A general and practical Ni-catalyzed C-H perfluoroalkylation of (hetero)arenes

Article abstract of DOI:10.1039/c9cc01971e

A direct perfluoroalkylation of (hetero)arenes using the air- and moisture-stable complex (dppf)Ni(o-tol)Cl was developed (23 examples). The novel procedure allows for the synthesis of various fluorinated products and tolerates sensitive functional groups including aldehydes, free amino groups and several heterocycles.

Full text of DOI:10.1039/c9cc01971e

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Rotta-Loria, F. Weniger, J. Rabeah, H. Neumann, C. Taeschler and M. Beller, Chem. Commun., 2019, DOI:
10.1039/C9CC01971E.
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DOI: 10.1039/C9CC01971E
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A General and Practical Ni-Catalyzed C-H Perfluoroalkylation of
(Hetero)Arenes
Received 00th January 20xx,
Accepted 00th January 20xx
Shaoke Zhang,a Nicolas Rotta-Loria,b Florian Weniger,a Jabor Rabeah,a Helfried Neumann,a
Christoph Taeschler,c and Matthias Beller*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
A direct perfluoroalkylation of (hetero)arenes using the air- and perfluoroalkyl reagents, e.g. RFSO2Na and RFSO2Cl.11
moisture-stable complex (dppf)Ni(o-tol)Cl was developed (23 Particularly, the direct perfluoroalkylation of (hetero)arenes
examples). The novel procedure allows for the synthesis of various with RFI, which are commercially available, is rare. Notably,
fluorinated products and tolerates sensitive functional groups Fuchikami and Ojima reported in 1982 the first example of
including aldehydes, free amino groups and several heterocycles.
perfluoroalkylation of arenes with RFI.12 Unfortunately, two
equivalents Cu and RFI were needed in this case. Later on, Loy
and Sanford made this transformation catalytic by using a
Pd2dba3/BINAP system.13 In 2015, our group reported the first
heterogeneous catalytic system (Pt/C) for such reactions,
which could be recycled to some extent.14 Despite such
recycling possibilities, the search for less expensive and more
general catalysts is ongoing. In this regard, the use of non-
noble metals, e.g. Ni, Co, Fe, Cu, Mn, is particularly attractive.
Herein, we present the first general and practical Ni-catalyzed
protocol for direct C-H perfluoroalkylation of (hetero)arenes in
the presence of air-stable pre-catalysts.15 To date, this kind of
catalysis is scarcely known with very limited substrate scope.16
In our initial studies, we investigated the perfluorodecylation
of benzene. Although nickel is an abundant and inexpensive
metal, its use in catalysis is sometimes difficult due to its
sensitivity. To avoid reproducibility problems, we used specific
metallated precursors, which allow for a more controlled
formation of the potentially active nickel(0) species. As shown
in Scheme 1, five defined nickel complexes were compared
with the in situ system consisting of NiCl2·H2O and dppf as
ligand. Although the in situ generated catalyst system showed
some conversion (38%), the desired product yield was low
(10%). Instead, using the defined (dppf)NiCl2 complex gave the
desired product in 21% yield. To our delight, the metallated
((dppf)Ni(o-tol)Cl) Ni2 performed significantly better giving
88% conversion of C10F21I and 60% yield of 2. Next, related pre-
catalysts Ni3 – Ni5 which were synthesized from different
ligands were tested, but showed no activity at all. Based on
these initial tests, the influence of key-reaction parameters on
this transformation was studied. As shown in Table 1 a control
experiment without any catalyst revealed only traces (2%) of
the desired product (Table 1, entry 2), while in the presence of
5 mol% catalyst 68% and 77% yield of 2 was observed at 130
and 150 °C, respectively (Table 1, entries 3 and 4).
