Pincer-Nickel-Catalyzed Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides

Article abstract of DOI:10.1002/ejoc.201500987

The nickel N,N,N-pincer complex 2 was demonstrated to effectively catalyze the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups. A nickel N,N,N-pincer complex effectively catalyzes the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups.

Full text of DOI:10.1002/ejoc.201500987

FULL PAPER
DOI: 10.1002/ejoc.201500987
Pincer-Nickel-Catalyzed Cross-Coupling of Aryl Sulfamates with Arylzinc
Chlorides
Jian-Long Tao[a] and Zhong-Xia Wang*[a,b]
Keywords: Homogeneous catalysis / Cross-coupling / Pincer complexes / Nickel / Ligand design / Sulfamates
The nickel N,N,N-pincer complex 2 was demonstrated to ef- able for a wide range of substrates, and tolerates various
fectively catalyze the cross-coupling of aryl sulfamates with
arylzinc chlorides under mild conditions. The reaction is suit-
functional groups.
Introduction
con, and -tin reagents and better functional-group compati-
bility than organomagnesium reagents. Hence, it would be
interesting to explore the reactions of aryl sulfamates with
arylzinc reagents to construct biaryl compounds. The reac-
tions of arylzinc reagents with various phenol derivatives,
including aryl pivalates and aryl methyl ethers, have been
reported. However, only reactive electrophiles such as naph-
thyl pivalates, electron-deficient phenyl pivalates, and elec-
tron-deficient aryl methyl ethers can be used in these reac-
tions.[9] This is another reason that we chose to investigate
the reactions of aryl sulfamates with arylzinc reagents. In
our previous studies on Negishi-type cross-coupling reac-
tions using aryl halides or aromatic ammonium salts as
electrophiles, nickel pincer complexes were shown to be ef-
fective catalysts.[10] For example, nickel P,N,N-pincer com-
plex [Ni(Cl){N(2-Ph2PC6H4)(2Ј-Me2NC6H4)}] catalyzes the
cross-coupling of aryltrimethylammonium triflates with
aryl- or heteroarylzinc chlorides under mild conditions with
extremely low catalyst loadings.[10a] On the basis of the re-
sults achieved, we intended to investigate nickel-pincer-
complex-catalyzed cross-coupling of aryl sulfamates with
arylzinc reagents. We found that phosphorus-free nickel
N,N,N-pincer complexes 1–4 (Scheme 1) can catalyze the re-
action, and we report the results in this paper.
Transition-metal-catalyzed cross-coupling reactions of
organometallic reagents with various electrophiles are
powerful tools for the synthesis of biaryls, which are an
important class of compounds in the areas of natural prod-
uct chemistry, agrochemicals, liquid crystals, pharmaceuti-
cals, and advanced materials.[1,2] Organic halides are the
electrophiles that have been used most often in recent dec-
ades.[1] Phenolic derivatives are also attractive electrophiles,
reacting through C–O bond cleavage, due to the wide avail-
ability of phenols from nature and industry. Aryl triflates
are the most widely investigated of the phenol-based elec-
trophiles due to their good reactivity. However, their high
cost and instability limit their use. Hence, other phenol-de-
rived electrophiles such as mesylates, tosylates, esters, carb-
onates, phosphates, carbamates, sulfamates, and ethers have
also been studied.[3] Of these, aryl sulfamates have recently
received attention. Aryl sulfamates are readily synthesized,
and they are more stable and less expensive than aryl tri-
flates. The O-sulfamate moiety is an effective directing
group for arene functionalization.[4] Hence sulfamates can
be used as an alternative to triflates, even though their C–
O bonds are less reactive than those in triflates. Cross-cou-
pling reactions that have been reported using aryl sulfam-
ates as electrophiles include Suzuki reactions,[4a,4b,5] Kum-
ada reactions,[4c,6] amination reactions,[7] and C–H bond
functionalizations.[8]
Organozinc reagents are readily prepared nucleophilic
species that show higher reactivity than organoboron, -sili-
[a] Department of Chemistry, University of Science and
Technology of China,
Hefei, Anhui 230026, People’s Republic of China
E-mail: zxwang@ustc.edu.cn
http://en.scms.ustc.edu.cn
[b] Collaborative Innovation Center of Chemical Science and
Engineering (Tianjin),
Tianjin 300072, People’s Republic of China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201500987.
Scheme 1. Nickel pincer complexes 1–4.
