Cross-coupling of aryltrimethylammonium iodides with arylzinc reagents catalyzed by amido pincer nickel complexes

Article abstract of DOI:10.1021/jo300209d

The cross-coupling reaction of aryltrimethylammonium iodides with aryl- or heteroarylzinc chlorides catalyzed by amido pincer nickel complexes was performed. The reaction requires low catalyst loading and displays broad substrate scope.

Full text of DOI:10.1021/jo300209d

Note
pubs.acs.org/joc
Cross-Coupling of Aryltrimethylammonium Iodides with Arylzinc
Reagents Catalyzed by Amido Pincer Nickel Complexes
Xue-Qi Zhang and Zhong-Xia Wang*
CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei,
Anhui 230026, People’s Republic of China
S
* Supporting Information
ABSTRACT: The cross-coupling reaction of aryltrimethyl-
ammonium iodides with aryl- or heteroarylzinc chlorides cat-
alyzed by amido pincer nickel complexes was performed.
The reaction requires low catalyst loading and displays broad
substrate scope.
ransition-metal-catalyzed cross-coupling reactions, includ-
ing Kumada, Negishi, Suzuki, and Stille cross-couplings,
complexes of nickel (I−V, Scheme 1). Catalytic properties of
these complexes in the reaction of aryltrimethylammonium
T
are powerful tools to construct carbon−carbon bonds in or-
ganic synthesis.1,2 The electrophiles exploited in these reactions
are principally organic iodides, bromides, triflates,1−3 and, more
recently, chlorides4 and other O-based substrates such as
tosylates, mesylates, and carboxylates.5 Reactions through C−N
bond cleavage of the electrophilic substrates are scarce, although
Wenkert and co-workers carried out the nickel-catalyzed reaction
of aryltrimethylammonium iodides with Grignard reagents in
the early stage of cross-coupling studies.6 On the other hand,
nitrogen-containing compounds such as aryl and alkylamines
are very important and widely available in the natural world and
in industry. The amino groups in arylamines are also important
activating and directing groups, which can lead to selective
functionalization of aromatic rings. Hence, the transformation
of N-containing compounds through catalytic activation of
C−N bonds is an attractive topic. Several related studies have
been reported. In 2007, Kakiuchi and co-workers reported a
ruthenium-catalyzed Suzuki coupling through C−N bond
cleavage of anilines with the aid of a carbonyl group at the
ortho position.7 In 2003, MacMillan et al. carried out the
Suzuki coupling of aryltrimethylammonium triflates with
Ni(cod)2/IMes as a catalyst.8 Recently, Reeves et al. developed
the coupling of aryltrimethylammonium triflates with Grignard
reagents using palladium as the catalyst.9 More recently, we re-
ported the coupling of aryltrimethylammonium iodides with
aryl or alkylzinc chlorides catalyzed by Ni(PCy3)2Cl2.10 After
that, we intended to develop new catalyst systems to improve
the coupling reaction. Amido pincer nickel complexes were
found to be very effective to catalyze cross-coupling of aryl
chlorides and arylzinc reagents.11 The preliminary experiments
showed that the pincer nickel complexes we reported pre-
viously can catalyze the reaction of aryltrimethylammonium
salts with arylzinc reagents, although the activity is lower than
Ni(PCy3)2Cl2. However, the catalytic properties could be
improved through modifying the ligands. For this purpose, we
designed new amido pincer ligands and synthesized their
Scheme 1. Complexes I−V Used for Catalyzing the Cross-
Coupling of an Arylammonium Salt with an Arylzinc
Reagent
salts with arylzinc chlorides were evaluated, and a series of ef-
ficient cross-couplings were carried out. Here we report the
results.
Synthetic routes of complexes I−V are summarized in the
Supporting Information. The catalytic investigation began with
+ −
an examination of the reaction of p-MeOC6H4NMe3 I with
p-MeC6H4ZnCl to evaluate the solvent effect and the catalytic
activities of complexes I−V. The screening results are listed in
Table 1. In the presence of 1 mol % I, the reaction can proceed
in either THF or a 1:1 mixture of THF and toluene, and each
gives the cross-coupling product in 40% yield, while in toluene,
no desired product was obtained (entries 1−3, Table 1). NMP
is often a good solvent or cosolvent in the catalyzed cross-
coupling of organozinc reagents. Hence, NMP and a mixture of
NMP and THF or toluene were examined as a solvent in
+ −
the I-catalyzed reaction of p-MeOC6H4NMe3 I with p-
MeC6H4ZnCl. The results showed that the suitable solvent is a
1:1 mixture of NMP and THF, which leads to 90% yield of cross-
coupling product (entries 4−8, Table 1). This solvent system was
Received: January 31, 2012
Published: March 9, 2012
© 2012 American Chemical Society
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The Journal of Organic Chemistry
Note
Table 1. Evaluation of the Catalytic Activity of Complexes
Table 2. Reaction of Aryltrimethylammonium Iodides with
Arylzinc Chlorides Catalyzed by Complex I
a
+
I−V in the Reaction of p-MeOC6H4NMe3 I− with
a
p-MeC6H4ZnCl
b
entry
Ar1
Ar2
yield (%)
1
2
3
4
5
6
7
Ph
Ph
Ph
Ph
p-MeC6H4
o-MeC6H4
p-MeOC6H4
p-Me2NC6H4
p-MeC6H4
p-MeC6H4
o-MeC6H4
o-MeC6H4
o-MeC6H4
p-Me2NC6H4
p-MeC6H4
p-MeC6H4
o-MeC6H4
o-MeC6H4
p-MeOC6H4
p-MeC6H4
p-MeOC6H4
p-Me2NC6H4
p-CF3C6H4
p-CF3C6H4
p-CF3C6H4
p-CF3C6H4
p-CF3C6H4
2-furyl
96
80
75
80
90
87
68
78
88
87
92
88
91
94
89
97
75
86
66
88
80
42
56
99
99
75
80
78
97
93
90
97
94
82
b
entry
complex
solvent
yield (%)
40
1
2
3
4
5
6
7
8
I
THF
c
p-MeOC6H4
m-MeOC6H4
p-MeOC6H4
p-MeOC6H4
p-MeOC6H4
m-MeOC6H4
p-EtOOCC6H4
p-PhC(O)C6H4
p-EtOOCC6H4
p-PhC(O)C6H4
p-EtOOCC6H4
o-MeC6H4
I
toluene
nr
I
THF/toluene (1:1)
NMP
40
62
62
56
67
90
72
67
74
52
45
I
c
8
I
NMP/toluene (1:1)
THF/NMP (1:2)
THF/NMP (2:1)
THF/NMP (1:1)
THF/NMP (1:1)
THF/NMP (1:1)
THF/NMP (1:1)
THF/NMP (1:1)
THF/NMP (1:1)
d
9
I
c
10
I
11
12
13
14
15
16
17
18
19
I
d
9
I
10
11
12
13
II
III
IV
V
o-MeC6H4
a
Unless otherwise stated, reactions were carried out according to the
conditions indicated by the above equation. 1.5 equiv of PhZnCl was
used. Isolated product yields. nr = no reaction. Reaction time was 9 h.