The introduction of fluorine atoms into a given organic
compound significantly changes its chemical and physical
properties.1 Consequently, the performance of perfluoro-
alkylated chemicals is drastically different compared to their
parent hydrocarbons.2 Owing to their distinctive
characteristics, perfluoroalkylated arenes continue to attract
the interest of researchers from life and material sciences,3
and have been used for the preparation of new
pharmaceuticals, agrochemicals, and hydrophobic materials.4
Hence, for the synthesis of this class of compounds, numerous
methods were developed including thermolysis,5 electrolysis,6
or treatment of arenes with stoichiometric reagents.7
However, all these approaches suffer from drawbacks such as
harsh reaction conditions and/or low atom efficiency. In this
respect, the recently disclosed photochemical8 and Cu-
mediated procedures9 are interesting as they proceed under
milder conditions. Despite all these achievements in the past
decades, the demand for more practical and convenient
procedures still exists. Here, transition-metal catalysis offers
interesting possibilities, as shown by the recent
perfluoroalkylation of aryl halides or aryl boronic acids.10
Obviously, C-H functionalizations of (hetero)arenes are more
desirable; however, only few reports are known using specific
a. S. Zhang, N. Rotta-Loria, F. Weniger, Dr. J. Rabeah, Dr. H. Neumann, and Prof. Dr.
M. Beller*
Leibniz-Institut für Katalyse an der Universität Rostock e.V.
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
E-mail: matthias.beller@catalysis.de
b. N. Rotta-Loria
Department of Chemistry, Dalhousie University
Halifax, Nova Scotia B3H 4R2 (Canada)
c. Dr. C. Taeschler
Lonza Ltd, Rottenstrasse 6, 3930 Visp (Switzerland)
Electronic
Supplementary
Information
(ESI)
available.
See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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regioselectivity-wise perfluoroalkylation occurredViinewgAertnicelerOanllianet
the most electron-rich position.
[Ni] (2 mol%)
Cs2CO3 (1 equiv.)
DOI: 10.1039/C9CC01971E
C10F21
C10F21
I
+
130 ºC, 16 h
Table 1. Ni-catalyzed perfluorodecylation of benzene with C10F21I.
1
2
Ni2
(0 - 5 mol%)
C10F21
Base (1 or 1.5 eq.)
Ph
Ph
Ph
Ph
C10F21
+
I
Ph
P
P
P
50 - 130 ºC, 16 h
Ph
Cl
Cl
1
2
+ NiCl2·H2O
Ni
Ni
Fe
Fe
Fe
Cl
Ph
Entr
y
Catalyst Base (equiv.)
(mol%)
Solvent[a T / °C
]
Conv.
P
P
P
Ph
Ph
Ph
Ph
(dppf)NiCl2
47% (21%)
Ph
(Yield) / %
88 (60)
9 (2)
dppf + NiCl2·H2O
38% (10%)
Ni1:
Ni2:
(dppf)Ni(o-tol)Cl
88% (60%)
1
Ni2 (2)
None
Cs2CO3 (1)
Cs2CO3 (1)
Cs2CO3 (1)
Cs2CO3 (1)
K3PO4 (1)
None
None
None
None
None
None
None
None
None
None
None
NMP
130
130
150
130
130
130
130
130
100
50
2
O
3
Ni2 (5)
Ni2 (5)
Ni2 (2)
Ni2 (2)
Ni2 (2)
Ni2 (2)
Ni2 (5)
Ni2 (5)
Ni2 (5)
Ni2 (5)
Ni2 (5)
Ni2 (5)
Ni2 (5)
Ni2 (5)
Ni2 (5)
100 (77)
100 (68)
0 (0)
O
Ph
4
Ph
O
Ph
Ph
P
5
P
P
P
Cl
Cl
Cl
6
KOAc (1)
0 (0)
Ni
Ni
Ni
O
7
CsOPv (1)
NaOtBu (1)
Cs2CO3 (1)
Cs2CO3 (1)
Cs2CO3 (1.5)
Cs2CO3 (1)
Cs2CO3 (1)
Cs2CO3 (1)
Cs2CO3 (1)
Cs2CO3 (1)
Cs2CO3 (1)
0 (0)
P
P
Ph
Ph
8
0 (0)
Ph
Ph
9
55 (36)
0 (0)
10
11
12
13
14
15
16
17
Ni3:
0 (0)
(dppe)Ni(o-tol)Cl Ni4:
Ni5:
(Xantphos)Ni(o-tol)Cl
(PAd-DalPhos)Ni(o-tol)Cl
0 (0)
0 (0)
100
100
97 (75)
99 (12)
98 (35)
57 (8)
44 (7)
0 (0)
Scheme 1. Perfluorodecylation of benzene catalyzed by different Ni
pre-catalysts. Reaction conditions: 0.2 mmol C10F21I, 0.5 mL benzene,
argon atmosphere. Yields and conversions were determined by 19F
NMR with 1,4-difluorobenzene as standard, the values within
parentheses refer to the yields while outsides refer to the conversions.