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Org. Chem. 2015, 6534–6540
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Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides
complex 3 led to the lowest product yield (Table 1, en-
tries 1–4). It seems that a strongly electron-donating group
on the pyridine ring of the ligand is disadvantageous to the
catalytic activity of the complexes. Then the effect of the
solvent was examined. A series of solvents or solvent com-
binations including THF, NMP, THF/DMA (N,N-dimeth-
ylacetamide), THF/toluene, and THF/NMP were tested,
and a 2:1 mixture of THF and NMP was found to be the
best (Table 1, entries 5–10). Examination of reaction tem-
perature showed that the reaction proceeded most effec-
tively at 50 °C, with higher or lower reaction temperatures
leading to lower yields (Table 1, entries 11–14). Testing the
salt effect showed that the zinc reagent p-Me2NC6H4ZnCl,
prepared from the corresponding Grignard reagent and
ZnCl2 in the presence of LiCl (2 equiv.) gave better results
than the reagents prepared from p-Me2NC6H4Li and
ZnCl2, p-Me2NC6H4MgBr and ZnCl2, or p-Me2NC6H4Li
and ZnCl2 in the presence of MgBr2 (1 equiv.) (Table 1, en-
tries 15–17). That is to say, lithium and magnesium ions
both play important roles in the reaction. This may be due
to the presence of a multimetallic synergistic effect in the
reaction process.[12] In addition, the role of LiCl may also
involve (1) breaking the aggregation of ArZnCl with the co-
product of MgCl2 through the formation of a trimetallic
adduct, and (2) enhancing the reactivity of the zinc reagents
by forming more nucleophilic zincates.[9b,12,13] When the re-
action time was shortened to 12 h, the reaction still gave a
99% yield of the product (Table 1, entry 18). We also noted
that the amount of catalyst could be reduced. A catalyst
loading of 1 mol-% resulted in a 95% yield of the product
using the optimized reaction solvent, temperature, and time
(Table 1, entry 19). It was reported that (Cy3P)2NiCl2 can
catalyze the cross-coupling of aryl/alkenyl pivalates with ar-
ylzinc reagents.[9a] For comparison, we also tested catalysis
of (Cy3P)2NiCl2 in the cross-coupling of PhOSO2NMe2
with p-Me2NC6H4ZnCl. We found that the catalytic effi-
ciency of (Cy3P)2NiCl2 is clearly lower than that of complex
2; when (Cy3P)2NiCl2 was used with catalyst loadings of 5
and 1 mol-%, the cross-coupling products were formed in
93 and 84% yields, respectively (Table 1, entries 20 and 21).
In addition, in the absence of any metal catalyst, the reac-
tion gave a 25% yield of the product at 50 °C, and 21%
yield at 80 °C (Table 1, entries 22 and 23). This means that
a direct nucleophilic substitution can take place with a low
efficiency.
Results and Discussion
The synthesis and characterization of complexes 1–4 are
presented in the Supporting Information. Each of these
complexes is diamagnetic, and was characterized by elemen-
1
tal analysis and H and 13C NMR spectroscopy. The struc-
ture of complex 2 was also determined by single-crystal X-
ray diffraction,[11] which showed the pincer coordination
mode. The fact that complexes 3 and 4 are diamagnetic im-
plies that in both of these structures the central Ni atom
has a square-planar coordination geometry. Hence, for each
of 3 and 4 an ion-pair structure consisting of a tridentate
chelate nickel chloride cation and an chloride anion was
proposed.
We used the reaction of PhOSO2NMe2 with p-
Me2NC6H4ZnCl to evaluate the catalytic properties of com-
plexes 1–4 and optimize the reaction conditions. The results
are listed in Table 1. Initially, the reaction was run in a 1:1
mixture of THF and NMP (N-methylpyrrolidine) at 80 °C
for 24 h using a catalyst loading of 5 mol-%. Each of the
complexes was found to be catalytically active. Complex 2
resulted in the highest yield of the desired product, and
Table 1. Catalyst evaluation and optimization of reaction condi-
tions.[a]
Entry
Cat. (mol-%)
Solvent
Temp. Yield
[°C]
[%][b]
1
2
3
4
5
6
7
8
1 (5)
THF/NMP (1:1)
THF/NMP (1:1)
THF/NMP (1:1)
THF/NMP (1:1)
THF
80
80
80
80
80
80
80
80
80
80
70
60
50
25
50
50
50
50
50
50
50
50
80
60
65
49
56
37
55
48
25
68
74
75
85
99
60
54
57
69
99
95
93
84
25
21
2 (5)
3 (5)
4 (5)
2 (5)
2 (5)
NMP
2 (5)
THF/DMA (1:1)
THF/toluene (1:1)
THF/NMP (1:2)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
THF/NMP (2:1)
2 (5)
9
2 (5)
10
11
12
13
14
15[c]
16[d]
17[e]
18[f]
19[f]
20
21
22[f]
23[f]
2 (5)
2 (5)
2 (5)
2 (5)
2 (5)
2 (5)
2 (5)
2 (5)
Under the optimized reaction conditions, the scope of
the reaction with respect to the arylzinc chloride and aryl
sulfamate components was examined (Table 2). As can be
seen from Table 2, the reaction of PhOSO2NMe2 with p-
MeOC6H4ZnCl gave a similar yield to that obtained using
p-Me2NC6H4ZnCl as the nucleophile (Table 2, entry 1).
The deactivated derivatives p-BnC6H4OSO2NMe2, p-Me-
C6H4OSO2NMe2, and m-MeC6H4OSO2NMe2 showed
good reactivity in the coupling reactions with p-
Me2NC6H4ZnCl, p-MeOC6H4ZnCl, and p-MeC6H4ZnCl
in the presence of 1 mol-% of complex 2 (Table 2, entries 2–
8). However, the reaction of o-MeC6H4OSO2NMe2 was
much more difficult than those of p-MeC6H4OSO2NMe2
2 (5)
2 (1)
(Cy3P)2NiCl2 (5)
(Cy3P)2NiCl2 (1)
none
none
[a] The reactions were carried out on a 0.5 mmol scale, 2.0 equiv.
of p-Me2NC6H4ZnCl were used. Unless otherwise specified, p-
Me2NC6H4ZnCl was prepared from p-Me2NC6H4MgBr and ZnCl2
in the presence of 2 equiv. of LiCl. [b] Isolated yield. [c] The zinc
reagent was prepared from p-Me2NC6H4Li and ZnCl2. [d] p-
Me2NC6H4ZnCl was prepared from p-Me2NC6H4MgBr and ZnCl2
(1 equiv.). [e] p-Me2NC6H4ZnCl was prepared from p-
Me2NC6H4Li and ZnCl2 (1 equiv.) in the presence of MgBr2
(1 equiv.). [f] The reaction time was 12 h.
