Geremia et al, this is the
first
perfluoroalkylation reactions using vitamin B12 derivatives.
In summary, we have developed straightforward
methodology to demonstrate the radical trifluoromethylation
and perfluoroalkylation of aromatic compounds using as a
report
of
catalytic
trifluoromethylation
and
perfluoroalkylation of 1,3,5ꢀtrimethoxybenzene
(
2
)
with
a
[
10d]
DMSOꢀCF
3
I
3 7 4 9 8
, n-C F I, n-C F I, n-C F17I, and n-C10F21 gave
the corresponding products in 37–84% yields. The slightly
1
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
View Article Online
DOI: 10.1039/C7CC06221D
COMMUNICATION
Journal Name
novel catalyst via an electrochemical technique. The reaction
mechanism involves homolytic cleavage of the cobalt–carbon
Hisaeda, Angew. Chem. Int. Ed., 2015, 54, 15439; (d) H.
Shimakoshi, Y. Hisaeda, ChemPlusChem, 2014, 79, 1250.
(a) K. Müller, C. Faeh, F. Diederich, Science, 2007, 317, 1881;
6
(
Co–R
to proceed under inert conditions. The use of simple and
costꢀeffective fluoroalkylating reagents (R I) is advantageous.
Moreover, as is a naturallyꢀderived cobalt catalyst, these
f f
) bond and generation of an R radical for the reaction
(
b) W. K. Hagmann, J. Med. Chem., 2008, 51, 4359; c) K. L.
Kirk, Org. Process Res. Dev., 2008, 12, 305; (d) S. Purser, P. R.
Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev., 2008,
37, 320; (e) O. A. Tomashenko, V. V. Grushin, Chem. Rev.,
f
1
2
011, 111, 4475; (f) Y. Zhou, J. Wang, Z. Gu, S. Wang, W. Zhu,
J. L. Aceña, V. A. Soloshonok, K. Izawa, H. Liu, Chem. Rev.,
016, 116, 422.
reaction systems avoid the use of expensive and toxic metal
catalysts. A relatively high TON (over 100) was observed due
to the inherent high stability of the vitamin B12 framework.
2
7
8
(a) J.-A. Ma, D. Cahard, Chem. Rev., 2004, 104, 6119; (b) T.
Furuya, A. S. Kamlet, T. Ritter, Nature, 2011, 473, 470; (c) A.
Studer, Angew. Chem. Int. Ed., 2012, 51, 8950; (d) C. Alonso,
E. M. d. Marigorta, G. Rubiales, F. Palacios, Chem. Rev., 2015,
Moreover, the discovery of
a
radical perfluoroalkylation
) bond is an
reaction mediated by a cobalt–carbon (Co–R
f
important development in organometallic chemistry because
common perfluoroalkyl organometallic species, such as
1
15, 1847.
Examples of palladium-catalyzed reactions: (a) X. Wang, L.
Truesdale, J.-Q. Yu, J. Am. Chem. Soc., 2010, 132, 3648; (b) E.
J. Cho, T. D. Senecal, T. Kinzel, Y. Zhang, D. A. Watson, S. L.
Buchwald, Science, 2010, 328, 1679; (c) X. Mu, S. Chen, X.
Zhen, G. Liu, Chem. Eur. J., 2011, 17, 6039; (d) R. N. Loy, M. S.
Sanford, Org. Lett., 2011, 13, 2548; (e) K. Natte, R. V.
Jagadeesh, L. He, J. Rabeah, J. Chen, C. Taeschler, S. Ellinger,
F. Zaragoza, H. Neumann, A. Brückner, M. Beller, Angew.
Chem. Int. Ed., 2016, 55, 2782.
Examples of copper-mediated reactions: (a) M. Oishi, H.
Kondo, H. Amii, Chem. Commun., 2009, 1909; (b) R. Shimizu,
H. Egami, T. Nagi, J. Chae, Y. Hamashima, M. Sodeoka,
Tetrahedron Lett., 2010, 51, 5947; (c) T. Knauber, F. Arikan,
lithium–carbon (R
f f
ꢀLi) and magnesium–carbon (R –Mg)
species, are unstable at room temperature and decompose
1
2
via
αꢀ or βꢀelimination of the fluoride anion. Based on these
preliminary results, we are currently investigating the
difluoromethylation,
perfluoroalkylation
trifluoromethylation
and
of
aromatic and heteroaromatic
compounds based on other cobaltꢀmediated catalytic
reactions.
9
This work was supported by JST PRESTO Grant Number
JPMJPR1414 and JSPS KAKENHI Grant Numbers JP16H04119
(
Grant-in-Aid for Scientific Research (B) for Y. H.), JP16H01035
Precisely Designed Catalysts with Customized Scaffolding for
G.-V. Röschenthaler, L. J. Gooßen, Chem. Eur. J., 2011, 17
,
(
2689; (d) J. Xu, D.-F. Luo, B. Xiao, Z.-J. Liu, T.-J. Gong, Y. Fu, L.
Liu, Chem. Commun., 2011, 47, 4300; (e) N. D. Litvinas, P. S.
Fier, J. F. Hartwig, Angew. Chem. Int. Ed., 2012, 51, 536; (f) T.
Liu, Q. Shen, Org. Lett., 2011, 13, 2342; (g) Y. Ye, M. S.
Sanford, J. Am. Chem. Soc., 2012, 134, 9034; (h) Y. Li, L. Wu,
H. Neumann, M. Beller, Chem. Commun., 2013, 49, 2628; (i)
Y. H.), JP17H04875 (Grant-in-Aid for Young Scientists (A) for T.
O.), and JP17H05161 (π-System Figuration for T. O.). We thank
3
TOSOH F-TECH INC. for the gift of CF I.
