Nickel-catalyzed cross-coupling of: O, N -chelated diarylborinates with aryl chlorides and mesylates

Article abstract of DOI:10.1039/c8nj05503c

A practical nickel catalyst system consisting of readily available components, trans-NiCl(Ph)(PPh₃)₂/[Iprmim]I/K₃PO₄·3H₂O in toluene, has been developed for efficient cross-coupling of 3-dimethylaminopropyl diarylborinates with aryl chlorides and mesylates. A small amount of water has been found to be crucial in achieving high efficiency in the system. The nickel catalyst system displayed remarkably higher activities to aryl chlorides and mesylates than the corresponding tosylates in cross-coupling with not only diarylborinates but also diarylborinic acids, arylboronic acids, anhydrides and trifluoroborates as indicated in control experiments. A variety of electronically various biaryls could be obtained in excellent yields by using 3-5 mol% loading of the nickel catalyst while sterically hindered biaryls were obtained in comparably lower yields.

Full text of DOI:10.1039/c8nj05503c

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Nickel-catalyzed cross-coupling of O,N-chelated
diarylborinates with aryl chlorides and mesylates†
Cite this: New J. Chem., 2019,
43, 1589
Chao Ren, Jingshu Zeng and Gang Zou
*
A practical nickel catalyst system consisting of readily available components, trans-NiCl(Ph)(PPh
3 2
) /
[
Iprmim]I/K PO O in toluene, has been developed for efficient cross-coupling of 3-dimethylaminopropyl
3
4
ꢀ3H
2
diarylborinates with aryl chlorides and mesylates. A small amount of water has been found to be crucial
in achieving high efficiency in the system. The nickel catalyst system displayed remarkably higher
activities to aryl chlorides and mesylates than the corresponding tosylates in cross-coupling with not
only diarylborinates but also diarylborinic acids, arylboronic acids, anhydrides and trifluoroborates as
indicated in control experiments. A variety of electronically various biaryls could be obtained in excellent
yields by using 3–5 mol% loading of the nickel catalyst while sterically hindered biaryls were obtained in
comparably lower yields.
Received 30th October 2018,
Accepted 19th December 2018
DOI: 10.1039/c8nj05503c
rsc.li/njc
light-sensitive Ni(0) precursors, most commonly Ni(cod)
2
, which
Introduction
is expensive and must be stored, handled and used under
1
6
The physiochemical properties, in particular stability and reac- rigorously light- and air-free conditions. To solve this problem,
tivities, of diarylborinates not only depend on their aryl groups air-stable, yet easily activated (Ar)NiCl(L) precatalysts supported by
but also could be finely tuned by coordination of the boron phosphine, N-heterocyclic carbene (NHC), or chelating diamine
1
7
18
19
center. As one of the most stable types of arylboron compounds, ligands have been developed by Yang, Percec, Jamison,
2
0
21
22
chelate stabilized four-coordinate diarylborinates are almost Hartwig, Buchwald, and many others and have proven to
infinitely air- and moisture-stable yet have tunable reactivities be highly active for specific reactions.
via the chelating ligands, therefore finding increasing impor-
tance in chemical, material and biological sciences. As part coupling of cost-effective substrates, we report herein a highly
To develop practical nickel catalyst systems for Suzuki
1
2
3
of our on-going research on practical synthetic methodology for efficient nickel catalyst system based on trans-NiCl(Ph)(PPh3)2
4
biaryls, we have recently reported that 3-dimethylaminopropyl and sterically unsymmetrical N-heterocyclic carbenes for Suzuki
diarylborinates featuring a six-membered O,N-chelated boron coupling of shelf-stable O,N-chelated diarylborinates with aryl
ring displayed a delicately balanced stability and reactivity via chlorides and mesylates for synthesis of biaryls.
5
the so-called through-bond interactions in palladium catalyzed
4e
Suzuki coupling of aryl chlorides. Although less popular than
palladium, homogeneous nickel catalysis has attracted increas-
ing interests, because nickel is not only more cost-effective and
Results and discussion
Coupling with aryl chlorides
6
less toxic but also has proven to be more versatile in catalyzing Initially, the cost-effective, readily available and air-stable
7
4b
Suzuki coupling of less reactive electrophiles, such as sulfonates,
NiCl (PPh ) /[Bmim]Br catalyst system, which we have estab-
2 3 2
8
9
10
11
11c,d,12
nitriles, ammonium salts, ethers, esters, amides,
lished for cross-coupling of aryl (pseudo)chlorides with diaryl-
However, the boronic acids, was used in the model reaction of 3-dimethyl-
1
3
14
11c,15
fluorides, sulfamates, and carbamates.