Eur. J. Org. Chem. 2015, 6534–6540
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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J.-L. Tao, Z.-X. Wang
FULL PAPER
and m-MeC6H4OSO2NMe2 due to steric hindrance. It re- tive due to steric hindrance. Its reaction with p-
quired a higher catalyst loading, and gave lower product MeC6H4ZnCl gave a 62% yield of the product, even in the
yields (Table 2, entries 9 and 10). Strongly deactivated presence of 5 mol-% of complex 2. The sterically hindered
derivatives
p-MeOC6H4OSO2NMe2,
p-Me2NC6H4O- zinc reagent o-MeC6H4ZnCl also showed a reactivity lower
SO2NMe2, and m-Me2NC6H4OSO2NMe2 also reacted than that of p-MeC6H4ZnCl. The reaction of o-
with arylzinc reagents including p-MeC6H4ZnCl, p- MeC6H4ZnCl with deactivated sulfamates such as p-MeO-
Me2NC6H4ZnCl, and PhZnCl when 3 mol-% of 2 was used, C6H4OSO2NMe2 and p-Me2NC6H4OSO2NMe2 gave the
giving the desired products in good to excellent yields desired products in quite low yields in the presence of
(Table 2, entries 11–18).
A series of electron-deficient 5 mol-% 2 (Table 2, entries 28–29). In contrast, the reaction
sulfamates including p-NCC6H4OSO2NMe2, p-MeOC(O)- of o-MeC6H4ZnCl with activated sulfamates such as p-Me-
C6H4OSO2NMe2, p-FC6H4OSO2NMe2, p-CF3C6H4O- OC(O)C6H4OSO2NMe2 and p-NCC6H4OSO2NMe2 re-
SO2NMe2, and p-PhC(O)C6H4OSO2NMe2 were tested, and sulted in good product yields using 3 mol-% of 2 as catalyst
each of them showed good reactivity and led to the prod- (Table 2, entries 30–31). The electron-poor arylzinc reagent
ucts in excellent yield in the presence of 1 mol-% 2 (Table 2, p-CF3C6H4ZnCl was also tested. Its reactions with the acti-
entries 19–26). o-MeOC(O)C6H4OSO2NMe2 was less reac- vated sulfamates p-MeOC(O)C6H4OSO2NMe2 and p-
NCC6H4OSO2NMe2 gave excellent results (Table 2, en-
tries 32–33). However, its reaction with deactivated sulfam-
Table 2. Cross-coupling of substituted phenyl sulfamates with aryl-
ates such as p-MeOC6H4OSO2NMe2 and p-Me2NC6H4O-
zinc chlorides catalyzed by complex 2.[a]
SO2NMe2 did not give any of the desired products.
Next, we tested the reactivity of naphthyl, pyridyl, and
quinolyl sulfamates in cross-coupling reactions with aryl-
zinc chlorides catalyzed by 2 (Table 3). Both 1- and 2-
naphthyl sulfamates showed excellent reactivity. Their reac-
tions with p-MeC6H4ZnCl, p-Me2NC6H4ZnCl, and p-Me-
Entry R1
R2
x
Yield [%][b]
OC6H4ZnCl proceeded smoothly at room temperature in
the presence of complex 2 (0.5 mol-%) to give the desired
products in excellent yields (Table 3, entries 1–6). The reac-
tion of 2-naphthyl sulfamate with the sterically hindered o-
MeC6H4ZnCl also gave an excellent result under the same
conditions. 2-Pyridyl and 8-quinolyl sulfamates both
showed lower reactivity than 1- and 2-naphthyl sulfamates.
They could react smoothly with p-MeC6H4ZnCl at 50 °C in
the presence of 1 mol-% of complex 2. Their reaction with
the electron-deficient zinc reagent p-CF3C6H4ZnCl required
1
2
3
4
5
6
7
8
H
p-Bn
p-Bn
p-Bn
p-Me
p-Me
m-Me
m-Me
o-Me
p-OMe
p-NMe2
p-OMe
p-Me
p-NMe2
p-OMe
p-NMe2
p-OMe
p-NMe2
p-OMe
p-Me
p-NMe2
H
p-Me
p-OMe
H
p-Me
1
1
1
1
1
1
1
1
5
5
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
5
5
5
3
3
3
3
98
89
90
88
90
80
85
80
57
35
94
94
92
80
81
80
81
80[c]
92
95
92
99
92
90
90[c]
85
62
20
17
88
88
87
86
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
o-Me
p-MeO
p-MeO
p-MeO
p-NMe2
p-NMe2
p-NMe2
m-NMe2
m-NMe2
p-CN
p-MeOC(O) p-Me
p-F
p-F
p-CF3
p-CF3
p-CF3
p-PhC(O)
o-MeOC(O) p-Me
p-MeO
Table 3. Cross-coupling of naphthyl, pyridyl, and quinolyl sulfam-
ates with arylzinc chlorides catalyzed by complex 2.[a]
p-OMe
p-Me
p-OMe
p-NMe2
p-NMe2
p-OMe
p-Me
Entry
Ar
R
x
Yield [%][b]
1
2
3
4
5
6
7
1-naphthyl
1-naphthyl
1-naphthyl
2-naphthyl
2-naphthyl
2-naphthyl
2-naphthyl
2-pyridyl
p-Me
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
97
95
95
98
96
98
92
88
82
89
83
p-MeO
p-NMe2
p-Me
p-MeO
p-NMe2
o-Me
p-Me
p-CF3
p-Me
p-Me
o-Me
o-Me
p-NMe2
p-MeOC(O) o-Me
p-CN
p-CN
p-MeOC(O) p-CF3
o-Me
p-CF3
8[c]
9[c]
10[c]
11[c]
2-pyridyl
8-quinolyl
8-quinolyl
3
1
3
p-CF3
[a] The reactions were carried out on a 0.5 mmol scale according
to the conditions indicated by the above equation; the zinc reagents
were prepared from the corresponding Grignard reagents and
ZnCl2 in the presence of LiCl (2 equiv.); 2.0 equiv. of zinc reagent
was used. [b] Isolated yield. [c] A mixture of cross-coupling product
and homocoupling product of the zinc reagent was obtained, and
their ratio was calculated using integrals of the 1H NMR spectrum.