o-MeC6H4
b
c
d
p-EtOOCC6H4
p-EtOOCC6H4
p-PhC(O)C6H4
p-MeOC6H4
p-MeOC6H4
p-EtOOCC6H4
p-PhC(O)C6H4
m-MeOC6H4
p-EtOOCC6H4
p-PhC(O)C6H4
2-Py
e
20
21
22
applied in the following tests. Further studies using complexes II−V
as the catalyst showed that each of them gives lower yield than I
(entries 10−13, Table 1). The yields are I > III > II > IV > V.
It was also noted that in the I-catalyzed reaction, shorter
reaction time results in lower product yield (entry 9, Table 1).
Next, the counterion effect was examined using phenyl-
trimethylammonium salts as the electrophilic substrates and
f
23
24
25
26
2-furyl
2-furyl
g
27
2-thienyl
g
Cl−, Br−, I−, BF4 , and OTf−, respectively, as the counterion.
−
28
2-thienyl
The reaction of p-MeOC6H4ZnCl with PhNMe3 X− was
+
29
30
31
32
33
34
p-MeC6H4
o-MeC6H4
p-MeOC6H4
p-Me2NC6H4
2-furyl
2-Py
carried out in the presence of 1 mol % I in a 1:1 mixture of
NMP and THF at 85 °C (eq 1). The results showed that the
2-Py
2-Py
2-Py
2-Py
p-CF3C6H4
a
Unless otherwise stated, reactions were performed with 0.5 mmol
aryltrimethylammonium iodides and 0.75 mmol arylzinc chlorides
b
according to the conditions indicated by the above equation. Isolated
c
d
product yields. 2 mol % I was employed as the catalyst. 1 mol % III
e
f
was employed as the catalyst. Bath temperature was 130 °C. 5 mol %
I was employed as the catalyst. 2.5 equiv of 2-thienylzinc chloride was
g
employed.
+ −
aryltrimethylammonium iodides p-MeOC6H4NMe3 I and m-
halide salts are the most reactive, while the tetrafluoroborate
salt exhibits the lowest reactivity. The chloride, bromide, and
iodide display similar reactivity.
+ −
MeOC6H4NMe3 I also react with p-MeC6H4ZnCl smoothly,
giving cross-coupling products in excellent yields (entries 5 and
+ −
6, Table 2). However, reaction of p-MeOC6H4NMe3 I with
With the optimized reaction conditions, we tested the scope
of the cross-coupling reaction of aryltrimethylammonium
iodides with arylzinc reagents (Table 2). Reaction of phenyl-
trimethylammonium iodide with a series of arylzinc chlorides
gives good to excellent product yields (entries 1−4, Table 2). It
was noted that both p-MeOC6H4ZnCl and p-Me2NC6H4ZnCl
are less reactive than p-MeC6H4ZnCl, although the former two
nucleophiles are electron-rich ones. A supposed reason is that
coordination of the OMe or NMe2 group to a metal center
(e.g., Zn2+) decreases the nucleophilic activity of 4-methoxy-
phenyl or 4-dimethylaminophenyl anion. The electron-rich
o-MeC6H4ZnCl seems to be more difficult because of the
hindered effect of the ortho-methyl group in o-MeC6H4ZnCl.
I (1 mol %) results in only 68% product yield. Higher catalyst
loadings (2 mol %) lead to higher product yields (entries 7 and
8, Table 2). These results are consistent with the conversion of
1
the ammonium salt determined by H NMR spectra of the
crude products, 1 mol % I giving 75% conversion and 2 mol % I
leading to 86% conversion. We also estimated the TON of the
+ −
reaction of p-MeOC6H4NMe3 I with o-MeC6H4ZnCl cata-
lyzed by I, which is about 120. These facts showed that I is not
very efficient in catalyzing the cross-coupling of p-MeOC6H4NMe3+I−
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The Journal of Organic Chemistry
Note
and o-MeC6H4ZnCl. Further studies proved that complex III is
a better catalyst for this reaction. It leads to 88% isolated yield
under the same conditions as those using I as the catalyst
(entry 9, Table 2). The reaction using II as the catalyst gave
similar yield to that using I, whereas the reaction using IV or V as
the catalysts led to low yields. Reaction of m-MeOC6H4NMe3+I−
with p-Me2NC6H4ZnCl catalyzed by I also requires higher
catalyst loadings, which results in excellent product yields
(entry 10, Table 2). The electron-deficient aryltrimethylammo-
nium iodides show good reactivity. Reactions of both p-
low catalyst loadings in most cases and tolerate functional
groups such as ester, keto, and CF3 groups. Moreover, this
investigation proves the potential of amido pincer nickel
catalyst system for the C−N bond activation of aryltrimethyl-
ammonium salts. Further modification and optimization of the
structure of the ligands to improve their activity are underway.
EXPERIMENTAL SECTION
■
All air or moisture sensitive manipulations were performed under dry
nitrogen using standard Schlenk techniques. Solvents were distilled
under nitrogen over sodium (benzene, toluene), sodium/benzophe-
none (n-hexane, THF, and diethyl ether) or CaH2 (CH2Cl2) and
degassed prior to use. NMP was dried over 4 Å molecular sieves,
fractionally distilled under reduced pressure, and stored under
nitrogen atmosphere. n-BuLi was purchased from Acros Organics
and used as received. CDCl3 and DMSO-d6 were purchased from
Cambridge Isotope Laboratories, Inc., and stored over 4 Å molecular
sieves. ArNC(Cl)Ph,12 p-MeC6H4N3,13 2-diphenylphosphanylani-
line,14 N-benzylidene-2-(diphenylphosphino) benzeneamine,15
(DME)NiCl2,16 and (1-methylimidazol-2-yl)lithium17 were prepared
according to literature methods. Aryltrimethylammonium salts were
obtained either by preparation according to the procedures we used
previously10 or by purchasing from commercial vendors. ArZnCl
were prepared in situ through reaction of ZnCl2 with corresponding
aryllithium (p-MeC6H4Li,18 o-MeC6H4Li,19 p-Me2NC6H4Li,20 p-
CF3C6H4Li,21 p-MeOC6H4Li,21 2-furyllithium,22 and 2-thienyllithium23).