Dioxane 100
DMSO
DMF
100
100
Acetone 100
TAA 100
0 (0)
Meanwhile, experiments in the presence of different bases
(K3PO4, KOAc, CsOPv and NaOtBu) clearly showed the special
role of Cs2CO3 for the perfluoroalkylation of benzene (Table 1,
entries 5-8). Attempts to decrease the reaction temperature
showed significantly lower product yields at 100 °C (Table 1,
entry 9), while at 50 °C no reaction took place. However, using
1,5 equiv. of Cs2CO3 gave 2 in satisfying 75% already at 100 °C
(Table 1, entry 11). Apart from the base, the reaction is also
sensitive to the solvent. Although significant conversions could
be obtained using NMP, DMF, DMSO or dioxane only low
yields of the perfluorinated benzene were observed (Table 1,
entries 12-15). Here, in most cases decomposition of the
starting material was observed. In NMP and dioxane the
corresponding RFH was generated in significant amounts, too.
Interestingly, in the latter solvent an oxidative
perfluoroalkylation was observed and the resulting coupling
Reaction conditions: 0.2 mmol C10F21I, 0.5 mL benzene, argon atmosphere.
Yields and conversions were determined by 19F NMR with 1,4-
difluorobenzene as standard. [a] In the case of using solvent: 10 equiv.
benzene, 0.32 mL solvent, NMP = N-methyl-2-pyrrolidone, DMSO =
dimethyl sulfoxide, TAA = 2-methyl-2-butanol.
Comparing multi-substituted arenes, meta-substituted
benzenes performed better than ortho- and para-ones (4d –
4i). From a synthetic point of view, it is interesting that aniline
derivatives including primary anilines with free NH2-group
underwent smooth transformation to the desired products in
70–96% yields (4j – 4n). Furthermore, various heterocycles
based on pyridine (4o and 4p), pyrrole (4q), thiophene (4r),
and imidazole (4s) were all successfully perfluoroalkylated to
give the products in good to excellent yields. Finally,
naphthalene was tested and gave the 1- and 2-perfluoroalkyl
product 5-(perfluorodecyl)-2,3-dihydro-1,4-dioxine could be isomers in a ratio of 79:21 (4t). Notably, in many of the
isolated in up to 29% yield (see SI, table S1). Other tested presented examples, the perfluoroalkylation reaction occurred
solvents (acetone, TAA) proved to be even worse (Table 1, at a specific position with high selectivity. In some cases (4d,
entries 16 and 17). With the optimized reaction conditions in 4g, 4m, 4n, 4p, and 4q), the product were obtained even with
hand, the perfluoroalkylation of structurally and electronically >99% selectivity. Furthermore, the other perfluoro sources
diverse arenes and heteroarenes with C10F21I, C8F17I, C4F9I, and (CF3Br, C4F9I and C8F17I) were also applicable to our general
more importantly CF3Br was tested (Scheme 2). Various catalytic system (4u – 4w). Notably, trifluoromethylation is
substrates bearing either electron-donating or electron- also possible using the comparably inexpensive CF3Br. Thus, N-
withdrawing substituents on the aryl ring were converted to methylpyrrole gave under slightly modified conditions 72%
the corresponding products in good to excellent yields. yield of 4w. To get mechanistic insights into this novel general
Notably, some nitrile- and carbonyl-substituted arenes as well perfluoroalkylation protocol, in situ EPR measurements were
as heteroarenes provided the desired products only in low performed. In detail, a mixture of C10F21I, Cs2CO3, and the
yields (see SI). Although there is no clear trend in reactivity catalyst Ni2 was investigated in benzene at low temperature
with respect to the electronic character of the substrate,
2 | J. Name., 2012, 00, 1-3
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(100 K) and close to the reaction temperature (346 K) (see SI, experiment in the presence of 1 equiv. of TEMPO, which
View Article Online
DOI: 10.1039/C9CC01971E
Figure S1).
resulted in no product formation and the decomposition of
C10F21I. On the other hand, in the presence of 1 equiv of BHT
product formation still occurred (yield 2: 72%). Further control
experiments revealed an extensive period (about 10 h!) for the
formation of the active Ni(0) catalyst (see SI, Figure S2).