[a] Unless otherwise specified, the reactions were carried out on a
0.5 mmol scale according to the conditions indicated by the above
equation. The zinc reagents were prepared from corresponding
Grignard reagents and ZnCl2 in the presence of LiCl (2 equiv.);
2.0 equiv. of the zinc reagent was used. [b] Isolated yield. [c] The
reaction was run at 50 °C for 12 h.
6536
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Eur. J. Org. Chem. 2015, 6534–6540

Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides
higher catalyst loadings. A catalyst loading of 3 mol-% of
complex 2 was necessary to drive the reaction to completion
(Table 3, entries 8–11).
A preliminary mechanistic study was carried out using
the reaction of PhOSO2NMe2 with p-Me2NC6H4ZnCl cata-
lyzed by 2 under the optimized conditions. When 1,1-di-
phenylethylene (10 mol-%) was added to the reaction mix-
Experimental Section
General: All air- or moisture-sensitive manipulations were carried
out under nitrogen using standard Schlenk techniques. Toluene was
distilled under nitrogen from sodium; THF and DME were distilled
under nitrogen from sodium/benzophenone; NMP and DMA were
dried with molecular sieves (4 Å), fractionally distilled under re-
duced pressure, and stored under a nitrogen atmosphere. CDCl3
ture, the cross-coupling product was obtained in 33% yield, was purchased from Cambridge Isotope Laboratories. The prepa-
ration of aryl sulfamates, ligand precursors, and complexes 1–4 is
given in the Supporting Information. NMR spectra were recorded
with a Bruker Avance III 400 spectrometer at ambient temperature.
which is slightly higher than the yield obtained by direct
nucleophlic substitution in the absence of a catalyst
(Table 1, entry 22). It seems that the reaction proceeded
through a free-radical process. A combination of Ni-
(COD)2 (1 mol-%; COD = cyclooctadienyl) and complex 5
(1 mol-%, prepared in situ by reaction of the ligand precur-
sor with nBuLi) (Scheme 2) led to only a 40% yield of the
cross-coupling product. Hence, the active catalyst should
not be a Ni0 species. In another experiment, a mixture of
complex 2 (0.5 mmol) and p-Me2NC6H4ZnCl (0.75 mmol)
in THF was stirred at room temperature for 4 h. The re-
sulting mixture was treated with PhOSO2NMe2 (0.5 mmol)
in THF/NMP (2:1) at 50 °C for 12 h. No cross-coupling
product was obtained. This observation contrasts with re-
ports of nickel pincer 6 catalyzed cross-coupling reactions
of alkyl halides with alkyl Grignard reagents reported by
Hu et al.[14] Based on the experimental facts given above
and the reported mechanistic studies of nickel-catalyzed
cross-coupling reactions,[15] we inferred that the catalytic
process may involve a NiI species, although we cannot yet
give a clear catalytic cycle.
1
The chemical shifts of H and 13C NMR spectra were referenced
to tetramethylsilane or to internal solvent resonances.
General Procedure: A Schlenk tube was charged with aryl sulfamate
(0.5 mmol), complex 2 (2.0 mg, 0.005 mmol), and NMP (1.0 mL).
ArZnCl solution (0.5 m solution in THF; 2 mL, 1.0 mmol) was
added by syringe to the stirred mixture. The reaction mixture was
stirred at 50 °C for 12 h. Water (10 mL) and several drops of glacial
acetic acid were then successively added. The mixture was extracted
with Et2O (3ϫ 10 mL). The combined organic phases were dried
with anhydrous Na2SO4, and concentrated by rotary evaporation,
and the residue was purified by column chromatography (silica gel).
4-Benzyl-4Ј-methylbiphenyl:[16] 1H NMR (400 MHz, CDCl3): δ =
2.38 (s, 3 H), 4.01 (s, 2 H), 7.18–7.26 (m, 7 H), 7.27–7.32 (m, 2 H),
7.46 (d, J = 8 Hz, 2 H), 7.49 (d, J = 8 Hz, 2 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 21.23, 41.72, 126.26, 126.98, 127.16,
128.65, 129.11, 129.42, 129.59, 136.96, 138.26, 139.11, 140.08,
141.21 ppm.
4Ј-Benzyl-N,N-dimethylbiphenyl-4-amine:[17] 1H NMR (400 MHz,
CDCl3): δ = 2.98 (s, 6 H), 4.00 (s, 2 H), 6.79 (d, J = 8.4 Hz, 2 H),
7.18–7.24 (m, 5 H), 7.30 (t, J = 7.6 Hz, 2 H), 7.47 (d, J = 8.4 Hz,
4 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 40.73, 41.69, 112.94,
126.18, 126.48, 127.70, 128.61, 129.10, 129.26, 129.35, 138.99,
139.19, 141.38, 149.98 ppm.