All other chemicals were obtained from commercial vendors and used
as received. NMR spectra were recorded on a 300 MHz spectrometer
+ −
+ −
EtOOCC6H4NMe3 I and p-PhC(O)C6H4NMe3 I with
either p-MeC6H4ZnCl or o-MeC6H4ZnCl gave excellent results
under the standard conditions (entries 11−14, Table 2).
+ −
Reaction of p-MeOC6H4ZnCl with p-EtOOCC6H4NMe3 I
also affords cross-coupling product in excellent yield (entry
+ −
15, Table 2). o-MeC6H4NMe3 I displays similar reactivity to
+ −
PhNMe3 I (entries 16−18, Table 2). The hindered effect of
its ortho-methyl group seems to be less than the corresponding
one in o-MeC6H4ZnCl. The electron-deficient nucleophiles
exhibit lower reactivity than electron-rich ones. Reactions of
p-EtOOCC6H4ZnBr with both unactivated and activated
aryltrimethylammonium iodides give poor results. However,
reaction of p-CF3C6H4ZnCl with activated aryltrimethylammo-
nium iodides generates cross-coupling products in good yields,
+ −
although reaction of p-EtOOCC6H4NMe3 I requires a higher
reaction temperature (entries 19−21, Table 2). Reaction of
+ −
1
at ambient temperature. The chemical shifts of the H and 13C NMR
deactivated p-MeOC6H4NMe3 I with p-CF3C6H4ZnCl gives a
spectra were referenced to TMS or internal solvent resonances; the 31P
NMR spectra were referenced to external 85% H3PO4. Elemental
analysis was performed by the Analytical Center of University of
Science and Technology of China. Column chromatography was
performed on silica gel (200−300 mesh).
poor result, only 42% yield of cross-coupling product being
isolated under the standard conditions. Catalyst loadings of
5 mol % for this reaction result in 56% product yield (entries 22
and 23, Table 2). In this reaction, the homocoupling of
p-CF3C6H4ZnCl is a main side reaction. Higher reaction tem-
peratures can not increase the yield of the cross-coupling product.
Heteroarylzinc reagents are also good nucleophilic substrates
in the reactions. Reactions of 2-furylzinc chloride with activated
Synthesis of 2-P(Ph2)C6H4NHC(Ph)N(p-MeC6H4) (1). A
mixture of 2-diphenylphosphanylaniline (1.20 g, 4.33 mmol), N-(p-
tolyl)benzimidoyl chloride (1.00 g, 4.35 mmol), and triethylamine
(0.66 mL, 4.57 mmol) in toluene (30 mL) was refluxed for 48 h.
(C2H5)3N·HCl was removed by filtration, and the filtrate was
concentrated to afford a yellow solid of 1 (0.915 g, 45%): mp 223−
224 °C; 1H NMR (CDCl3) δ 2.06 (s), 2.15 (s), 2.23 (s), 2.35 (s), 5.69
(b), 6.20−6.37 (m), 6.53−6.79 (m), 6.89−7.05 (m), 7.15−7.56 (m),
7.87 (d, J = 3.3 Hz); 13C NMR (CDCl3) δ 20.9, 21.1, 29.8, 120.6,
120.9, 122.5, 125.8, 127.8, 128.3, 128.4, 128.4, 128.8, 128.9, 129.3,
130.2, 130.4, 132.9, 134.0, 134.2, 134.3, 134.4, 138.2, 139.0, 156.6; 31P
NMR (CDCl3) δ −23.96, −16.94, −15.60, 26.42. Anal. Calcd for
C32H27N2P: C 81.68, H 5.78, N 5.95. Found: C 81.66, H 5.77, N 6.08.
Compounds 2 and 3 Were Synthesized Using the Same Method
+ −
aryltrimethylammonium iodides, p-EtOOCC6H4NMe3 I and
+ −
p-PhC(O)C6H4NMe3 I , afford cross-coupling products in
almost quantitative yields (entries 24 and 25, Table 2). How-
ever, the reaction using deactivated aryltrimethylammonium
+ −
salt, m-MeOC6H4NMe3 I , results in a relatively low yield
(entry 26, Table 2). 2-Thienylzinc chloride displays lower
reactivity than 2-furylzinc chloride. Reactions of 2-thienylzinc
+ −
chloride with either p-EtOOCC6H4NMe3 I or p-PhC(O)-
+ −
C6H4NMe3 I require excess zinc reagents (2.5 equiv) and
1
form corresponding cross-coupling products in 80 and 78%
yields, respectively (entries 27 and 28, Table 2). 2-Pyridyl-
trimethylammonium iodide is a highly active electrophilic species
in the reaction. Its reactions with a range of electron-rich zinc re-
agents proceed smoothly, giving corresponding cross-coupling
products in excellent yields (entries 29−33, Table 2).
2-Pyridyltrimethylammonium iodide also reacts with
p-CF3C6H4ZnCl, but the reaction gives a little lower product
yield (entry 34, Table 2).
In summary, we have synthesized several new amido pincer
nickel complexes and found them to be able to catalyze cross-
coupling of aryltrimethylammonium salts and arylzinc reagents.
Complex I, [Ni(Cl){2-P(Ph2)C6H4NC(Ph)N(p-
MeC6H4)}], exhibits the highest catalytic activity among I−V
and also shows higher catalytic activity than Ni(PCy3)2Cl2. It
leads to cross-coupling of activated, unactivated, and de-
activated aryltrimethylammonium iodides as well as 2-pyri-
dyltrimethylammonium iodide with aryl- or heteroarylzinc
reagents in moderate to excellent yields. The reactions require
as for 1. 2, (0.70 g, 33%), yellow solid: mp 203−205 °C; H NMR
(CDCl3) δ 6.10−6.67 (m), 6.77−6.98 (m), 7.11−7.27 (m), 7.34 (s),
7.48−7.78 (m), 8.94 (s), 10.17 (s); 13C NMR (CDCl3) δ 121.7, 121.9,
122.3, 122.4, 123.5, 123.8, 128.4, 128.65, 128.74, 129.4, 129.6, 129.9,
132.2, 132.3, 133.1, 134.0, 134.3; 31P NMR (CDCl3) δ −20.68,
−17.03, 25.53, 32.61. Anal. Calcd for C31H24N2ClP·0.2H2O (the
sample for elemental analysis was purified by recrystallization in a
mixture of ethanol and water): C 75.29, H 4.97, N 5.66. Found: C
75.17, H 4.83, N 5.58.
