Nickel-Catalyzed Cross-Electrophile Coupling between C(sp2)-F and C(sp2)-Cl Bonds by the Reaction of ortho-Fluoro-Aromatic Amides with Aryl Chlorides

Article abstract of DOI:10.1021/acscatal.1c01102

Ni-catalyzed cross-electrophile coupling between C(sp2)-F bonds in ortho-fluoro-substituted aromatic amides and C(sp2)-Cl bonds in aryl chlorides in the presence of Zn as a reductant and LiOtBu as a base, and LiCl and ZnCl2 as additives is reported. The reaction displayed excellent functional group tolerance and a broad substrate scope. The reaction was also applicable to cross-electrophile coupling between C(sp2)-F and C(sp2)-O bonds in an aryl tosylate and a triflate derivative.

Full text of DOI:10.1021/acscatal.1c01102

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Letter
Nickel-Catalyzed Cross-Electrophile Coupling between C(sp2)−F and
C(sp2)−Cl Bonds by the Reaction of ortho-Fluoro-Aromatic Amides
with Aryl Chlorides
Itsuki Nohira and Naoto Chatani*
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ABSTRACT: Ni-catalyzed cross-electrophile coupling between C(sp2)−
F bonds in ortho-fluoro-substituted aromatic amides and C(sp2)−Cl
bonds in aryl chlorides in the presence of Zn as a reductant and LiOtBu as
a base, and LiCl and ZnCl2 as additives is reported. The reaction displayed
excellent functional group tolerance and a broad substrate scope. The
reaction was also applicable to cross-electrophile coupling between C(sp2)−F and C(sp2)−O bonds in an aryl tosylate and a triflate
derivative.
KEYWORDS: cross-electrophile coupling, C−F activation, C−O activation, nickel, arylation
Scheme 1. Cross-Electrophile Coupling to Form C(aryl)-
C(aryl) Bonds
ross-electrophile coupling in which two different carbon
Celectrophiles are coupled under reductive conditions has
been recognized as a viable alternative to conventional cross-
coupling reactions between nucleophiles and electrophiles, and
has provided a powerful tool for forming C−C bonds.1 In fact,
this type of transformations has been extensively studied over
the past few decades. A wide variety of combinations of two
electrophiles has been employed in the cross-electrophile
coupling reactions that have been reported thus far. In
comparison with cross-electrophile coupling to form C(sp2)-
C(sp3), C(sp2)-C(sp), or C(sp3)-C(sp3) bonds, the corre-
sponding C(sp2)-C(sp2) bond formation is more challenging
because the reactivity of the two C(sp2)-electrophiles is similar.
Thus, both electrophiles can compete for oxidative addition to
the catalyst. To achieve selective cross-electrophile coupling
and to avoid the formation of homocoupling products, the use
of two electrophiles that have electronically and/or sterically
different reactivities,2 the use of an excess amount of a less
reactive coupling partner,3 or utilizing different activation
modes for each electrophile are typically employed.4 In 2015,
Weix reported a new strategy using a Ni/Pd dual catalytic
system for cross-electrophile coupling between aryl bromides
and aryl triflates. In this reaction, aryl bromides selectively
oxidatively added to the Ni catalyst and aryl triflates oxidatively
add to the Pd catalyst selectively (Scheme 1).5 Since then, dual
catalytic systems have been used in cross-electrophile coupling
reactions between aryl tosylates/aryl triflates6a,b and aryl
chloride/aryl triflates.6c Another strategy for achieving selective
cross-coupling involves the use of chelation assistance. Zeng
recently reported the Cr-catalyzed cross-electrophile coupling
between C(sp2)-OMe and C(sp2)-O2CR, in which C(sp2)-
OMe is selectively activated by utilizing chelation assistance.7a
This system was also extended to cross-electrophile coupling
between C(sp2)-NMe2 and C(sp2)-O2CR structures.7b Ruep-
ing recently reported the Ni-catalyzed cross-electrophile
coupling between C(sp2)-F bond and C(sp2)-Br bonds
under irradiation conditions.8 Chu also reported on similar
Received: March 10, 2021
Revised: March 25, 2021
Published: April 2, 2021
https://doi.org/10.1021/acscatal.1c01102
© 2021 American Chemical Society
ACS Catal. 2021, 11, 4644−4649
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Letter
transformation using a Pd catalyst under visible light
conditions.9 However, these reactions were limited to only
perfluoroaromatic compounds, which are highly reactive,
electron-deficient substrates. Cross-electrophile coupling be-
tween C(sp2)-F and C(sp2)-Cl bonds continues to pose a
challenge because both bonds are known to undergo oxidative
addition to the Ni(0) center.10 A new system for the selective
activation of each bonds is clearly required if more progress is
to be made in this area.