4-Benzyl-4Ј-methoxybiphenyl:[18] 1H NMR (400 MHz, CDCl3): δ =
3.83 (s, 3 H), 4.00 (s, 2 H), 6.95 (d, J = 8.8 Hz, 2 H), 7.19–7.25 (m,
5 H), 7.29 (t, J = 7.2 Hz, 2 H), 7.46 (d, J = 8.4 Hz, 2 H), 7.49 (d,
J = 8.8 Hz, 2 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 41.70,
55.46, 114.31, 126.25, 126.92, 128.14, 128.64, 129.09, 129.43,
133.71, 138.79, 139.74, 141.24, 159.15 ppm.
Scheme 2. Lithium (5) and nickel (6) pincer complexes.
N,N-Dimethylbiphenyl-4-amine:[10c] 1H NMR (400 MHz, CDCl3): δ
= 2.99 (s, 6 H), 6.81 (d, J = 8.8 Hz, 2 H), 7.23–7.27 (m, 1 H), 7.39
(t, J = 7.8 Hz, 2 H), 7.51 (d, J = 8.8 Hz, 2 H), 7.54–7.57 (m, 2 H)
ppm. 13C NMR (101 MHz, CDCl3): δ = 40.64, 112.88, 126.08,
126.37, 127.79, 128.76, 129.32, 141.32, 150.07 ppm.
Conclusions
4-Methoxybiphenyl:[10c] 1H NMR (400 MHz, CDCl3): δ = 3.85 (s,
3 H), 6.98 (d, J = 8.8 Hz, 2 H), 7.28–7.32 (m, 1 H), 7.41 (t, J =
7.8 Hz, 2 H), 7.51–7.56 (m, 4 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 55.49, 114.35, 126.80, 126.88, 128.30, 128.86, 133.93,
140.98, 159.29 ppm.
N,N,4Ј-Trimethylbiphenyl-4-amine:[16] 1H NMR (400 MHz,
CDCl3): δ = 2.28 (s, 3 H), 2.88 (s, 6 H), 6.68–6.71 (m, 2 H), 7.11
(d, J = 8.0 Hz, 2 H), 7.33–7.42 (m, 4 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 21.16, 40.74, 112.96, 126.29, 127.64, 129.45, 129.49,
135.71, 138.51, 149.94 ppm.
4-Methoxy-4Ј-methylbiphenyl:[18] 1H NMR (400 MHz, CDCl3): δ =
2.36 (s, 3 H), 3.80 (s, 3 H), 6.94 (d, J = 8.8 Hz, 2 H), 7.20 (d, J =
8.0 Hz, 2 H), 7.43 (d, J = 8.0 Hz, 2 H), 7.49 (d, J = 8.8 Hz, 2 H)
ppm. 13C NMR (101 MHz, CDCl3): δ = 21.15, 55.40, 114.28,
126.68, 128.05, 129.56, 133.84, 136.43, 138.08, 159.06 ppm.
We have synthesized nickel N,N,N-pincer complexes 1–4
and evaluated their catalytic behavior in the cross-coupling
reaction of aryl sulfamates with arylzinc reagents. Complex
2, a phosphorus-free and air-stable catalyst, can effectively
catalyze the cross-coupling of activated, unactivated, and
deactivated aryl sulfamates and heteroaryl sulfamates with
arylzinc chlorides, forming biaryls in high yields. The reac-
tions required low catalyst loadings and mild reaction con-
ditions in most cases. A range of functional groups includ-
ing MeO, Me2N, PhC(O), COOMe, CN, CF3, and F
groups, and also nitrogen-containing heterocycles were tol-
erated. The extension to more challenging substrate combi-
nations using these nickel pincer catalysts is currently un-
derway in our laboratory.
Eur. J. Org. Chem. 2015, 6534–6540
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6537

J.-L. Tao, Z.-X. Wang
N,N,3Ј-Trimethylbiphenyl-4-amine:[19] 1H NMR (400 MHz, 132.90, 137.07 (d, J = 3.2 Hz), 159.24, 162.21 (d, J = 246.3 Hz)
FULL PAPER
CDCl3): δ = 2.30 (s, 3 H), 2.86 (s, 6 H), 6.69 (d, J = 8.8 Hz, 2 H),
6.97 (d, J = 7.2 Hz, 1 H), 7.18 (t, J = 7.4 Hz, 1 H), 7.26 (d, J =
9.2 Hz, 2 H), 7.40 (d, J = 9.2 Hz, 2 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 20.70, 39.67, 111.87, 122.53, 125.88, 126.21, 126.81,
127.67, 128.50, 137.22, 140.32, 149.03 ppm.
ppm.
N,N-Dimethyl-4Ј-(trifluoromethyl)biphenyl-4-amine:[10c] 1H NMR
(400 MHz, CDCl3): δ = 3.01 (s, 6 H), 6.80 (d, J = 8.8 Hz, 2 H),
7.52 (d, J = 8.8 Hz, 2 H), 7.61–7.66 (m, 4 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 40.56, 112.77, 124.67 (J = 272.7 Hz),
125.73 (J = 4.0 Hz), 126.34, 127.42, 127.97 (J = 32.3 Hz), 128.01,
4Ј-Methoxy-3-methylbiphenyl:[20] 1H NMR (400 MHz, CDCl3): δ =
2.38 (s, 3 H), 3.79 (s, 3 H), 6.94 (d, J = 8.8 Hz, 2 H), 7.10 (d, J = 144.80, 150.64 ppm.
7.6 Hz, 1 H), 7.28 (t, J = 7.4 Hz, 1 H), 7.33 (d, J = 10.0 Hz, 2 H),
4-Methoxy-4Ј-(trifluoromethyl)biphenyl:[10c] 1H NMR (400 MHz,
7.50 (d, J = 8.8 Hz, 2 H) ppm. 13C NMR (101 MHz, CDCl3): δ =
21.65, 55.38, 114.25, 123.95, 127.52, 127.65, 128.25, 128.74, 133.98,
138.36, 140.92, 159.20 ppm.