Apparently, reductive elimination in the Ni(II) complex Ni2
proceeds very slow. To shorten such long reduction period,
typical reductants (e.g. phenylboronic acid, ammonium
formate, sodium formate) were added to the reaction, which
afforded nearly full conversion and more than 40% yield of the
desired product within 2 h (see SI, Table S2). Obviously, this
opens the possibility for further improved protocols, too.
Ni2
(5 mol%)
Cs2CO3 (1.5 equiv.)
-C10F21
Ar
Ar-H
HeteroAr-H
C10F21
OMe
I
+
-C10F21
HeteroAr
80 - 130 ºC
16 - 30 h
3
4
CHO
2
C10F21
MeO
OMe
2
C10F21
C10F21
3
3
C10F21
4
4
4a [a]
100 oC; 16h
OMe
: 130 oC; 16 h
: 100 oC; 16h
4d
4c [a]
:
120 oC; 16 h
:
4b
75%
91% (2-, 3-, 4- =
39%, 17%, 44%)
86%
55% (2-, 3-, 4- =
45%, 16%, 39%)
F
2
OMe
OMe
C10F21
In order to understand the pre-formation of the catalyst in
more detail, control experiments using Ni2 with base, solvent
and perfluorinated substrate at 100 °C for 16 h were
performed (see SI, Table S3). Interestingly, among all the
tested cases, a signal change in the 31P NMR was found only in
the presence of Ni2 and C10F21I. Thus, we conclude that Ni2
can be activated in the presence of C10F21I to form the active
catalytic species; however, this needs high temperature and
long reaction time. Running the reaction of Ni2 and C10F21I on
a larger scale gave a brown powder, which unfortunately could
not structurally resolved due to its extremely low solubility.
(see SI) Nevertheless, some product of 2 was obtained from
the mixing of this brown powder and benzene at 100 °C for 16
C10F21
OMe
100 oC; 24 h
C10F21
3
MeO
4f [a]
MeO
OMe
4
4
4h [a]
C10F21
4g [a]
: 100 oC; 16h
:
:
130 oC; 16 h
:
130 oC; 17 h
4e
73% (2-, 4- =
66%, 34%)
54%
66% (3-, 4- =
27%, 73%)
73%
OMe
NH2
N
NH2
C10F21
6
2
C10F21
C10F21
3
C10F21
3
4
4
OMe
120 oC; 16h
: 100 oC; 16h
: 100 oC; 30 h
: 100 oC; 30 h
4l
4i [a]
4j
4k
:
78%
70% (2-, 4- =
27%, 73%)
95% (3-, 6- =
34%, 66%)
96% (3-, 4- =
10%, 90%)
NH2
NH2
C10F21
C10F21
MeO
N
OMe
C10F21
N
2
C10F21
h (see SI).
3
Ph
4
OMe
F
: 120 oC; 24h
4n [b]
P
130 oC; 16 h 4o [a]
4p
:
130 oC; 26 h
: 130 oC; 16 h
96%
4m
:
Cl
Ph
74%
73%
60% (2-, 3-, 4- =
44%, 9%, 47%)
NiII
Fe
Ph
1
P
S
N
2
N
C10F21
Ph
2
5
C10F21
C10F21
N
Ni2
C10F21
4
4q [a]
4s [a]
:
130 oC; 17 h
: 120 oC; 16h
4t [a]
130 oC; 26 h
:
80 oC; 16 h
4r
:
Step 1,
Cl
86%
55%
61% (2-, 4-, 5- =
37%, 28%, 35%)
50% (1-, 2- =
79%, 21%)
reductive
elimination
C10F21
I
C8F17
C4F9
N
CF3
Step 2,
oxidative
addition
4u [a]
4v [a]
4w [a, c]
:
120 oC; 16 h
:
120 oC; 22 h
:
100 oC; 16 h
Ph
Ph
76%
50%
72%
P
P
I
Scheme 2. Substrate scope of Ni-catalyzed perfluoroalkylation with of
(hetero)arenes. Reaction conditions: 0.2 mmol C10F21I, 0.5 mL
(hetero)arenes (2 mmol for solid substrates), argon atmosphere.