nickel-catalyzed Suzuki coupling is still much less used in aminopropyl diphenylborinate (1a) with 4-chloroactetophenone
practical synthesis than the palladium-catalyzed one. One of (2a) (Table 1, entry 1). The desired biaryl product 3aa was
the major causes to this disparity is the requirement of either obtained in a modest yield (73%) significantly lower than the
strong reducing conditions to activate the inexpensive Ni(II) almost quantitative yield (98%) in the control reaction of
precatalysts, e.g. nickel halide (NiX (L) ), or highly air- and the corresponding borinic acid (anhydride). The decrease in
2
2
catalysis efficiency could be partly attributed to the increased
stability of chelated diarylborinates than free borinic acids,
thus the decreased ability in activation of Ni(II) chloride pre-
catalyst. Therefore, the easily activated organonickel complex
School of Chemistry & Molecular Engineering, East China University of Science &
Technology, 130 Meilong Rd, Shanghai, China. E-mail: zougang@ecust.edu
†
Electronic supplementary information (ESI) available: Experimental procedure,
characterization data for products, and copies of NMR spectra. See DOI: 10.1039/
c8nj05503c
trans-NiCl(Ph)(PPh
3
)
2
was tested as the precatalyst and the yield
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a
Table 1 Optimization of Ni-catalyzed cross-coupling of diarylborinate 1a with aryl chloride 2a
b
Entry
Ni(II) (mol %)
NiCl (PPh (3)
L (mol %)
Base
Sol.
Yield (%)
1
2
3
4
5
6
7
8
9
2
3
)
2
[Bmim]Br (3)
[Bmim]Br (3)
[Bmim]Br (3)
—
[diBim]Br (3)
IPrꢀHCl (3)
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
K
3
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
2
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol/25% H
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
DMF
Dioxane
DMSO
73
81
19
49
84
89
76
80
89
97
90
86
86
85
83
trans-NiCl(Ph)(PPh
NiCl (3)
3
)
2
(3)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
3
3
3
3
3
3
3
3
3
3
3
3
3
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(1)
(1)
(3)
IMesꢀHCl (3)
[diOim]Br (3)
[Omim]Br (3)
[Iprmim]I (3)
[Ipreim]Br (3)
[Iprbim]Br (3)
[Mesmim]I (3)
[Iprmim]I (1)
[Iprmim]I (2)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
[Iprmim]I (3)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
c
94
trans-NiCl(o-Tol)(PPh
trans-NiCl(1-Naph)(PPh
trans-NiCl(Ph)(PCy (3)
trans-NiCl(o-Tol)(PCy (3)
trans-NiCl(o-Tol)(dppf) (3)
3
)
2
(3)
)
91
60
84
77
30
53
53
75
95
61
47
43
Trace
35
45
74
20
3
2
(3)
3
)
2
3
)
2
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
trans-NiCl(Ph)(PPh
3
3
3
3
3
3
3
3
3
3
3
3
3
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
)
2
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
2
O
+ H
+ 5H
+ 10H
2
O
2
O
2
O
NaOH
KOH
t
KO Bu
K
2
K
3
K
3
K
3
K
3
CO
3
PO
PO
PO
PO
4
4
4
4
ꢀ3H
ꢀ3H
ꢀ3H
ꢀ3H
2
2
2
2
O
O
O
O
d
CH
3
CN
13
a
b
c
d
2
Reaction conditions: 1a (0.65 mmol), 2a (1 mmol), base (2 mmol), solvent (5 mL), N , 12 h, reflux. Isolated yields. 6 h. At reflux.