3, (1.41 g, 67%), yellow solid: mp 170−172 °C; 1H NMR (DMSO-d6)
δ 3.42 (s), 3.50 (s), 3.57 (s), 3.67 (s), 6.23 (s), 6.41 (s), 6.53−6.73
(m), 6.84−6.96 (m), 7.12 (s), 7.29 (s), 7.40 (s), 7.54−7.75 (m), 7.99
(d, J = 6.6 Hz), 8.35 (s), 9.10 (s), 9.16 (s); 13C NMR (DMSO-d6)
δ 55.0, 55.3, 79.2, 113.1, 113.2, 113.4, 113.6, 113.7, 120.2, 120.7, 121.1,
121.2, 121.7, 122.0, 122.5, 126.8, 127.7, 128.0, 128.5, 128.6, 128.9,
129.0, 129.4, 129.7, 129.8, 130.3, 131.3, 131.8, 131.9, 133.6, 133.9,
134.1, 134.9, 137.3, 137.4, 153.6, 153.9, 154.3; 31P NMR (DMSO-d6)
δ −19.30, −18.53, −17.54, 23.70. Anal. Calcd for C32H27N2OP: C
78.99, H 5.59, N 5.76. Found: C 78.95, H 5.78, N 5.69.
Synthesis of [Ni(Cl){2-P(Ph2)C6H4NC(Ph)N(p-MeC6H4)}] (I).
To a stirred suspension of 1 (0.37 g, 0.79 mmol) in THF (10 mL) was
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Note
1
added dropwise LDA [prepared from diisopropylamine (0.12 mL,
0.85 mmol) and n-BuLi (0.34 mL, a 2.5 M of solution in hexane,
0.85 mmol) in THF (10 mL)] at about −80 °C. The mixture was
warmed to room temperature and stirred for 3 h. The resultant
solution was added dropwise to a stirred suspension of (DME)NiCl2
(0.17 g, 0.79 mmol) in THF (10 mL) at about −80 °C. The mixture
was warmed to room temperature and stirred overnight. Solvent was
removed in vacuo. The residue was dissolved in toluene. The resultant
solution was filtered, and the filtrate was concentrated to give brown
crystals of I (0.24 g, 53%): mp 252−254 °C; 1H NMR (CDCl3) δ 2.14
(s, 3H), 6.17 (dd, J = 4.2, 8.4 Hz, 1H), 6.69 (d, J = 8.1 Hz, 2H), 6.72−
6.82 (m, 3H), 6.90 (t, J = 7.8 Hz, 1H), 7.15 (t, J = 8.4 Hz, 1H), 7.37−
7.57 (m, 11H), 7.91−7.98 (m, 4H); 13C NMR (CDCl3) δ 20.8, 115.2
(d, J = 9.4 Hz), 121.7 (d, J = 7.2 Hz), 123.6, 127.6, 128.7, 128.9, 129.1,
129.3, 130.7, 131.2 (d, J = 2.3 Hz), 132.4, 132.9, 133.2, 133.4, 133.5,
139.8, 151.7, 152.0, 169.4; 31P NMR (CDCl3) δ 25.23. Anal. Calcd
for C32H26N2PClNi: C 68.18, H 4.65, N 4.97. Found: C 67.81, H 4.59,
N 4.76.
(0.24 g, 63%): mp 242−244 °C; H NMR (CDCl3) δ 3.38 (s, 3H),
5.15 (s, 1H), 6.15−6.29 (m, 2H), 6.63 (s, 1H), 6.80−6.98 (m, 2H),
7.06 (s, 1H), 7.12−7.33 (m, 4H), 7.35−7.55 (m, 5H), 7.74 (d, J = 6.9
Hz, 2H), 7.83−8.04 (m, 4H); 13C NMR (CDCl3) δ 34.3, 63.0, 112.4,
113.2, 121.1, 123.9, 128.1 128.2, 128.6, 128.8, 128.9, 130.8 (d, J = 12.1
Hz), 132.8, 133.1, 133.2, 133.3, 133.8 (d, J = 10.3 Hz), 139.3; 31P
NMR (CDCl3) δ 26.35. Anal. Calcd for C29H25N3PClNi·0.15C7H8: C
65.09, H 4.76, N 7.58. Found: C 64.96, H 4.76, N 7.47.
Synthesis of 2-(p-MeC6H4NPPh2)C6H4NHC(Ph)CN(CH)2NMe (6).
To a stirred solution of 5 (0.31 g, 0.69 mmol) in CH2Cl2 (10 mL) was
added dropwise p-MeC6H4N3 (0.097 g, 0.73 mmol). The mixture was
stirred at room temperature for 2 h. Solvent was removed in vacuo.
The residue was washed with hexane to afford a yellow powder
1
(0.30 g, 79%): mp 163−165 °C; H NMR (CDCl3) δ 2.17 (s, 3H),
3.12 (s, 3H), 5.94 (d, J = 4.8 Hz, 1H), 6.39 (d, J = 8.1 Hz, 2H), 6.57
(dt, J = 2.4, 7.5 Hz, 1H), 6.67 (s, 1H), 6.74 (d, J = 8.1 Hz, 2H), 6.79−
6.93 (m, 2H), 6.96 (s, 1H), 7.15−7.32 (m, 7H), 7.38−7.61 (m, 6H),
7.63−7.77 (m, 4H), 9.47 (d, J = 4.8 Hz, 1H); 13C NMR (CDCl3)
δ 14.2, 20.6, 22.8, 29.8, 33.0, 56.2, 112.6 (d, J = 8.5 Hz), 116.0 (d,
J = 14.3 Hz), 122.2, 122.3, 122.6, 126.8, 127.1, 127.5, 128.8, 128.9 (d,
J = 5.1 Hz), 129.4, 132.0, 132.8, 132.9, 133.0, 133.3, 133.4, 133.6,
138.9, 147.1, 151.6 (d, J = 3.4 Hz); 31P NMR (CDCl3) δ 8.20. Anal.
Calcd for C36H33N4P: C 78.24, H 6.02, N 10.14. Found: C 78.08,
H 6.03, N 9.81.
