Kumada coupling of aryl, heteroaryl, and vinyl chlorides catalyzed by amido pincer nickel complexes

Article abstract of DOI:10.1021/jo201821g

A series of amido pincer complexes of nickel were examined for their catalysis in the Kumada cross-coupling reaction. The P,N,O-pincer nickel complexes tested are active catalysts for the cross-coupling of aryl, heteroaryl, and vinyl chlorides with aryl Grignard reagents. The reactions can proceed at room temperature and tolerate functional groups in aryl chlorides with the aid of LiCl and ZnCl₂ additives (Figure presented).

Full text of DOI:10.1021/jo201821g

Article
pubs.acs.org/joc
Kumada Coupling of Aryl, Heteroaryl, and Vinyl Chlorides Catalyzed
by Amido Pincer Nickel Complexes
Ning Liu 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: A series of amido pincer complexes of nickel were
examined for their catalysis in the Kumada cross-coupling reaction.
The P,N,O-pincer nickel complexes tested are active catalysts for
the cross-coupling of aryl, heteroaryl, and vinyl chlorides with aryl
Grignard reagents. The reactions can proceed at room temperature
and tolerate functional groups in aryl chlorides with the aid of LiCl
and ZnCl additives.
2
1
1,33−40
INTRODUCTION
The transition-metal-catalyzed Kumada cross-coupling reaction
is one of the most important methods to construct new C−C
bonds in organic synthesis.
nickel-catalyzed cross-coupling of a Grignard reagent with
alkenyl or aryl halides by Kumada and Corriu independently,
the reaction has been extensively investigated and widely used
in modern synthetic chemistry. Aryl, alkenyl, or alkyl bromides
and iodides have been predominately used as the electrophilic
reagents or functionalized halides are very rare.
■
Exploration of the catalytic systems for the functionalized
substrates is still challenging.
1
−3
Recently, we reported the synthesis of several P,N,O- and
P,N,S-pincer nickel complexes (Scheme 1) and their catalysis in
Since the initial report of the
4,5
Scheme 1. Amido-Pincer Nickel Complexes 1−4b
6−14
partners in the last decades.
Organic chlorides, as the more
useful substrates because of their lower cost in industrial
15,16
processes and the diversity of available compounds,
have
attracted considerable attention in recent years. Several types of
catalysts have proven to be highly effective for the coupling of
organic chlorides with Grignard reagents. For example,
Herrmann and co-workers reported that a mixture of Ni(acac)2
and imidazolium salts catalyzed cross-coupling of aryl chlorides
17
with aryl Grignard reagents efficiently. Nolan and Organ
respectively carried out biaryl Kumada coupling using
1
8,19
palladium−NHC catalysts.
Chen and co-workers described
a series of Ni−NHC complexes that provide good results for
Kumada coupling of aryl chlorides at room temperature.
20−22
4
1
Nickel and palladium with phosphine or phosphine oxide
ligands are also effective catalysts for the Kumada coupling of
the Negishi cross-couplings of aryl chlorides.
As a
continuation, we investigated catalysis of the complexes in
the Kumada coupling of aryl, heteroaryl, and alkenyl chlorides.
For the substrates that tolerate the background reactivity of a
Grignard reagent, Kumada cross-coupling offers a more direct
access to the desired products and hence is a more atom-
23−27
aryl or alkyl chlorides.
We found that nickel complexes
supported by pincer ligands exhibited good catalytic activity in
the cross-coupling of aryl chlorides with aryl Grignard
2
8−30
reagents.
Iron and cobalt complexes were also reported
31,32
to catalyze the Kumada coupling of aryl or alkyl chlorides.
Although this progress has been achieved, investigations of
widely applicable catalysts are still of interest. In addition,
catalysts for the reactions using functionalized Grignard
Received: September 8, 2011
Published: November 11, 2011
©
2011 American Chemical Society
10031
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Article
a
Table 1. Evaluation of Complexes 1−4b in the Reaction of PhCl with p-MeC H MgBr
6
4
b
entry
catalyst (mol %)
solvent
time (h)
yield (%)
1
2
3
4
5
6
7
8
9
1 (1)
THF
24
24
12
24
12
24
24
12
24
12
12
24
12
51
71
93
99
39
69
60
85
95
81
88
96
82
1 (1)
toluene
THF
2 (0.5)
2 (0.5)
2 (0.5)
3 (1)
THF
toluene
THF
3 (1)
toluene
THF
4a (0.5)
4a (0.5)
4a (0.5)
4b (0.5)
4b (0.5)
4b (0.5)
THF
10
11
12
13
toluene
THF
THF
toluene
a
b
Reactions were carried out with 0.5 mmol PhCl and 0.75 mmol p-MeC H MgBr in 2.5 mL of solvent at 25 °C. Isolated product yields.