of 3aa was increased to 81% (Table 1, entry 2). The in situ excellent yield (Table 1, entries 5–13). In fact, 3aa could be
generated NHC ligand also proved to be necessary since the obtained in 94% yield within half reaction time (6 h) albeit the
trans-NiCl(Ph)(PPh
9% yield (Table 1, entry 4). Screening of a variety of NHC trans-NiCl(Ph)(PPh
precursors revealed an unusual steric effect of the NHC ligand structurally various analogs of trans-NiCl(Ph)(PPh
on the catalysis efficiency, that is sterically unsymmetrical NHC to aryl and phosphine ligands showed no improvement on the
appeared to match the precursor trans-NiCl(Ph)(PPh ) better. catalytic efficiency. For example, only trans-NiCl(o-Tol)(PPh ) gave
3
)
2
in the absence of [Bmim]Br gave only yields deceased significantly to 83–85% with a lower (1 mol%)
loading (Table 1, entries 14–16). The tests of
with respect
4
3 2
)
3 2
)
3
2
3 2
For example, a remarkable increase in yields of 3aa was a comparable yield (91%) (Table 1, entry 17) while naphthyl
observed from symmetrical NHC precursors, [diBim]Br, IPrꢀHCl, complex trans-NiCl(1-Naph)(PPh
3
)
2
, tricyclohexylphosphine com-
0
IMesꢀHCl and [diOim]Br (76–89%), to unsymmetrical analogs, plexes, trans-NiCl(Ph)(PCy
)
3 2
and trans-NiCl(o-Tol)(PCy
3
)
2
and 1,1 -
[Omim]Br, [Ipreim]Br, [Iprbim]Br, [Mesmim]I and [Iprmim]I bis(diphenylphosphino) ferrocene complex trans-NiCl(o-Tol)(dppf)
(86–97%), among which [Iprmim]I performed best to give an gave significantly lower yields (Table 1, entries 18–21).
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1
2a,23
Use of anhydrous K
3
PO
4
led to a remarkably lower yield nickel catalysis in literaure,
although large amount of
(
53%) than that with trihydrate one (K
3
PO O), in consistent water was deleterious (Table 1, entries 22, 24 and 26). Base
4
ꢀ3H
2
with the observed positive effects of small amount of water on and solvent screening failed to improve the reaction compared
a
Table 2 Scope of the Ni-catalyzed cross-coupling of O,N-chelated diarylborinates with aryl chlorides
Entry Borinate (1)
Chloride (2)
Biaryl (3)
Entry Borinate (1)
Chloride (2)
Biaryl (3)
1
10
2
2a
11
1a
3
4
5
2a
2a
2a
12
13
14
1a
1a
1a
6
7
8
2a
2a
2a
15
16
17
1a
1a
1a
9
2a
18
1a
1a
19
a
Reaction conditions: 1 (0.65 mmol), 2 (1 mmol), 3 mol% trans-NiCl(Ph)(PPh
3
)
2
/3 mol% [Iprmim]I, K
3
PO
4
2 2
ꢀ3H O (2 mmol), toluene (5 mL), N , 6 h,
b
3 2
reflux. 5 mol% trans-NiCl(Ph)(PPh ) /5 mol% [Iprmim]I, 12 h.
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with the K
3
PO
4
ꢀ3H
2
O in toluene system (Table 1, entries 27–34).
For example, use of NaOH or KOH led to much lower yields while
the system deactivated totally with KO Bu (Table 1, entries 27–29).
t
Low to modest yields were obtained in the common solvents,
e.g. DMF, dioxane, DMSO and CH CN (Table 1, entries 31–34).
3
Therefore, the optimal condition was set as 3 mol% trans-
NiCl(Ph)(PPh
3
)
2
/[Iprmim]I in toluene using K
3
PO
4
ꢀ3H
2
O as base.
Scope and limitations of the nickel-catalyzed cross-coupling
of O,N-chelate stabilized diarylborinates with aryl chlorides
were briefly explored (Table 2). A low yield (25%) was obtained
with dimethylaminoethyl diarylborinate (1b) confirming the
privilege of the six-membered O,N-chelated boron ring with
3
-dimethyl aminopropanol for the reactivity of O,N-chelated
diarylborinates. Electron-donating 3-Me (1d, 92%), 4-Me (1e, 91%),
-MeO (1f, 90%), or withdrawing 4-F (1i, 94%), 3-F (1j, 91%), except
for 4-CF (1h, 68%), groups at the phenyl ring of diarylborinates
4
3
appeared not to significantly affect their reactivity in cross-
coupling with 2a while an ortho-group, e.g. 2-Me (1c, 76%) or
2-OMe (1g, 74%), decreased the yields of biaryls remarkably
(Table 2, entries 2–9). In contrast, both electronic and steric
factors of aryl chlorides affected their cross-coupling with diaryl-
borinates. For example, 4-chlorobenzaldehyde (2d, 92%), methyl
4-chlorobenzoate (2e, 93%), 3-chloroactetophenone (2c, 90%)
Scheme 1 Reactivities of aryl chlorides and sulfonates in the nickel-
and 4-chloronitrobenzene (2f, 92%) reacted similarly to 2a, while catalyzed cross-coupling with arylborons.