CDCl3): δ = 3.84 (s, 3 H), 6.99 (d, J = 8.8 Hz, 2 H), 7.53 (d, J =
8.8 Hz, 2 H), 7.61–7.66 (m, 4 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 55.48, 114.57, 124.54 (J = 272.7 Hz), 125.81 (J =
3.8 Hz), 126.99, 128.48, 128.82 (J = 32.3 Hz), 132.29, 144.43,
160.00 ppm.
N,N,2Ј-Trimethylbiphenyl-4-amine:[10c] 1H NMR (400 MHz,
CDCl3): δ = 2.22 (s, 3 H), 2.89 (s, 6 H), 6.70 (d, J = 8.8 Hz, 2 H),
7.09–7.19 (m, 6 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 20.80,
40.72, 112.22, 125.85, 126.64, 130.07, 130.21, 130.40, 135.64,
142.14, 149.52 ppm.
(4Ј-Methylbiphenyl-4-yl)(phenyl)methanone:[10c]
1H
NMR
(400 MHz, CDCl3): δ = 2.41 (s, 3 H), 7.28 (d, J = 7.9 Hz, 2 H),
7.49 (t, J = 7.4 Hz, 2 H), 7.55 (d, J = 8.4 Hz, 2 H), 7.57–7.61 (m,
4Ј-Methoxy-2-methylbiphenyl:[10c] 1H NMR (400 MHz, CDCl3): δ 1 H), 7.68 (d, J = 8.4 Hz, 2 H), 7.81–7.85 (m, 2 H), 7.88 (d, J =
= 2.27 (s, 3 H), 3.84 (s, 3 H), 6.95 (d, J = 8.8 Hz, 2 H), 7.19–7.28
8.4 Hz, 2 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 21.30, 126.83,
(m, 6 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 20.68, 55.41, 127.26, 128.42, 129.83, 130.11, 130.87, 132.45, 136.07, 137.19,
113.63, 125.89, 127.11, 130.04, 130.38, 130.43, 134.52, 135.62,
141.69, 158.65 ppm.
137.97, 138.31, 145.32, 196.49 ppm.
4Ј-Methylbiphenyl-4-carbonitrile:[10c] 1H NMR (400 MHz, CDCl3):
δ = 2.42 (s, 3 H), 7.29 (d, J = 8.0 Hz, 2 H), 7.49 (d, J = 8.0 Hz, 2
H), 7.67 (d, J = 8.6 Hz, 2 H), 7.71 (d, J = 8.6 Hz, 2 H) ppm. 13C
Methyl 4Ј-Methylbiphenyl-2-carboxylate:[21] 1H NMR (400 MHz,
CDCl3): δ = 2.38 (s, 3 H), 3.65 (s, 3 H), 7.20 (s, 4 H), 7.33–7.39
(m, 2 H), 7.46–7.51 (m, 1 H), 7.77–7.81 (m, 1 H) ppm. 13C NMR NMR (101 MHz, CDCl3): δ = 21.33, 110.70, 119.19, 127.21,
(101 MHz, CDCl3): δ = 21.30, 52.02, 127.02, 128.29, 128.91,
127.62, 129.98, 132.71, 136.43, 138.90, 145.76 ppm.
129.80, 130.83, 130.94, 131.30, 137.00, 138.43, 142.54, 169.33 ppm.
2Ј-Methylbiphenyl-4-carbonitrile:[26] 1H NMR (400 MHz, CDCl3):
δ = 2.26 (s, 3 H), 7.19 (d, J = 7.3 Hz, 1 H), 7.25–7.34 (m, 3 H),
7.44 (d, J = 8.4 Hz, 2 H), 7.71 (d, J = 8.4 Hz, 2 H) ppm. 13C NMR
Methyl 4Ј-Methylbiphenyl-4-carboxylate:[5g] 1H NMR (400 MHz,
CDCl3): δ = 2.29 (s, 3 H), 3.82 (s, 3 H), 7.15 (d, J = 7.9 Hz, 2 H),
7.41 (d, J = 8.1 Hz, 2 H), 7.52 (d, J = 8.4 Hz, 2 H), 7.98 (d, J = (101 MHz, CDCl3): δ = 20.45, 110.84, 119.10, 126.23, 128.42,
8.4 Hz, 2 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 21.23, 52.14,
126.85, 127.17, 128.67, 129.73, 130.16, 137.14, 138.17, 145.63,
167.10 ppm.
129.55, 130.12, 130.79, 132.10, 135.17, 140.12, 146.91 ppm.
4Ј-(Trifluoromethyl)biphenyl-4-carbonitrile:[27] 1H NMR (400 MHz,
CDCl3): δ = 7.69–7.71 (m, 4 H), 7.74–7.79 (m, 4 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 112.11, 118.73, 124.13 (J = 273.7 Hz),
126.22 (J = 3.7 Hz), 127.77, 128.10, 130.82 (J = 32.9 Hz), 132.93,
142.79, 144.27 ppm.
Methyl 2Ј-Methylbiphenyl-4-carboxylate:[22] 1H NMR (400 MHz,
CDCl3): δ = 2.17 (s, 3 H), 3.84 (s, 3 H), 7.11–7.19 (m, 4 H), 7.30
(d, J = 8.3 Hz, 2 H), 7.99 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 19.47, 51.20, 125.01, 126.94, 127.71,
128.37, 128.52, 128.62, 129.59, 134.25, 139.96, 145.86, 166.14 ppm.