6
4
a
Table 2. Reaction of Aryl Chlorides with Aryl Grignard Reagents Catalyzed by 2, 4a, and 4b
b
entry
ArCl
R
catalyst (mol %)
time (h)
yield (%)
1
2
3
4
5
6
7
8
9
p-MeOC H Cl
p-Me
p-Me
p-Me
p-Me
p-Me
p-Me
p-Me
p-Me
p-Me
p-Me
o-Me
2 (1)
2 (4)
24
24
18
12
24
24
24
24
24
24
24
24
18
12
12
12
12
24
24
24
24
24
24
24
12
24
97
98
88
99
96
98
99
99
68
65
96
93
83
98
94
93
95
97
98
95
97
92
82
81
90
80
6
4
p-Me NC H Cl
2
6
4
p-MOMOC H Cl
2 (2)
6
4
p-NCC H Cl
2 (1)
6
4
p-MeOC H Cl
4a (2)
4b (2)
4a (4)
4b (4)
4a (2)
4b (2)
2 (0.5)
2 (1)
6
4
p-MeOC H Cl
6
4
p-Me NC H Cl
2
6
4
p-Me NC H Cl
2
6
4
o-MeOC H Cl
6
4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
o-MeOC H Cl
6 4
PhCl
p-MeOC H Cl
o-Me
6
4
p-Me NC H Cl
o-Me
2 (5)
2
6
4
c
c
p-Me NC H Cl
o-Me
2 (3)
2
6
4
p-MOMOC H Cl
o-Me
2 (2)
6
4
PhCl
PhCl
o-Me
4a (1)
4b (1)
4a (2)
4b (2)
2 (1)
o-Me
p-MeOC H Cl
o-Me
6
4
p-MeOC H Cl
o-Me
6
4
PhCl
PhCl
p-OMe
p-OMe
p-OMe
p-OMe
p-OMe
p-OMe
p-OMe
4a (1)
4a (1.5)
4a (3)
4a (5)
4a (3)
4a (3)
o-MeC H Cl
6
4
2,5-Me C H Cl
2
6
3
p-Me NC H Cl
2
6
4
c
p-Me NC H Cl
2
6
4
p-MOMOC H Cl
6
4
a
Reactions were performed with 0.5 mmol aryl chlorides and 0.75 mmol Grignard reagents in 2.5 mL of THF at 25 °C unless otherwise stated.
Isolated product yields. Reactions were carried out at 70 °C.
b
c
economical reaction. On the other hand, we found that in the
presence of additives, this Ni-catalyzed Kumada cross-coupling
is compatible with a series of functionalized aryl chlorides.
Herein, we report the results.
activities of complexes 1−4b. The screening results are listed in
Table 1. Among the complexes tested, the P,N,S-pincer nickel
complexes (1 and 3, Scheme 1) exhibited relatively low
catalytic activity. By contrast, the P,N,O-pincer nickel
complexes (2, 4a, and 4b, Scheme 1) showed excellent
catalytic activity. The desired biaryls were isolated in 93%
yield by using 0.5 mol % of 2 in THF within 12 h (entry 3,
Table 1). The lengthening of the reaction time to 24 h
RESULTS AND DISCUSSION
■
The investigation began with an examination of the reaction
between PhCl and p-MeC H MgBr to evaluate the catalytic
6
4
1
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Article
improved the yield of the coupling product to 99% (entry 4,
Table 1). Complexes 4a and 4b displayed nearly same catalytic
activity as 2 either in THF or in toluene (entries 8−13, Table
Table 3. Reaction of Heteroaryl Chlorides with Aryl
Grignard Reagents Catalyzed by 2 and 4a
a
1
). The higher activity of the P,N,O-pincer nickel complexes
may be due to the ease of dissociation of the Ni−O bond to
generate coordinatively unsaturated active species. The similar
trend of catalytic activity was noted in the nickel-catalyzed
Kuamda cross-coupling of aryl chlorides and fluorides when
secondary phosphine sulfides and secondary phosphine oxides
42−44
were employed as the ligands.
It was also proven that for
this reaction, THF is a better solvent than toluene.