Ph
Ph
Ni0 solv.
NiII
Fe
Fe
Ph
Ph
C10F21
P
P
Ph
Ph
1
Isolated yields, selectivity for different isomers was determined by H
Step 3,
reductive
elimination
A
and 19F NMR of the isolated product. [a] Yields determined by 19F NMR
with 1,4-difluorobenzene as standard. [b] 10 mol% Ni2. [c] 0.5 mmol
N-methylpyrrole, 5 bar CF3Br, 40 bar N2, 10 mol% phenylboronic acid
as additive, 1 mL perfluorobenzene, yield was determined respect to
N-methylpyrrole with the average of two runs.
C10F21
H
HI Base
+
+
Base
Scheme 3. Activation of pre-catalyst and mechanistic proposal.
In agreement with previous observations,14 an organic radical
and a decrease of the signal intensity (as a function of time)
were detected which confirmed the participation of organic
radicals in this reaction. However, there is no signal split in the
obtained EPR spectrum, so it was not possible to resolve the
exact structure of the observed radical. The occurrence of
Based on the obtained results and former reports on related
Ni- and Pd-complexes,17 we propose the following catalytic
cycle (Scheme 3). Initially, Ni2 undergoes reductive elimination
to afford the corresponding Ni(0) intermediate A. Typically,
this step is rate determining. A is highly active and may be
stabilized by iodide ions. After oxidative addition with the
perfluoroalkyl iodide and subsequent activation of the
radical intermediates was further proven by
a typical
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and E. Magnier, Eur. J. Org. Chem., 2012, 2012, 2479-2494; (c) S.
(hetero)arene, the desired perfluoroalkylated product is
obtained. At this point, we do not know how the latter
reaction steps proceed and the involvement of radical
intermediates vide supra is likely.
View Article Online
Purser, P. R. Moore, S. Swallow and V. Gouverneur, Chem. Soc.
Rev., 2008, 37, 320-330; (d) K. L. Kirk, J. DFOluIo: 1r0in.1e03C9h/Ce9mC.C, 021090716E,
127, 1013-1029.
5. (a) L. K. San, E. V. Bukovsky, I. V. Kuvychko, A. A. Popov, S. H.
Strauss and O. V. Boltalina, Chem. Eur. J., 2014, 20, 4373-4379;
(b) A. B. Cowell and C. Tamborski, J. Fluorine Chem., 1981, 17,
345-356.
6. M. Médebielle, S. Fujii and K. Kato, Tetrahedron, 2000, 56,
2655-2664.
7. (a) T. Shirai, M. Kanai and Y. Kuninobu, Org. Lett., 2018, 20,
1593-1596; (b) D. Leifert, D. G. Artiukhin, J. Neugebauer, A.
Galstyan, C. A. Strassert and A. Studer, Chem. Commun., 2016,
52, 5997-6000; (c) T. Kino, Y. Nagase, Y. Ohtsuka, K. Yamamoto,
D. Uraguchi, K. Tokuhisa and T. Yamakawa, J. Fluorine Chem.,
2010, 131, 98-105; (d) X.-T. Huang, Z.-Y. Long and Q.-Y. Chen, J.
Fluorine Chem., 2001, 111, 107-113; (e) B.-N. Huang and J.-T. Liu,
J. Fluorine Chem., 1993, 64, 37-46.
In conclusion, we have developed a general and practical Ni-
catalyzed perfluoroalkylation of (hetero)arenes using the
defined Ni-complex Ni2. This kind of catalyst is air- and
moisture-stable and thus can be easily handled. The reported
protocol allows the effective perfluoroalkylation of various
(hetero)arenes in moderate to good yields. Control
experiments revealed the importance of the activation of the
pre-catalyst as rate determining step. We believe these studies
will be also of interest for related Ni-catalyzed coupling
processes.