Complexes II and III Were Synthesized from 2 and 3 Using the
Same Procedure as for I. II, (0.20 g, 43%), brown solid: mp 238−240
1
°C; H NMR (CDCl3) δ 6.20 (dd, J = 4.5, 8.4 Hz, 1H), 6.71 (d, J =
8.7 Hz, 2H), 6.79 (t, J = 7.2 Hz, 1H), 6.92 (d, J = 8.7 Hz, 1H), 6.95 (d,
J = 8.7 Hz, 2H), 7.17 (t, J = 8.4 Hz, 1H), 7.39 (d, J = 6.9 Hz, 2H),
7.44−7.59 (m, 9H), 7.94 (dd, J = 7.2, 12.3 Hz, 4H); 13C NMR
(CDCl3) δ 115.6 (d, J = 9.2 Hz), 122.3 (d, J = 6.7 Hz), 122.8, 125.0,
127.7, 128.5, 128.6, 129.2 (d, J = 10.9 Hz), 129.6, 131.06, 131.5, 132.6,
132.8, 133.4 (d, J = 10.7 Hz), 133.7, 141.4, 151.5, 151.8, 169.9; 31P
NMR (CDCl3) δ 25.82. Anal. Calcd for C31H23N2Cl2PNi: C 63.74, H
3.97, N 4.80. Found: C 63.42, H 3.88, N 4.87.
Synthesis of [Ni(Cl){2-(p-MeC6H4NPPh2)C6H4NC(Ph)-
CN(CH)2NMe] (V). To a stirred suspension of 6 (0.34 g, 0.62 mmol)
in THF (15 mL) was added dropwise n-BuLi (0.25 mL, a 2.5 M solution
in hexanes, 0.63 mmol) at about −80 °C. The mixture was warmed to
room temperature and stirred for 3 h. The resultant solution was added
dropwise to a stirred suspension of (DME)NiCl2 (0.14 g, 0.94 mmol) in
THF(10 mL) at about −80 °C. The mixture was warmed to room
temperature and stirred overnight. Solvent was removed in vacuo, and the
residue was dissolved in CH2Cl2. The resultant solution was filtered, and
the filtrate was concentrated to give blue crystals of V (0.28 g, 70%): mp
1
III·0.8C7H8, (0.186 g, 36%), brown solid: mp 221−222 °C; H
NMR (CDCl3) δ 2.36 (s), 3.66 (s, 3H), 6.16 (dd, J = 4.2, 8.1 Hz, 1H),
6.56 (d, J = 8.7 Hz, 2H), 6.74 (d, J = 8.7 Hz, 2H), 6.91 (t, J = 8.1 Hz,
1H), 7.15 (t, J = 8.4 Hz, 1H), 7.34−7.57 (m, 11H), 7.95 (dd, J = 7.2,
12 Hz, 4H); 13C NMR (CDCl3) δ 55.4, 113.8, 115.3 (d, J = 9.7 Hz),
121.4, 121.6 (d, J = 7.2 Hz), 122.1, 124.9, 125.4, 127.8, 128.4, 128.9,
129.1, 129.2, 129.5, 130.8, 131.3 (d, J = 2 Hz), 132.5, 133.0, 133.4,
133.5, 133.7, 152.0, 152.2, 169.1; 31P NMR (CDCl3) δ 25.39. Anal.
Calcd for C32H26N2ClPONi·0.8C7H8: C 69.12, H 5.00, N 4.29. Found:
C 69.11, H 5.06, N 4.36.
1
275−278 °C; H NMR (CDCl3) δ 2.24 (s, 3H), 3.22 (s, 3H), 5.30 (s),
5.63 (s, 1H), 6.07 (dt, J = 2.4, 7.2 Hz, 1H), 6.55 (s, 1H), 6.61−6.69 (m,
2H), 6.86 (d, J = 7.8 Hz, 2H), 6.92 (s, 1H), 7.13−7.40 (m, 8H), 7.45−
7.59 (m, 5H), 7.60−7.68 (m, 1H), 7.87 (d, J = 7.5 Hz, 1H), 7.91 (d, J =
7.2 Hz, 1H), 8.09 (d, J = 7.2, 2H); 13C NMR (CDCl3) δ 20.9, 34.3, 53.6
(CH2Cl2), 62.0, 111.8 (d, J = 13.4 Hz), 119.4, 123.0, 127.8, 128.1, 128.4,
128.6, 128.65, 128.72, 128.8, 132.2, 132.6, 132.8, 133.0, 133.1, 134.3 (d,
J = 9.8 Hz), 134.8 (d, J = 9.9 Hz), 141.9, 144.6, 154.3, 157.7; 31P NMR
(CDCl3) δ 17.01. Anal. Calcd for C36H32N4PClNi·0.5CH2Cl2: C 63.70, H
4.83, N 8.14. Found: C 63.79, H 4.83, N 8.13.
Synthesis of 2-(PPh2)C6H4NHC(Ph)CN(CH)2NMe (5). A solution
of compound 4 (0.45 g, 1.23 mmol) in THF (15 mL) was cooled
to about −80 °C. To the stirred solution was added dropwise a THF
solution of C4H5N2Li [prepared from 1-methylimidazole (0.10 g,
1.21 mmol) and n-BuLi (0.50 mL, a 2.5 M of solution in hexane,
1.25 mmol) in THF (10 mL)]. The mixture was warmed to room
temperature and stirred for 12 h. Water (15 mL) was added to the
mixture. The organic phase was separated, and the water phase was
extracted with diethyl ether (3 × 10 mL). The combined organic
phases were dried over anhydrous Na2SO4, concentrated by rotary
evaporation, and recrystallized in toluene to afford a white solid of
5 (0.40 g, 72%): mp 150−151 °C; 1H NMR (CDCl3) δ 3.26 (s, 3H),
5.74−5.80 (m, 2H), 6.61−6.70 (m, 3H), 6.79−6.83 (m, 1H), 6.96 (s,
1H), 7.12−7.16 (m, 3H), 7.20−7.25 (m, 3H), 7.32−7.35(m, 10H);
13C NMR (CDCl3) δ 33.0, 56.0, 111.4, 118.1, 120.2 (d, J = 8.3 Hz),
122.0, 126.9, 127.6 (d, J = 12.8 Hz), 128.6, 128.7, 128.8, 129.0, 130.7,
133.7, 133.9 (d, J = 3 Hz), 134.2, 134.3 (d, J = 2.3 Hz), 135.3 (d, J =
7.2 Hz), 139.4, 147.1, 149.0, 149.3; 31P NMR (CDCl3) δ −25.45. Anal.
Calcd for C29H26N3P: C 77.83, H 5.86, N 9.39. Found: C 77.48, H
5.84, N 9.29.
General Procedure for Reaction of ArZnCl with Aryltrime-
thylammonium Iodides. A Schlenk tube was charged with
aryltrimethylammonium iodides (0.5 mmol), catalyst (0.005 mmol),
and NMP (or other solvent needed) (1.5 mL). To the stirred mixture
was added ArZnCl solution (1.5 mL, 0.5 M solution in THF,
0.75 mmol) by syringe. The reaction mixture was stirred at 85 °C
(bath temperature) for 12 h and then cooled to room temperature.