We next examined the reactions using different aryl chlorides
and aryl Grignard reagents catalyzed by the P,N,O-pincer
nickels (Table 2). As seen in Table 2, the deactivated aryl
chlorides, such as p-Me NC H Cl, p-MeOC H Cl and p-
2
6
4
6
4
MOMOC H Cl, can react efficiently with p-MeC H MgBr at
6
4
6
4
room temperature in the presence of complex 2 (entries 1−3,
Table 2). The reaction of p-Me NC H Cl required higher
2
6
4
catalyst loading (entry 2, Table 2). Both 4a and 4b also
catalyzed the reaction of p-Me NC H Cl and p-MeOC H Cl
2
6
4
6
4
with p-MeC H MgBr efficiently, giving the products in nearly
6
4
quantitative yield (entries 5−8, Table 2). However, o-
MeOC H Cl showed lower reactivity. Its reaction with p-
6
4
MeC H MgBr catalyzed by either 4a or 4b gave relatively low
6
4
product yields (entries 9 and 10, Table 2). This is ascribed to
its steric hindrance. o-MeC H MgBr showed simlar reactivity to
6
4
p-MeC H MgBr when PhCl and p-MeOC H Cl were
6
4
6
4
employed as the electrophiles. It was found that p-
Me NC H Cl and p-MOMOC H Cl are more difficult to
2
6
4
6
4
react with o-MeC H MgBr at room temperature. For example,
6
4
reaction of p-Me NC H Cl with o-MeC H MgBr at room
2
6
4
6
4
temperature in the presence of 2 (5 mol %) afforded 83% yield
of cross-coupling product. This can be improved by raising
reaction temperature (entries 14 and 15, Table 2). The reaction
of p-Me NC H Cl with o-MeC H MgBr at 70 °C using 3 mol
2
6
4
6
4
%
2 generated 98% yield of cross-coupling product. The
electron-rich Grignard reagent p-MeOC H MgBr also reacted
6
4
efficiently with aryl chlorides in the presence of 2 or 4a.
However, the reactivity of p-MeOC H MgBr seems to be lower
6
4
than that of p-MeC H MgBr, although p-MeOC H MgBr is a
6
4
6
4
stronger nucleophilic species. Reaction of activated aryl
chloride, p-NCC H Cl, with p-MeC H MgBr in the presence
6
4
6
4
of 2 proceeded smoothly. The cross-coupling product was
obtained in 99% yield (entry 4, Table 2). However, p-
NCC H Cl is incompatible with other Grignard reagents. Each
6
4
of the reactions of p-NCC H Cl with o-MeC H MgBr and
6
4
6
4
2
,4,6-Me C H MgBr catalyzed by 2 afforded an addition
3 6 2
product of the Grignard reagent to the CN group in almost
quantitative yield. o-NCC H Cl is incompatible with Grignard
6
4
reagents. We tried reactions of o-NCC H Cl with p-
6
4
a
MeC H MgBr, o-MeC H MgBr, and 2,4,6-Me C H MgBr in
6
4
6
4
3
6
2
Reactions were performed with 0.5 mmol heteroaryl chlorides and
the presence of 2 and found that each of the reactions afforded
addition products.
0.75 mmol Grignard reagents in 2.5 mL of Et O at 25 °C unless
2
b
c
otherwise stated. Isolated product yields. THF was used as a solvent.
Heteroarenes are important constituents of natural products,
pharmaceuticals, and fine chemicals. Synthesis of heteroaryl
derivatives through cross-coupling methodology has received
with p-MeC H MgBr catalyzed by 2 or 4a. The reaction in
6 4
THF gave cross-coupling products in 74 and 64% yields,
respectively (entries 1 and 2, Table 3), whereas reactions in
45−49
much attention in recent years.
catalysts are thus highly desired in this area.
Development of effective
50,51
We tested the
Et O led to 90 and 99% product yields, respectively (entries 3
2
catalysis of complexes 2 and 4a in the reaction of heteroaryl
chlorides with aryl Grignard reagents, and the results are listed
in Table 3. For the catalytic reaction between a heteroaryl
chloride and an aryl Grignard reagent, diethyl ether is a suitable
solvent. This was revealed by the reaction of 2-chloropyridine
and 4, Table 3). Complex 4a also showed higher catalytic
activity than 2a in Et O. Hence, further screening was carried
2
out in Et O using 4a as a catalyst. The reaction of o-
2
MeC H MgBr with 2-chloropyridine required much higher
6
4
catalyst loading compared with that of p-MeC H MgBr, giving
6
4
1
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The Journal of Organic Chemistry
Article
coupling product in 87% yield by using 4 mol % 4a (entry 5,
Table 3). This may be because the reaction is very sensitive to
the steric hindrance of an ortho methyl group in o-
MeC H MgBr. As expected, the reaction of electron-rich
methyl group in o-MeC H MgBr seems not to cause a decrease
in the coupling product yields.