M. Chen, S. L. Buchwald, Angew. Chem. Int. Ed., 2013, 52
11628; (j) S. Cai, C. Chen, Z. Sun, C. Xi, Chem. Commun.,
013, 49, 4552; (k) Z. Gonda, S. Kovács, C. Wéber, T. Gáti, A.
Mészáros, A. Kotschy, Z. Novák, Org. Lett., 2014, 16, 4268.
0 (a) D. A. Nagib, D.W. C. MacMillan, Nature, 2011, 480, 224;
,
Notes and references
2
1
2
(a) Vitamin B12 and B -Protein, ed. B. Kräutler, D. Arigoni, B.
12
T. Golding, Wiley-VCH, Weinheim, 1998; (b) Chemistry and
Biochemistry of B , ed. R. Banerjee, Wiley-Interscience, New
1
1
2
(
b) Y. Ji, T. Brueckl, R. D. Baxter, Y. Fujiwara, I. B. Seiple, S. Su,
D. G. Blackmond, P. S. Baran, Proc. Natl. Acad. Sci. USA,
011, 108, 14411; (c) A. G. O’ Brien, A. Maruyama, Y.
York, 1999; (c) R. Banerjee, S. W. Ragsdale, Annu. Rev.
Biochem., 2003, 72, 209; (d) T. Toraya, Chem. Rev., 2003,
2
103, 2095; (e) K. L. Brown, Chem. Rev., 2005, 105, 2075; (f) G.
Inokuma, M. Fujita, P. S. Baran, D. G. Blackmond, Angew.
Chem. Int. Ed., 2014, 53, 11868; (d) F. Sladojevich, E. McNeill,
J. Börgel, S.-L. Zheng, T. Ritter, Angew. Chem. Int. Ed., 2015,
54, 3712; (e) L. Cui, Y. Matusaki, N. Tada, T. Miura, B. Uno, A.
Itoh, Adv. Synth. Catal., 2013, 355, 2203; (f) H. Sawada, M.
Nakayama, J. Fluorine Chem., 1990, 46, 423; (g) B. H.
N. Schrauzer, E. Deutsch, J. Am. Chem. Soc., 1969, 91, 3341.
(a) C. J. Gantzer, L. P. Wackett, Environ. Sci. Technol., 1991,
25,
715; (b) T. Darbre, R. Keese, V. Siljegovic,
Chem.Commun., 1996, 1561; (c) D.-L. Zhou, C. K. Njue, J. F.
Rusling, J. Am. Chem. Soc., 1999, 121, 2909; (d) F. Sunand, T.
Darbre, Org. Biomol. Chem., 2003,
McGinley, H. A. Relyea, W. A. van der Donk, Synlett, 2006,
11; (f) H. V. Motwani, S. Qiu, B. T. Golding, H. Kylin, M.
1, 3154; (e) C. M.
Langlois, E. Laurent, N. Roidot, Tetrahedron Lett., 1991, 32
525; (h) T. Kino, Y. Nagase, Y. Ohtsuka, K. Yamamoto, D.
Uraguchi, K. Tokuhisa, T. Yamakawa, J. Fluorine Chem., 2010,
31, 98; (i) L. He, K. Natte, J. Rabeah, C. Taeschler, H.
Neumann, A. Brückner, M. Beller, Angew. Chem. Int. Ed.
015, 54, 4320.
,
7
2
Törnqvist, Food Chem. Toxicol., 2011, 49, 750; g) Y. Hisaeda,
H. Shimakoshi, in Handbook of Porphyrin Science, ed. K. M.
Kadish, K. M. Smith, R. Guilard, World Scientific, 2010, vol.
1
2
10, pp. 313–370.
1
1
1 L. Randaccio, G. Brancatelli, N. Demitri, R. Dreos, N. Hickey,
P. Siega, S. Geremia, Inorg. Chem., 2013, 52, 13392.
2 (a) X. Wang, K. Hirano, D. Kurauchi, H. Kato, N. Toriumi, R.
Takita, M. Uchiyama, Chem. Eur. J., 2015, 21, 10993; (b) D. J.
Burton, Z.-Y. Yang, Tetrahedron, 1992, 48, 189.
3
See reviews: (a) M. Giedyk, K. Goliszewska, D. Gryko, Chem.
Soc. Rev., 2015, 44, 3391; (b) K. Gruber, B. Puffer, B. Kräutler,
Chem. Soc. Rev., 2011, 40, 4346; (c) W. Buckel, B. T. Golding,
Annu. Rev. Microbiol., 2006, 60, 27; (d) R. Banerjee, S. W.
Ragsdale, Annu. Rev. Biochem., 2003, 72, 209; (e) H.
Shimakoshi, Y. Hisaeda, ChemPlusChem, 2017, 82, 18.
(a) Y. Murakami, Y. Hisaeda, A. Kajihara, Bull. Chem. Soc.
Jpn., 1983, 56, 3642; (b) Y. Murakami, Y. Hisaeda, A. Kajihara,
T. Ohno, Bull. Chem. Soc. Jpn., 1984, 57, 405.
4
5
(a) H. Shimakoshi, M. Tokunaga, Y. Hisaeda, Dalton Trans.,
2004, 878; (b) H. Shimakoshi, M. Abiru, S.-i. Izumi, Y.
Hisaeda, Chem. Commun., 2009, 6427; (c) H. Shimakoshi, Y.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
Electrochemical trifluoromethylation and perfluoroalkylation of aromatic
compounds mediated by a Vitamin B derivative as a cobalt-based catalyst
1
2
has been developed.