Water (10 mL) and several drops of acetic acid were successively
added. The resulting mixture was extracted with Et2O (3 × 10 mL).
The extract was dried over Na2SO4, filtered, and concentrated. The
residue was purified by column chromatography on sillca gel.
Spectral Data for the Cross-Coupling Products. 4-Methoxy-
4′-methylbiphenyl.10 Spectral data: 1H NMR (CDCl3) δ 2.28 (s,
3H), 3.72 (s, 3H), 6.86 (d, J = 8.7 Hz, 2H), 7.12 (d, J = 7.8 Hz,
2H), 7.35 (d, J = 7.8 Hz, 2H), 7.41 (d, J = 8.7 Hz, 2H); 13C
NMR (CDCl3) δ 21.2, 55.4, 114.2, 126.7, 128.0, 129.6, 133.8,
136.4, 138.0, 159.0.
Synthesis of [Ni(Cl){2-(PPh2)C6H4NC(Ph)CN(CH)2NMe}] (IV).
To a stirred suspension of 5 (0.31 g, 0.69 mmol) in THF (10 mL) was
added dropwise n-BuLi (0.28 mL, a 2.5 M solution in hexanes,
0.70 mmol) at about −80 °C. The mixture was warmed to room
temperature and stirred for 3 h. The resultant solution was added
dropwise to a stirred suspension of (DME)NiCl2 (0.15 g, 0.69 mmol)
in THF (10 mL) at about −80 °C. The mixture was warmed to room
temperature and stirred overnight. Solvent was removed in vacuo, and
the residue was dissolved in toluene. The resultant solution was
filtered, and the filtrate was concentrated to give green crystals of IV
4-Methoxybiphenyl.10 Spectral data: H NMR (CDCl3) δ 3.88 (s,
1
3H), 7.03 (d, J = 8.7 Hz, 2H), 7.35 (t, J = 7.5 Hz, 1H), 7.46 (t, J =
7.5 Hz, 2H), 7.57−7.62 (m, 4H); 13C NMR (CDCl3) δ 55.4, 114.3,
126.8, 126.8, 128.2, 128.3, 133.8, 140.9, 159.3.
4-Methylbiphenyl.10 Spectral data: H NMR (CDCl3) δ 2.39 (s,
1
3H), 7.24 (d, J = 7.5 Hz, 2H), 7.31 (t, J = 7.2 Hz, 1H), 7.42 (t, J = 7.5
Hz, 2H), 7.49 (d, J = 8.1 Hz, 2H), 7.57 (d, J = 7.8 Hz, 2H); 13C NMR
3661
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The Journal of Organic Chemistry
Note
(CDCl3) δ 21.2, 126.9, 127.1, 127.1, 128.8, 129.6, 129.6, 137.1, 138.5,
4′-Methoxy-4-(trifluoromethyl)biphenyl.27 Spectral data: 1H NMR
(CDCl3) δ 3.84 (s, 3H), 6.98 (d, J = 8.7 Hz, 2H), 7.52 (d, J = 9 Hz,
2H),7.64 (s, 4H); 13C NMR (CDCl3) δ 55.5, 114.6, 122.8, 125.8 (q,
J = 3.8 Hz), 126.4, 127.0, 128.5, 128.6, 129.0, 132.3, 144.4, 160.0.
Ethyl 4-(Furan-2-yl)benzoate.10 Spectral data: 1H NMR (CDCl3) δ
1.39 (t, J = 7.2 Hz, 3H), 4.37 (q, J = 7.2 Hz, 2H), 6.48 (dd, J = 1.8, 3.6
Hz, 1H), 6.76 (d, J = 3.3 Hz, 1H), 7.49 (d, J = 1.5 Hz, 1H), 7.70 (d,
J = 8.7 Hz, 2H), 8.05 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3) δ 14.4,
61.0, 107.2, 112.1, 123.4, 128.9, 130.1, 134.7, 143.1, 153.0 166.4.
(4-(Furan-2-yl)phenyl)(phenyl)methanone.11a Spectral data: 1H
NMR (CDCl3) δ 6.53 (dd, J = 1.8, 3.6 Hz, 1H), 6.82 (dd, J = 0.6, 3.3
Hz, 1H), 7.46−7.63 (m, 4H), 7.75−7.87 (m, 6H); 13C NMR (CDCl3)
δ 107.5, 112.2, 123.4, 128.4, 130.0, 130.9, 132.4, 134.6, 136.0, 137.9,
143.4, 153.0, 196.1.
141.3.
2-Methylbiphenyl.10 Spectral data: H NMR (CDCl3) δ 2.26 (s,
1
3H), 7.20−7.26 (m, 4H), 7.28−7.33 (m, 3H), 7.37−7.42 (m, 2H); 13C
NMR (CDCl3) δ 20.6, 125.9, 126.9, 127.4, 128.2, 129.3, 129.9, 130.4,
135.5, 142.1, 142.1.
N,N-Dimethylbiphenyl-4-amine.10 Spectral data: 1H NMR
(CDCl3) δ 2.86 (s, 6H), 6.69 (d, J = 9 Hz, 2H), 7.11−7.17 (m,
1H), 7.28 (t, J = 7.5 Hz, 2H), 7.40 (d, J = 8.7 Hz, 2H), 7.44−7.47 (m,
2H); 13C NMR (CDCl3) δ 40.7, 112.9, 126.1, 126.4, 127.8, 128.8,
129.4, 141.4, 150.1.
3-Methoxy-4′-methylbiphenyl.10 Spectral data: 1H NMR (CDCl3)
δ 2.37 (s, 3H), 3.82 (s, 3H), 6.85 (dd, J = 2.1, 8.1 Hz, 1H), 7.10 (t, J =
2.1, 1H), 7.15 (d, J = 7.8 Hz, 1H), 7.22 (d, J = 8.1 Hz, 2H), 7.32 (t, J =
8.1 Hz, 1H), 7.47 (d, J = 8.1 Hz, 2H); 13C NMR (CDCl3) δ 21.2, 55.4,
112.5, 112.8, 119.6, 127.1, 129.6, 129.8, 137.3, 138.3, 142.8, 160.1.
1-(4-Methoxyphenyl)-2-methylbenzene.10 Spectral data: 1H NMR
(CDCl3) δ2.27 (s, 3H), 3.82 (s, 3H), 6.93 (d, J = 8.4 Hz, 2H), 7.18−
7.25 (m, 6H); 13C NMR (CDCl3) δ 20.6, 55.3, 113.6, 125.9, 127.1,
129.4, 130.0, 130.3, 130.4, 134.5, 135.6, 141.7, 158.6.