Methyl 4Ј-(Trifluoromethyl)biphenyl-4-carboxylate:[28] 1H NMR
(400 MHz, CDCl3): δ = 3.86 (s, 3 H), 7.57 (d, J = 8.4 Hz, 2 H),
7.63 (s, 4 H), 8.05 (d, J = 8.4 Hz, 2 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 51.35, 123.28 (J = 272.7 Hz), 125.00 (J = 3.0 Hz),
4Ј-Methoxy-N,N-dimethylbiphenyl-4-amine:[10c]
1H
NMR
(400 MHz, CDCl3): δ = 2.95 (s, 6 H), 3.81 (s, 3 H), 6.78 (d, J =
8.8 Hz, 2 H), 6.93 (d, J = 8.8 Hz, 2 H), 7.44 (d, J = 8.8 Hz, 2 H), 126.37, 126.74, 128.95, 129.30 (J = 33.3 Hz), 142.65, 143.17,
7.47 (d, J = 8.8 Hz, 2 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 165.87 ppm.
39.77, 54.43, 112.04, 113.23, 126.40, 126.42, 128.26, 133.07, 148.72,
1-p-Tolylnaphthalene:[29] 1H NMR (400 MHz, CDCl3): δ = 2.45 (s,
157.37 ppm.
3 H), 7.29 (d, J = 7.8 Hz, 2 H), 7.37–7.53 (m, 6 H), 7.83 (d, J =
N,N,4Ј-Trimethylbiphenyl-3-amine:[23] 1H NMR (400 MHz, 8.1 Hz, 1 H), 7.90 (t, J = 8.1 Hz, 2 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 2.37 (s, 3 H), 2.98 (s, 6 H), 6.80 (d, J = 8.8 Hz, 2 H),
CDCl3): δ = 21.38, 125.54, 125.84, 126.06, 126.24, 127.02, 127.57,
7.20 (d, J = 7.9 Hz, 2 H), 7.45 (d, J = 8.0 Hz, 2 H), 7.48 (d, J = 128.39, 129.11, 130.09, 131.86, 133.96, 137.05, 137.96, 140.39 ppm.
8.8 Hz, 2 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 21.16, 40.73,
N,N-Dimethyl-4-(naphthalen-1-yl)aniline:[29] 1H NMR (400 MHz,
112.97, 126.28, 127.63, 129.45, 129.50, 135.71, 138.50, 149.93 ppm.
CDCl3): δ = 2.99 (s, 6 H), 6.83 (d, J = 8.4 Hz, 2 H), 7.37–7.49 (m,
4Ј-Fluoro-N,N-dimethylbiphenyl-4-amine:[24] 1H NMR (400 MHz, 6 H), 7.78 (d, J = 8.0 Hz, 1 H), 7.86 (d, J = 8.0 Hz, 1 H), 8.02 (d,
CDCl3): δ = 2.98 (s, 6 H), 6.79 (d, J = 8.8 Hz, 2 H), 7.07 (t, J =
8.8 Hz, 2 H), 7.40–7.52 (m, 4 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 39.68, 111.93, 114.54 (d, J = 21.4 Hz), 126.70, 126.81
(d, J = 7.8 Hz), 127.45, 136.51 (d, J = 3.1 Hz), 149.05, 160.86 (d,
J = 245.4 Hz) ppm.
J = 8.4 Hz, 1 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 40.72,
112.38, 125.61, 125.70, 125.82, 126.46, 126.87, 126.96, 128.33,
128.87, 130.93, 132.09, 134.06, 140.62, 149.91 ppm.
1-(4-Methoxyphenyl)naphthalene:[29] 1H NMR (400 MHz, CDCl3):
δ = 3.86 (s, 3 H), 7.01 (d, J = 8.7 Hz, 2 H), 7.38–7.42 (m, 4 H),
4-Fluoro-4Ј-methoxybiphenyl:[25] 1H NMR (400 MHz, CDCl3): δ = 7.44–7.50 (m, 2 H), 7.81 (d, J = 8.2 Hz, 1 H), 7.88 (d, J = 7.6 Hz,
3.84 (s, 3 H), 6.96 (d, J = 8.7 Hz, 2 H), 7.09 (t, J = 8.7 Hz, 2 H), 1 H), 7.92 (d, J = 8.4 Hz, 1 H) ppm. 13C NMR (101 MHz, CDCl3):
7.43–7.52 (m, 4 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 55.39, δ = 55.46, 113.86, 125.54, 125.83, 126.05, 126.20, 127.04, 127.46,
114.36, 115.63 (d, J = 21.4 Hz), 128.12, 128.31 (d, J = 8.0 Hz),
128.39, 131.24, 131.98, 133.26, 133.99, 140.05, 159.09 ppm.
6538
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 6534–6540

Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides
2-p-Tolylnaphthalene:[16] 1H NMR (400 MHz, CDCl3): δ = 2.43 (s,
3 H), 7.26–7.34 (m, 2 H), 7.46–7.51 (m, 2 H), 7.59–7.67 (m, 2 H),
7.72–7.76 (m, 1 H), 7.82–7.94 (m, 3 H), 8.03 (s, 1 H) ppm. 13C
NMR (101 MHz, CDCl3): δ = 21.28, 125.57, 125.70, 125.91,
126.37, 127.40, 127.77, 128.28, 128.49, 129.74, 132.65, 133.87,
137.30, 138.37, 138.63 ppm.
(Eds.), Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.,
Wiley-VCH, Weinheim, Germany, 2004.