8. (a) Y. Ouyang, X. H. Xu and F. L. Qing, Angew. Chem. Int. Ed.
Engl., 2018, 57, 6926-6929; (b) E. Torti, S. Protti and M. Fagnoni,
Chem. Commun., 2018, 54, 4144-4147; (c) Y. Wang, J. Wang, G.
X. Li, G. He and G. Chen, Org. Lett., 2017, 19, 1442-1445; (d) J.
W. Beatty, J. J. Douglas, R. Miller, R. C. McAtee, K. P. Cole and C.
R. J. Stephenson, Chem, 2016, 1, 456-472; (e) M. Nappi, G.
Bergonzini and P. Melchiorre, Angew. Chem. Int. Ed., 2014, 53,
4921-4925; (f) N. J. Straathof, H. P. Gemoets, X. Wang, J. C.
Schouten, V. Hessel and T. Noel, ChemSusChem, 2014, 7, 1612-
1617; (g) L. Cui, Y. Matusaki, N. Tada, T. Miura, B. Uno and A.
Itoh, Adv. Synth. Catal., 2013, 355, 2203-2207; (h) M. Neumann,
S. Fuldner, B. König and K. Zeitler, Angew. Chem. Int. Ed., 2011,
50, 951-954.
We are grateful for financial support from Lonza, Switzerland,
BMBF and the State of Mecklenburg-Western Pommerania,
Germany. S.Z. thanks the Chinese Scholarship Council, China.
Keywords: Nickel
•
catalysis
•
perfluoroalkylation
•
(hetero)arenes • fluorinated compounds
Conflicts of interest
There are no conflicts to declare.
9. (a) C. P. Zhang, Z. L. Wang, Q. Y. Chen, C. T. Zhang, Y. C. Gu
and J. C. Xiao, Angew. Chem. Int. Ed., 2011, 50, 1896-1900; (b) L.
Chu and F.-L. Qing, Org. Lett., 2010, 12, 5060-5063; (c) G. G.
Dubinina, H. Furutachi and D. A. Vicic, J. Am. Chem. Soc., 2008,
130, 8600-8601; (d) J. Leroy, M. Rubinstein and C. Wakselman, J.
Fluorine Chem., 1985, 27, 291-298.
10. (a) X. Bao, L. Liu, J. Li and S. Fan, J. Org. Chem., 2018, 83, 463-
468; (b) S. Zhang, H. Neumann and M. Beller, Chem. Eur. J.,
2018, 24, 67-70; (c) K. Aikawa, Y. Nakamura, Y. Yokota, W. Toya
and K. Mikami, Chem. Eur. J., 2015, 21, 96-100; (d) T. Knauber, F.
Arikan, G. V. Röschenthaler and L. J. Goossen, Chem. Eur. J.,
2011, 17, 2689-2697; (e) K. A. McReynolds, R. S. Lewis, L. K. G.
Ackerman, G. G. Dubinina, W. W. Brennessel and D. A. Vicic, J.
Fluorine Chem., 2010, 131, 1108-1112; (f) M. Oishi, H. Kondo and
H. Amii, Chem. Commun., 2009, 1909-1911.
Notes and references
1. (a) Y. Zhu, J. Han, J. Wang, N. Shibata, M. Sodeoka, V. A.
Soloshonok, J. A. S. Coelho and F. D. Toste, Chem. Rev., 2018,
118, 3887-3964; (b) S. Barata-Vallejo, M. V. Cooke and A.
Postigo, ACS Catal., 2018, 8, 7287-7307; (c) C. Ni and J. Hu,
Chem. Soc. Rev., 2016, 45, 5441-5454; (d) H. Egami and M.
Sodeoka, Angew. Chem. Int. Ed., 2014, 53, 8294-8308; (e) V.
Bizet, R. Kowalczyk and C. Bolm, Chem. Soc. Rev., 2014, 43,
2426-2438; (f) T. Liang, C. N. Neumann and T. Ritter, Angew.