Table 1. Optimization of the Reaction Conditions
We recently reported the Ni-catalyzed reaction of 2-
fluorobenzamides with alkynes using a base-promoted strategy,
in which a C−F bond at the ortho-position is selectively
activated under both mild reaction and ligand-free con-
ditions.11 We hypothesized that this strategy could be used
in cross-electrophile coupling between C(sp2)-F and C(sp2)-X
(X= halogens or O) bonds and, in fact, this has been realized.
We wish to report herein on a new strategy for the Ni-
catalyzed cross-electrophile coupling between C(sp2)-F and
C(sp2)-Cl bonds (Scheme 2).12
NMR yields (%)
entry
variations from above conditions
3aa
4a
a
a
1
2
3
4
5
6
7
8
none
without LiOtBu
without LiCl
without ZnCl2
entry 4, Mn instead of Zn
without dtbbpy
bpy instead of dtbbpy
PPh3 instead of dtbbpy
NaH instead of LiOtBu
Ar′−I instead of Ar′−Cl
Ar′−Br instead of Ar′−Cl
90 (88)
55
8 (4)
42
26
28
24
3
51
60
38
trace
73
Scheme 2. Cross-Electrophile Coupling between C(sp2)-F
and C(sp2)-Cl bonds
20
8
15
71
10
27
9
10
11
23
62
60
a
Isolated yields are given in parentheses.
Scheme 3. Scope of N-Substituents on Aromatic Amides
The reaction of 2-fluoro-N-(4-methoxyphenyl)benzamide
(1a) with 2 equiv of 4-tolyl chloride (2a) in the presence of
NiCl2 (10 mol %) and 4,4′-di-tert-butyl-2,2′-dipyridine
(dtbbpy) (12 mol %), LiOtBu (1 equiv), Zn (3 equiv),
ZnCl2 (30 mol %) and LiCl (2 equiv) in DMA (N,N-
dimethylacetamide) at 80 °C for 14 h gave the N-(4-
methoxyphenyl)-4′-methyl-[1,1′-biphenyl]-2-carboxamide
(3aa) in 90% NMR yield, along with the protodefluorinated
product 4a in 8% and a trace amount of the homocoupling
product 5a as byproducts (entry 1 in Table 1) . Control
experiments showed that the reaction parameters, such as
LiOtBu, LiCl, and ZnCl2 were all needed for an efficient
reaction to take place (entry 1 vs entries 2−4). If any one of
these components are lacking, the product yield was decreased.
It was found that Zn is superior than Mn as a reductant (entry
5). The use of dtbbpy or bpy (2,2′-bipyridine) as a ligand is
essential for the success of the reaction (entries 6−8). NaH
also functioned as a base in place of LiOtBu (entry 9). The
reaction with 4-tolyl iodide and bromide in place of 2a resulted
in protodefluorination to give 4a as the main product (entries
10 and 11).
The scope of the N-substituent on the amide nitrogen was
examined using 4-methoxyphenyl chloride (2b) as a coupling
partner under the optimized conditions (Scheme 3). While
both electron-donating (OMe) 1a and electron-withdrawing
(CF3) groups 1c gave the corresponding arylated products, 1c
gave the expected product 3cb in a slightly lower yield. The
use of N-alkyl groups, such as benzyl, hexyl, and tert-butyl
groups also gave the corresponding products, 3db, 3eb, and
3fb. In sharp contrast, the reaction of N,N-diethyl-2-
fluorobenzamide, which contains no proton on the amide
nitrogen did not give the expected product 3gb, indicating that
the presence of an NH proton is crucial for the reaction to
proceed.