2-(3-Methoxyphenyl)furan.28 Spectral data: 1H NMR (CDCl3)
δ 3.77 (s, 3H), 6.40 (dd, J = 1.8, 3.3 Hz, 1H), 6.59 (d, J = 3.3, Hz, 1H),
6.72−6.79 (m, 1H), 7.16−7.23 (m, 3H), 7.40 (d, J = 1.2 Hz, 1H); 13C
NMR (CDCl3) δ 55.3, 105.4, 109.3, 111.8, 113.3, 116.5, 129.8, 132.3,
142.2, 153.9, 160.0.
2-(4-Ethoxycarbonylphenyl)thiophene.29 Spectral data: H NMR
1
3′-Methoxy-N,N-dimethylbiphenyl-4-amine. Spectral data: 1H
NMR (CDCl3) δ 2.95 (s, 6H), 3.82 (d, 3H), 6.75−6.81 (m, 3H),
7.09 (t, J = 2.1 Hz, 1H), 7.12−7.16 (m, 1H), 7.29 (t, J = 8.1 Hz, 1H),
7.47−7.51 (m, 2H); 13C NMR (CDCl3) δ 40.8, 55.3, 111.5, 112.1,
113.0, 119.0, 127.9, 129.5, 129.7, 142.8, 150.0, 160.0; HR-MS (EI)
m/z 228.1388 [M + H]+, calcd for C15H18NO 228.1382.
(CDCl3) δ 1.41 (t, J = 6.9 Hz, 3H), 4.39 (q, J = 6.9 Hz, 2H), 7.11 (dd,
J = 4.2, 4.8 Hz, 1H), 7.35 (d, J = 4.8 Hz, 1H), 7.42 (d, J = 3.6 Hz, 1H),
7.67 (d, J = 8.4 Hz, 2H), 8.04 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3)
δ 14.5, 61.1, 124.6, 125.6, 126.3, 128.4, 129.3, 130.4, 138.7, 143.3,
166.4.
Phenyl(4-(thiophen-2-yl)phenyl)methanone.30 Spectral data: 1H
NMR (CDCl3) δ 7.13 (dd, J = 3.9, 5.1 Hz, 1H), 6.81 (dd, J = 0.9, 5.1
Hz, 1H), 7.45 (dd, J = 1.2, 3.6 Hz, 1H), 7.47−7.53 (m, 2H), 7.57−
7.63 (m, 1H), 7.70−7.74 (m, 2H), 7.80−7.86 (m, 4H); 13C NMR
(CDCl3) δ 124.7, 125.6, 126.5, 128.4, 128.5, 130.1, 131.1, 132.5, 136.2,
137.8, 138.4, 143.1, 196.1.
Ethyl 4′-Methylbiphenyl-4-carboxylate.11a Spectral data: 1H NMR
(CDCl3)) δ 1.41 (t, J = 7.2 Hz, 3H), 2.41 (s, 3H), 4.40 (q, J = 7.2 Hz,
2H), 7.27 (d, J = 8.7 Hz, 2H), 7.53 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 8.4
Hz, 2H), 8.09 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3) δ 14.5, 21.2,
61.0,126.8, 127.2, 129.0, 129.7, 130.1, 137.2, 138.1, 145.5, 166.7.
Phenyl(p-tolyl)methanone.10 Spectral data: 1H NMR (CDCl3)
δ 2.32 (s, 3H), 7.19 (d, J = 7.8 Hz, 2H), 7.37−7.53 (m, 5H), 7.59 (d,
J = 8.7 Hz, 2H), 7.72−7.81 (m, 4H); 13C NMR (CDCl3) δ 21.3, 126.8,
127.2, 128.4, 129.8, 130.1, 130.8, 132.4, 136.1, 137.2, 138.0, 138.3,
145.3, 196.4.
p-Tolylpyridine.11a Spectral data: 1H NMR (CDCl3) δ 2.29 (s, 3H),
7.02−7.18 (m, 1H), 7.17 (d, J = 8.4 Hz, 2H), 7.55−7.59 (m, 2H), 7.79
(d, J = 8.4 Hz, 2H), 8.56 (dt, J = 1.5, 4.8 Hz, 1H); 13C NMR (CDCl3)
δ 21.3, 120.3, 121.8, 126.8, 129.5, 136.7, 139.0, 149.6, 157.5.
o-Tolylpyridine.24 Spectral data: 1H NMR (CDCl3) δ 2.27 (s, 3H),
7.11−7.21 (m, 4H), 7.28−7.31 (m, 2H), 7.63 (dt, J = 1.8, 7.8 Hz Hz,
1H), 8.59 (d, J = 4.5 Hz, 1H); 13C NMR (CDCl3) δ 20.3, 121.7, 124.2,
125.9, 128.3, 129.7, 130.8, 135.8, 136.2, 140.5, 149.2, 160.1.
2-(4′-Methoxyphenyl)pyridine.24 Spectral data: 1H NMR (CDCl3)
δ 3.83 (s, 3H), 6.99 (d, J = 8.7 Hz, 2H), 7.12−7.16 (m, 1H), 7.62−
7.70 (m, 2H), 7.95 (d, J = 8.7 Hz, 2H), 8.64 (d, J = 4.8 Hz, 1H); 13C
NMR (CDCl3) δ 55.4, 114.2, 119.9, 121.5, 128.2, 132.1, 136.7, 149.6,
157.2, 160.5.
Ethyl 2′-Methylbiphenyl-4-carboxylate.11a Spectral data: 1H NMR
(CDCl3) δ 1.31 (t, J = 7.2 Hz, 3H), 2.16 (s, 3H), 4.30 (q, J = 7.2 Hz,
2H), 7.12−7.17 (m, 4H), 7.29 (d, J = 7.8 Hz, 2H), 8.00 (d, J = 8.1 Hz,
2H); 13C NMR (CDCl3) δ 14.5, 20.4, 61.0, 126.0, 127.9, 129.1, 129.3,
129.5, 129.6, 130.6, 135.2, 141.0, 146.7, 166.6.
(2′-Methylbiphenyl-4-yl)(phenyl)methanone.11a Spectral data: H
1
NMR (CDCl3) δ 2.17 (s, 3H), 7.11−7.16 (m, 4H), 7.28−7.38 (m,
4H), 7.43−7.48 (m, 1H), 7.71−7.75 (m, 4H); 13C NMR (CDCl3)
δ 20.5, 126.0, 127.9, 128.4, 129.2, 129.6, 130.1, 130.6, 132.4, 135.2,
136.0, 137.8, 140.9, 146.4, 196.4.