-chloroactetophenone (2b) and 2-chloronitrobenzene (2g) gave
2
the corresponding products in comparable lower yields (85%)
and (77%), respectively (Table 2, entries 10–15). An electron- possibly due to the steric factor given the fact that the latter
donating group, e.g. 4-Me (2h, 84%) and 4-OMe (2k, 82%), signi- is generally more electronically active than the former. Control
ficantly decreased the reactivity of aryl chorides, in particular, experiments with 3-dimethylaminopropyl di( p-tolyl)borinate (1d)
at ortho-position of the aryl ring, e.g. 2-Me (2i, 71%), therefore and the corresponding free borinic acids, di( p-tolyl)borinic acid,
higher loading (5 mol%) of the catalyst and longer reaction time which is dehydration-resisting, thus more accurate in stoichio-
were required to obtain satisfactory yields (Table 2, entries 16, 17 metry than its phenyl analog (Ph B(OH)), as well as p-tolyl
2
and 19). However, reaction of sterically demanding 2,6-dimethyl boronic acid, anhydride (boroxine) and trifluoroborate carried
phenyl chloride (2j) with 1a still gave a low yield (40%) even with under otherwise identical conditions confirmed the privilege
5
mol% catalyst loading (Table 2, entry 18).
of aryl mesylates as electrophiles, irrespective of nucleophile
counterparts although the reacivities of the latter two boron
reagents appeared to be significantly lower. No reaction was
Coupling with aryl mesylates
Although aryl halides have been recognized as the standard observed with pinacol p-tolylboronate in all cases.
electrophile counterpart in Suzuki coupling for construction of Investigation on the scope of the cross-coupling of
biaryl structure, the required halides are sometimes difficult, O,N-chelated diarylborinates with aryl mesylates revealed that
even extremely challenging, to access. Therefore, many efforts the electronic and steric influences from both nucleophile and
have been made to use readily accessible phenol derivatives, in electrophile counterparts are similar to those observed in the
2
4
particular sulfonates, i.e. triflates, tosylates and mesylates. reaction of aryl chlorides (Table 3). For example, diarylbori-
Among these sulfonates, tosylates have been most intensively nates bearing 3-Me (1d, 92%), 4-MeO (1f, 92%) or 4-F (1i, 96%)
used since they possess low cost, fair stability and good reactivity. group at phenyl rings coupled with 4a giving the diaryls 3ca-3ia
Comparably, the closely related mesylates were hampered by the in excellent yields, while the 2-Me (1c, 77%) or 2-OMe (1g, 79%)
poorer leaving ability of the mesylate group. However, mesylates substituent decreased the biaryl yields (Table 3, entries 1–6).
have better environmentally friendly profile than tosylates, Electronically deficient aryl mesylates with 4-CHO (4b, 91%)
2
e.g. higher atom economy and natural biodegradation of by- or 4-CO Me (4c, 97%) group gave higher yields than those of
2
5
product. Having established the nickel-based catalyst system electron-rich ones 4f (4-OMe, 84%) and 4d (4-Me, 87%) (Table 3,
for cross-coupling of O,N-chelated diarylborinates with aryl entries 7–9 and 11). Similar to chlorides, an ortho-substituent
chlorides, we further investigated its performance in the corres- also decreased the reactivity of aryl mesylates.
ponding coupling with aryl mesylates (Scheme 1).
Mechanistic discussion
Surprisingly, 4-acetylphenyl mesylate (4a) displayed signi-
0
0
2+
ficantly higher reactivity than its tosylate (4a ) in the trans- Although the general M /M cycle has been widely accepted
NiCl(Ph)(PPh /[Iprmim]I catalyzed cross-coupling with 1a, for both nickel- and palladium-catalyzed Suzuki coupling the
3 2
)
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a
Table 3 Scope of the Ni-catalyzed cross-coupling of O,N-chelated diarylborinates with aryl mesylates
Entry Borinate (1)
Mesylate (4)
Biaryl (3)
Entry Borinate (1) Mesylate (4)
Biaryl (3)
1
7
2
3
4a
4a
8
9
1a
1a
4
5
4a
10
1a
4a
4a
11
12
1a
1a
6
a
Reaction conditions: 1 (0.65 mmol), 4 (1 mmol), 3 mol% trans-NiCl(Ph)(PPh
3
)
2
/3 mol% [Iprmim]I, K
3
PO
4
2 2
ꢀ3H O (2 mmol), toluene (5 mL), N , 6 h,
b
3 2
reflux. 5 mol% trans-NiCl(Ph)(PPh ) /5 mol% [Iprmim]I, 12 h.