The scope of this cross-electrophile coupling was also
investigated, with respect to 2-fluoro-N-(4-methoxyphenyl)-
benzamide derivatives (top-left in Scheme 4). A variety of
important functional groups were tolerated in the reaction.
Remarkably, no arylation at C−OMe and C−OPiv bonds in
the substrates was detected, which are known to undergo the
oxidative addition to a Ni(0) center,13 as in 3hb, 3mb, and
3ob. In all cases, the arylation occurred exclusively at the ortho
C−F bond. Even when substrates containing another C−F
bond were used, only the ortho C−F bonds were selectively
arylated, as in 3kb and 3pb.10 The reaction was not
significantly affected by steric environments, as in 3ob and
3pb. The scope of aryl chlorides was also examined (top-right
in Scheme 4). Various functional groups, which could be used
for further transformations, such as alkene, phosphonate,
acetal, and boronic esters were tolerated in the reaction, as in
3ad, 3ae, 3af, and 3ah. 5-Chloroindole and 2-chloronaph-
thalene also participated in the reaction to give 3al and 3qn,
respectively. The use of 1-chloro-2-fluorobenzene (3b) as a
coupling partner under the standard reaction conditions gave
the phenanthridin-6(5H)-one derivative 6a in 63% yield,
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Letter
a
Scheme 4. Scope of Amides and Aryl Electrophiles
a
Reaction conditions: amide 1 (0.25 mmol), aryl chloride 2 (0.5 mmol), NiCl2 (0.025 mmol), dtbbpy (0.03 mmol), LiOtBu (0.25 mmol), Zn (0.75
b
c
mol), LiCl (0.5 mmol), ZnCl2 (0.075 mmol), and DMA (0.5 mL) at 80 °C for 14 h. Ar = 4-MeOC6H4. dtbbpy (0.005 mmol). At 100 °C.
which appears to form as a result of further intramolecular
SNAr reaction of the initial product 3ao (bottom-left in
Scheme 4). In fact, the reaction of 3ao in the presence of a
base in the absence of Ni catalyst in DMA at 80 °C gave 6a in
quantitative yield. The reaction with 2-fluoro-4-methoxy-1-
chlorobenzene and 2,4-difluoro-1-chlorobenzene also gave the
corresponding products 6b and 6c in good yields. While the
use of 4-tolyl iodide and bromide in place of 4-tolyl chloride
(2a) gave the protodefluorinated product 4a as the major
product (entries 10 and 11 in Table 1), gratifyingly the present
reaction was found to be applicable to 4-tolyl tosylate and
triflate reactants to afford good yields of 3aa, even under
unoptimized reaction conditions (bottom-right in Scheme 4).
To shed additional light on the mechanism, some
mechanistic experiments were conducted (Scheme 5). We
were able to isolate a single crystalline sample of the expected
azanickelacycle 7 by the reaction of 1a with equimolar
amounts of Ni(cod)2, bpy, and NaH in THF at 80 °C and
the structure of 7 was confirmed by an X-ray crystallographic
analysis (Scheme 5a). The use of dtbbpy as the ligand in place
of bpy also gave a similar complex (8), the structure of which
Scheme 5. Mechanistic Studies
1
was confirmed by H NMR (see the SI for details). We used
complex 8 in further mechanistic studies, because of its good
solubility in organic solvents. The reaction of 1a under the
standard reaction conditions, using 8 as the catalyst, gave 3aa
in 68% yield (Scheme 5b). The stoichiometric reaction of 8
with 2a in the presence Zn and LiCl in DMA at 80 °C gave 3aa
in 82% NMR yield, along with 4a and the dimerization product
5a (Scheme 5c). The reaction of 8 with PhZnCl also gave 3ac
in 87% NMR yield, suggesting that an arylzinc species is
generated under the reaction conditions employed and
functions as a nucleophile in the catalytic reaction.14
As shown in Table 1, the addition of ZnCl2 (30 mol %) gave
a higher product yield. To gain further insights regarding the
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Letter
Scheme 6. Proposed Mechanism
effect of ZnCl2, the time dependence study was conducted (see
the Supporting Information (SI) for details). As a result, it was
found that there is an induction period for the reaction. When
the reaction was performed in the absence of ZnCl2, no
reaction occurred during the first 2 h, after which the reaction
was initiated. On the other hand, the induction period was
decreased to 30 min when 30 mol % of ZnCl2 was added.