Chem. Int. Ed. Engl., 2013, 52, 8214-8264; (g) G. S. Prakash and
A. K. Yudin, Chem. Rev., 1997, 97, 757-786.
2. M. Yoshida, N. Kamigata, H. Sawada and M. Nakayama, J.
Fluorine Chem., 1990, 49, 1-20.
11. (a) L. Chu and F. L. Qing, J. Am. Chem. Soc., 2012, 134, 1298-
1304; (b) I. Popov, S. Lindeman and O. Daugulis, J. Am. Chem.
Soc., 2011, 133, 9286-9289; (c) W.-Y. Huang, J.-T. Liu and J. Li, J.
Fluorine Chem., 1995, 71, 51-54; (d) N. Kamigata, T. Ohtsuka, T.
Fukushima, M. Yoshida and T. Shimizu, J. Chem. Soc., Perkin
Trans. 1, 1994, 1339-1346.
12. T. Fuchikami and I. Ojima, J. Fluorine Chem., 1983, 22, 541-
556.
13. R. N. Loy and M. S. Sanford, Org. Lett., 2011, 13, 2548-2551.
14. L. He, K. Natte, J. Rabeah, C. Taeschler, H. Neumann, A.
Brückner and M. Beller, Angew. Chem. Int. Ed., 2015, 54, 4320-
4324.
15. (a) D. D. Beattie, T. Schareina and M. Beller, Org. Biomol.
Chem., 2017, 15, 4291-4294; (b) E. A. Standley and T. F. Jamison,
J. Am. Chem. Soc., 2013, 135, 1585-1592.
16. Q.-L. Zhou and Y.-Z. Huang, J. Fluorine Chem., 1988, 39, 87-
98.
17. (a) Y. Ye, N. D. Ball, J. W. Kampf and M. S. Sanford, J. Am.
Chem. Soc., 2010, 132, 14682-14687; (b) G. G. Dubinina, W. W.
Brennessel, J. L. Miller and D. A. Vicic, Organomet., 2008, 27,
3933-3938; (c) V. V. Grushin and W. J. Marshall, J. Am. Chem.
Soc., 2006, 128, 12644-12645.
3. (a) S. Barata-Vallejo, S. M. Bonesi and A. Postigo, RSC Adv.,
2015, 5, 62498-62518; (b) T. Bříza, V. Král, P. Martásek and R.
Kaplánek, J. Fluorine Chem., 2008, 129, 235-247; (c) T.
Umemoto, J. Fluorine Chem., 2000, 105, 211-213; (d) V.
Krishnamurti, S. B. Munoz, X. Ispizua-Rodriguez, J. Vickerman, T.
Mathew and G. S. Prakash, Chem. Commun., 2018, 54, 10574-
10577; (e) J. A. Pike and J. W. Walton, Chem. Commun., 2017,
53, 9858-9861; (f) X. Fang, P. Yu and B. Morandi, Science, 2016,
351, 832-836; (g) 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-
2786; (h) J. Xie, T. Zhang, F. Chen, N. Mehrkens, F. Rominger, M.
Rudolph and A. S. K. Hashmi, Angew. Chem. Int. Ed., 2016, 55,
2934-2938; (i) Y. Kuninobu, M. Nagase and M. Kanai, Angew.
Chem. Int. Ed., 2015, 54, 10263-10266; (j) F. Sladojevich, E.
McNeill, J. Borgel, S. L. Zheng and T. Ritter, Angew. Chem. Int.
Ed., 2015, 54, 3712-3716; (k) N. D. Litvinas, P. S. Fier and J. F.
Hartwig, Angew. Chem. Int. Ed., 2012, 51, 536-539; (l) E. J. Cho,
T. D. Senecal, T. Kinzel, Y. Zhang, D. A. Watson and S. L.
Buchwald, Science, 2010, 328, 1679-1681.
4. (a) N. V. Kirij, A. A. Filatov, G. Y. Khrapach and Y. L.
Yagupolskii, Chem. Commun., 2017, 53, 2146-2149; (b) Y. Macé
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