N,N-Dimethyl-4-(pyridin-2-yl)benzenamine.10 Spectral data: 1H
NMR (CDCl3) δ 3.02 (s, 6H), 6.80 (d, J = 8.7 Hz, 2H), 7.07−7.12 (m,
1H), 7.63−7.70 (m, 2H), 7.92 (d, J = 9 Hz, 2H), 8.61 (d, J = 4.8 Hz,
1H); 13C NMR (CDCl3) δ 40.4, 112.3, 119.1, 120.6, 127.3, 127.7,
136.5, 149.4, 151.1, 157.6.
Ethyl 4′-Methoxybiphenyl-4-carboxylate.24 Spectral data: 1H
NMR (CDCl3) δ 1.41 (t, J = 7.2, 3H), 3.86 (s, 3H), 4.40 (q, J =
7.2, 2H), 7.00 (d, J = 8.7 Hz, 2H), 7.57 (d, J = 8.7 Hz, 4H), 7.62 (d,
J = 8.4 Hz, 4H), 8.08 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3) δ 14.5,
55.5, 61.1, 114.5, 126.6, 128.5, 128.8, 130.2, 132.6, 145.3, 160.0, 166.8.
2-(Furan-2-yl)pyridine.11a Spectral data: H NMR (CDCl3) δ 6.52
1
(dd, J = 1.8, 3.6 Hz, 1H), 7.05 (dd, J = 0.6, 3.3 Hz, 1H), 7.09−7.18 (m,
1H), 7.52 (dd, J = 0.6, 1.8 Hz, 1H), 7.65−7.73 (m, 2H), 8.58 (dt, J =
1.2, 4.8 Hz, 1H); 13C NMR (CDCl3) δ 108.7, 112.2, 118.7, 122.0,
136.7, 143.4, 149.5, 149.7, 153.7.
2,4′-Dimethylbiphenyl.25 Spectral data: H NMR (CDCl3) δ 2.26
1
(s, 3H), 2.37 (s, 3H), 7.16- 7.24 (m, 8H); 13C NMR (CDCl3) δ 20.6,
21.3, 125.9, 126.9, 127.2, 128.9, 129.2, 129.6, 130.0, 130.4, 135.5,
136.4, 139.2, 142.0.
2-(4-(Trifluoromethyl)phenyl)pyridine.31 Spectral data: 1H NMR
(CDCl3) δ 7.28−7.32 (m, 1H), 7.72−7.83 (m, 4H), 8.11 (d, J = 8.1
Hz, 2H), 8.73 (d, J = 4.8 Hz, 1H); 13C NMR (CDCl3) δ 120.9, 122.6,
123.1, 125.8 (J = 3.8 Hz), 126.2, 127.3, 130.7, 131.1, 137.1, 142.8,
150.1, 156.0.
2′-Methyl-N,N-dimethylbiphenyl-4-amine.24 Spectral data: 1H
NMR (CDCl3) δ 2.22 (s, 3H), 2.89 (d, 6H), 6.69 (d, J = 8.7 Hz,
2H), 7.09−7.17 (m, 6H); 13C NMR (CDCl3) δ 20.8, 40.8, 112.3,
125.9, 126.7, 130.1, 130.4, 135.6, 142.1, 149.4.
Ethyl 4-[4-(Trifluoromethyl)phenyl]benzoate.10 Spectral data: H
1
NMR (CDCl3) δ 1.42 (t, J = 7.2 Hz, 3H), 4.41 (q, J = 7.2 Hz, 2H),
7.65 (d, J = 8.7 Hz, 2H), 7.71 (s, 4H), 8.14 (d, J = 8.7 Hz, 2H); 13C
NMR (CDCl3) δ 14.4, 61.2, 125.9 (q, J = 3.7 Hz), 122.5, 127.3, 127.7,
128.5, 129.7, 130.2, 130.3, 143.6, 144.0, 166.3.
ASSOCIATED CONTENT
■
S
* Supporting Information
Synthetic routes of the ligand precursors and nickel complexes.
Crystal structure determination details, crystal data, and ORTEP
Phenyl-[4-[4-(trifluoromethyl)phenyl]phenyl]methanone.26 Spec-
tral data: 1H NMR (CDCl3) δ 7.48- 7.54 (m, 2H), 7.59−7.65 (m, 1H),
7.71 (d, J = 8.7 Hz, 2H), 7.75 (s, 4H), 7.83−7.87 (m, 2H), 7.92 (d, J =
8.4 Hz, 2H); 13C NMR (CDCl3) δ 122.5, 126.1 (q, J = 3.8 Hz), 127.3,
127.8, 128.5, 130.2, 130.9, 132.7, 137.3, 137.7, 143.67, 143.69, 143.73,
196.3.
drawings of complexes I and V. Copies of H and 13C NMR
1
spectra of the cross-coupling products, ligand precursors, and
nickel complexes. This material is available free of charge via the
Internet at http://pubs.acs.org.
3662
dx.doi.org/10.1021/jo300209d | J. Org. Chem. 2012, 77, 3658−3663

The Journal of Organic Chemistry
Note
(20) Pereira, R.; Furst, A.; Iglesias, B.; Germain, P.; Gronemeyer, H.;
de Lera, A. R. Org. Biomol. Chem. 2006, 4, 4514.
(21) Jin, L.; Xin, J.; Huang, Z.; He, J.; Lei, A. J. Am. Chem. Soc. 2010,
132, 9607.
(22) Wakefield, B. J. Organolithium Methods; Academic Press:
London, 1988.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: zxwang@ustc.edu.cn.
Notes
The authors declare no competing financial interest.
(23) Takahashi, K.; Suzuki, T.; Akiyama, K.; Ikegami, Y.; Fukazawat,
Y. J . Am. Chem. Soc. 1991, 113, 4511.
ACKNOWLEDGMENTS
(24) Liu, N; Wang, Z.-X. J. Org. Chem. 2011, 76, 10031.
(25) Xi, Z.-X.; Liu, B.; Chen, W.-Z. J. Org. Chem. 2008, 73, 3955.
(26) Denmark, S. E.; Smith, R. C.; Chang, W.-T. T.; Muhuhi, J. M.
J. Am. Chem. Soc. 2009, 131, 3104.
(27) Ackermann, L.; Althammer, A. Org. Lett. 2006, 8, 3457.
(28) Nadres, E. T.; Lazareva, A.; Daugulis, O. J. Org. Chem. 2011, 76,
471.
■
This research was supported by the National Basic Research
Program of China (Grant No. 2009CB825300) and the
National Natural Science Foundation of China (Grant No.
20772119).
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