mechanism with nickel catalysts is much more complicated
than that of palladium ones because of the redox diversity of
nickel. Therefore, only a tentative explanation is given based on
0
2+
3 2
the Ni /Ni cycle (Scheme 2). The ArNiCl(PR ) precatalysts are
reduced to Ni(0) species by transmetalation with aryl boron
species followed by reductive elimination, which depends
on not only the ArNiCl(PR ) structure, i.e. Ar and PR , but also
3
2
3
the reaction conditions as well as activity of the arylboron
species. The inactivity of pinacol borate in the reaction could
be reasonably attributed to the failure of precatalyst activation
due to its low activity in transmetalation. The delicate balance
between availability, stability and activity of the catalytically
active Ni(0) species determines the efficiency of the catalyst
system. Presence of the in situ generated sterically unsym-
metrical NHC ligand helps to prevent the active Ni(0) species
from deactivation via comproportionation with Ni(II) species yet
reserves their reactivity, therefore performing best. The two-
coordinate nickel(0) complex co-supported by phosphine and
0
NHC, Ni (PR
3
)(NHC), generated via PR
3
/NHC ligand exchange
should be the most active Ni(0) species since both NHC Scheme 2 A plausible mechanistic explanation.
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3
and PPh have proven to be necessary to achieve the optimal Typical procedure for cross-coupling
catalyst system.
Under a N
2
atmosphere, to a 10 ml dry flask were added aryl
The key role played by the NHC/PR3 co-supported Ni(0)
species in the catalytic cycle is also consistent with the observa-
tion of the decreased catalytic efficiency using nickel precursors
chloride/mesylates (1 mmol), diarylborinates (0.65 mmol), trans-
NiCl(Ph)(PPh (3 mol%), [Iprmim]I (3 mol%), K PO
ꢀ3H
2 mmol), and toluene (5 ml). The mixture was stirred at 110 1C
)
3 2
3
4
2
O
(
ArNiCl(PR
dppf ligand since their exchange with NHC should be slower
than that of PPh , in particular in the case of dppf. The observed
3 2 3
) with electron-rich PCy or chelating diphosphine
for a given time or monitored by TLC until the starting material
was completely consumed. The reaction mixture was diluted with
CH Cl (15 ml), followed by washing with H O (3 ꢁ 10 ml). The
3
2
2
2
differences in reactivities of mesylates vs tosylates as well as
various arylboron derivatives, i.e. 3-dimethylaminopropyl diaryl-
borinates, diarylborinic acids, arylboronic acid and derivatives,
e.g. boroxine(anhydride), pinacol borate and trifluoroboronate,
in control experiments implies that both oxidative addition of
aryl sulfonates to the Ni (PR
organic layer was dried over anhydrous Na SO , filtered, and
2
4
evaporated under reduced pressure to give crude product, which
was purified by column chromatography on silica gel to afford
biaryl compound (see ESI† for details).
0
3
)(NHC) and the following aryl trans-
metalation from boron should be involved in rate-determining Conflicts of interest
steps in the catalytic cycle.
There are no conflicts to declare.
Conclusions
Acknowledgements
In summary, a triphenylphosphine and NHC co-supported
We are grateful for financial support provided by the National
Natural Science Foundation of China (21472041).
organonickel-based catalyst system, trans-NiCl(Ph)(PPh
3 2
) /
[
Iprmim]I/K PO ꢀ3H O in toluene, has been developed for cross-
3
4
2
coupling of shelf-stable O,N-chelate stabilized 3-dimethylamino-
propyl diarylborinates with aryl chlorides and mesylates. A small
amount of water appeared to play an important role in the
catalysis, which could be readily introduced by use of trihydrate
potassium phosphate. Sterically unsymmetrical NHCs appeared
to match the organonickel precursor better than the symmetrical
ones. The nickel-based catalyst system showed remarkably higher
activity to the environmentally friendly aryl mesylates than the
corresponding tosylates in cross-coupling with diarylborinates,
which was unmistakably confirmed in control experiments of
diarylborinic acids and the traditional arylboronic acid deriva-
tives. A variety of electronically various biaryls could be obtained
in excellent yields by using 3–5 mol% loading of the nickel catalyst
while a significant steric effect was observed from both diaryl-
borinates and aryl chlorides and mesylates.
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1594 | New J. Chem., 2019, 43, 1589--1596
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