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2004; b) Y. Nishihara (Ed.), Applied Cross-Coupling Reactions,
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N,N-Dimethyl-4-(naphthalen-2-yl)aniline:[10c] 1H NMR (400 MHz,
CDCl3): δ = 3.01 (s, 6 H), 6.84 (d, J = 8.8 Hz, 2 H), 7.39–7.49 (m,
2 H), 7.64 (d, J = 8.8 Hz, 2 H), 7.73 (dd, J = 1.8, 8.5 Hz, 1 H), 7.80–
7.89 (m, 3 H), 7.97 (s, 1 H) ppm. 13C NMR (101 MHz, CDCl3): δ
= 40.73, 113.00, 124.32, 125.38, 125.46, 126.21, 127.73, 128.08,
128.11, 128.33, 129.15, 132.20, 134.04, 138.70, 150.20 ppm.
[4]
[5]
2-o-Tolylnaphthalene:[30] 1H NMR (400 MHz, CDCl3): δ = 2.31 (s,
3 H), 7.24–7.35 (m, 4 H), 7.45–7.53 (m, 3 H), 7.77 (s, 1 H), 7.83–
7.90 (m, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 20.68,
125.97, 125.99, 126.30, 127.52, 127.64, 127.82, 127.88, 127.93,
128.15, 130.15, 130.51, 132.42, 133.46, 135.72, 139.69, 142.00 ppm.
2-(4-Methoxyphenyl)naphthalene:[10c] 1H NMR (400 MHz, CDCl3):
δ = 3.85 (s, 3 H), 7.01 (d, J = 8.8 Hz, 2 H), 7.42–7.50 (m, 2 H),
7.65 (d, J = 8.8 Hz, 2 H), 7.70 (dd, J = 1.8, 8.6 Hz, 1 H), 7.81–7.90
(m, 3 H), 7.97 (s, 1 H) ppm. 13C NMR (101 MHz, CDCl3): δ =
55.50, 114.46, 125.16, 125.57, 125.78, 126.36, 127.76, 128.19,
128.48, 128.56, 132.46, 133.76, 133.90, 138.29, 159.39 ppm.
2-p-Tolylpyridine:[16] 1H NMR (300 MHz, CDCl3): δ = 2.38 (s, 3
H), 7.11–7.19 (m, 1 H), 7.26 (d, J = 8.0 Hz, 2 H), 7.64–7.70 (m, 2
H), 7.89 (d, J = 8.1 Hz, 2 H), 8.66 (d, J = 4.8 Hz, 1 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 21.16, 120.26, 121.83, 126.84, 129.53,
136.69, 138.97, 149.65, 157.53 ppm.
[6]
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CCDC-1402816 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
2-[4-(Trifluoromethyl)phenyl]pyridine:[29] 1H NMR (300 MHz,
CDCl3): δ = 7.27–7.31 (m, 1 H), 7.70–7.81 (m, 4 H), 8.11 (d, J =
8.2 Hz, 2 H), 8.72 (d, J = 4.6 Hz, 1 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 120.96, 123.07, 124.34 (J = 273.2 Hz), 125.79 (J =
3.8 Hz), 127.31, 130.91 (J = 33.3 Hz), 137.09, 142.81, 150.05,
155.98 ppm.
[8]
8-p-Tolylquinoline:[31] 1H NMR (400 MHz, CDCl3): δ = 2.42 (s, 3
H), 7.30 (d, J = 7.8 Hz, 2 H), 7.34–7.38 (m, 1 H), 7.54–7.60 (m, 3
H), 7.70 (dd, J = 1.5, 7.1 Hz, 1 H), 7.77 (dd, J = 1.4, 8.1 Hz, 1 H),
8.15 (dd, J = 1.8, 8.3 Hz, 1 H), 8.93 (dd, J = 1.8, 4.2 Hz, 1 H) ppm.
13C NMR (101 MHz, CDCl3): δ = 21.38, 121.00, 126.34, 127.36,
128.82, 128.85, 130.16, 130.56, 136.26, 136.72, 137.11, 141.02,
146.26, 150.27 ppm.
[9]
[10]
8-[4-(Trifluoromethyl)phenyl]quinoline:[31] 1H NMR (400 MHz,
CDCl3): δ = 7.43 (dd, J = 4.2, 8.3 Hz, 1 H), 7.59–7.63 (m, 1 H),
7.71–7.82 (m, 5 H), 7.86 (dd, J = 1.4, 8.1 Hz, 1 H), 8.21 (dd, J =
1.8, 8.3 Hz, 1 H), 8.94 (dd, J = 1.8, 4.2 Hz, 1 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 121.39, 124.57 (J = 272.7 Hz), 125.02 (J =
3.8 Hz), 126.39, 128.49, 128.87, 129.42 (J = 32.3 Hz), 130.51,
131.05, 136.49, 139.50, 143.34, 145.87, 150.60 ppm.
[11]
Acknowledgments
[12]
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D. R. Armstrong, W. Clegg, P. García-Álvarez, A. R. Kennedy,
M. D. McCall, L. Russo, E. Hevia, Chem. Eur. J. 2011, 17,
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Financial support from the National Natural Science Foundation
of China (NSFC) (grant number 21172208) and the National Basic
Research Program of China (grant number 2015CB856600) is
greatly acknowledged. Professor D.-Q. Wang is thanked for the
crystal-structure determination.
[14]
[1] a) N. Miyaura (Ed.), Cross-Coupling Reactions: A Practical
Guide, Springer, Berlin, 2002; b) A. de Meijere, F. Diederich
Eur. J. Org. Chem. 2015, 6534–6540
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6539

J.-L. Tao, Z.-X. Wang
FULL PAPER
[15]
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Received: July 27, 2015
Published Online: August 24, 2015
6540
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Eur. J. Org. Chem. 2015, 6534–6540