These results suggest that ZnCl2 accelerates the generation of
ArZnCl (discussed below).
An alternative mechanism involves the one-electron
reduction of complex C with Zn and LiCl to give the Ni(I)-
nickelacycle F, followed by the oxidative addition of ArCl to
give G, which then undergoes reductive elimination to give H,
along with the generation of Ni(I), which is reduced by Zn to
regenerate the Ni(0) species. To examine the possibility that C
could be reduced by elemental Zn, we examined the reduction
potential of the Ni(II) complex 8 (correspond to C), which
shows −2.00 (V vs Fc+/Fc). These findings suggest that the
reduction of 8 by Zn appears to be less likely (see the SI for
details).16
In summary, we report on the first example of cross-
electrophile coupling between C(sp2)−F and C(sp2)−Cl
bonds. Although there are many reports of transformations
involving chelation-assisted C(sp2)−F bond activation, most of
the examples reported thus far have involved polyfluorinated
substrates at high reaction temperatures.10,17 In contrast, the
activation of C(sp2)−F bonds using our base-promoted
strategy proceeds efficiently, even under mild reaction
conditions. The reaction shows a high functional group
compatibility and was also applicable to cross-electrophile
coupling reactions between C(sp2)−F and C(sp2)−O bonds in
an aryl tosylate and a triflate derivative.
A mechanism for the reaction is proposed based on
experimental results, as well as literature findings, as shown
in Scheme 6. The base, LiOtBu abstracts the NH proton of the
amide 1 to generate the amidate anion A. The coordination of
A with Ni(0) gives the nickel ate complex B, which then
oxidatively adds to a C−F bond to generate the nickelacycle C
with the extraction of LiF.11a,15 The transmetalation between C
and ArZnCl gives D, which then undergoes reductive
elimination to afford E with the regeneration of Ni(0). The
protonation of E gives the final product 3. ArZnCl is formed by
the oxidative addition of ArCl to Ni(0), followed by a one-
electron reduction by Zn and transmetalation with ZnCl2
through cycles B and C.16 While ZnCl2 is gradually generated
as the reaction progress, the addition of additional ZnCl2
would be predicted to accelerate the production of ArZnCl.
The addition of LiCl also has an important role in the effective
cross-coupling by accelerating the reduction of Ni(II) to Ni(0)
(cycle B).6c Both C−F and C−Cl bonds can compete for
oxidative addition to a Ni catalyst. If cycle B is faster than cycle
A, then homocoupling of an aryl chloride occurs with the
generation of Ar−Ar becomes a major path and the yield of the
desired product 3 is low, because there is no chance for
intermediate C to react with ArZnCl. In fact, when an aryl
iodide or bromide were used in place of a chloride, protonation
product 4 was the main product, as shown in Table 1. In these
cases, the oxidative addition of an aryl iodide or bromide is
faster than the generation of intermediate C. Similarly, if cycle
A is faster than cycles B and C, the protonation of C leading to
the formation of 4 would be a dominant path because only a
small amount ArZnCl is generated via cycle B and C,
compared with the generation of intermediate C.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.1c01102.
■
sı
Experimental procedure, synthesis of starting materials,
and characterization of compounds (PDF)
Crystallographic data (CIF)
Crystallographic data (PDF)
AUTHOR INFORMATION
Corresponding Author
■
Naoto Chatani − Department of Applied Chemistry, Faculty of
Engineering, Osaka University, Suita, Osaka 565-0871,
Japan; orcid.org/0000-0001-8330-7478;
Email: chatani@chem.eng.osaka-u.ac.jp
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Author
Itsuki Nohira − Department of Applied Chemistry, Faculty of
Engineering, Osaka University, Suita, Osaka 565-0871,
Japan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.1c01102
Funding
This work was supported by a Grant in Aid for Specially
Promoted Research by MEXT (No. 17H06091).
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors wish to thank Dr. Yuma Morimoto (Osaka
University) for his assistance with the measurement of cycle
voltammograms.
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