6
4
Because of the high reactivity of Grignard reagents relative to
other organometallic species such as organozinc, organotin, and
organoboron reagents, Kumada reaction is often incompatible
with the functionalized substrates. However, organozinc
reagents, organostannanes, and organoboronic acid and esters
used in metal-catalyzed C−C coupling reactions are generally
derived from the corresponding magnesium or lithium reagents.
Therefore, direct use of Grignard reagents is an attractive
alternative that eliminates an additional synthetic step. For this
reason, we examined 2- or 4a-catalyzed reactions of
functionalized aryl chlorides with aryl Grignard reagents. The
initial test by reaction of p-ClC H COOEt with p-
6
4
Grignard reagents, p-MeOC H MgBr and p-Me NC H MgBr,
6
4
2
6
4
with 2-chloropyridine in the presence of 4a proceeded
smoothly, forming corresponding cross-coupling products in
9
8 and 96% yields, respectively. 2-Chloro-6-methoxypyridine
was expected to be less reactive than 2-chloropyridine in the
cross-coupling. Its reaction with p-MeC H MgBr did require
6
4
higher catalyst loading and gave a little lower yield than that of
-chloropyridine. However, the reaction of 2-chloro-6-methox-
ypyridine with p-MeOC H MgBr gave a comparable result to
2
6
4
6
4
2
-chloropyridine under the same conditions. 2-Chloro-4-
MeC H MgBr in THF using 4a as a catalyst showed only
6
4
methylquinoline behaved similarly to 2-chloropyridine in the
trace cross-coupling product to be formed. In an earlier study,
catalytic reactions. Its reaction with each of p-MeC H MgBr, o-
6
4
we found that suitable additives such as LiCl and ZnCl can
2
MeC H MgBr, and p-MeOC H MgBr gave excellent product
36
6
4
6
4
improve the compatibility of functional groups. This strategy
yields. Both 2-chloro-1,3-benzothiazole and 2-chloro-1,3-
benzoxazole were also tested in the catalyzed coupling reaction
using 4a as a catalyst. Reaction between 2-chloro-1,3-
benzothiazole and p-MeOC H MgBr afforded relatively low
was used in the current reaction. When 1 equiv of LiCl was
added and NMP was employed as a cosolvent, the reaction
mentioned above gave cross-coupling product in 74% yield.
More LiCl additives led to higher product yield. When 3 equiv
of LiCl was employed, the reaction in a mixed solvent of THF
and NMP gave 90% product yield. However, in the absence of a
NMP cosolvent, the reaction gave a relatively low product yield
6
4
product yield (74%). However, each of the reactions of 2-
chloro-1,3-benzothiazole and 2-chloro-1,3-benzoxazole with p-
MeC H MgBr, o-MeC H MgBr, or p-MeOC H MgBr in the
6
4
6
4
6
4
presence of 0.5−3 mol % 4a led to excellent product yields. A
(
49%), although 3 equiv of LiCl were still employed. When
very bulky nucleophilic reagent, 2,4,6-Me C H MgBr, can react
3
6
2
DMA was used to replace NMP as a cosolvent, no cross-
coupling product can be isolated (entry 6, Table 5). Further
investigations showed that 1 equiv of LiCl and 2 mol % ZnCl2
additives led to the same result as the 3 equiv of LiCl additives
(entry 8, Table 5). Complex 2 exhibited a similar behavior to
complex 4 in the reaction of p-ClC H COOEt with p-
very well with 2-chloro-1,3-benzoxazole at room temperature in
the presence of 5 mol % 4a. The reaction gave cross-coupling
product in 99% isolated yield (entry 18, Table 3).
Alkenyl chlorides were also used as coupling partners with
aryl Grignard reagents. Both 2 and 4a are efficient catalysts for
the coupling of 1-chloro-2-methylprop-1-ene and 1-chlorocy-
clopent-1-ene with p-MeC H MgBr, o-MeC H MgBr, or p-
6
4
MeC H MgBr (entries 9 and 10, Table 5). It was also noted
6
4
that excess Grignard reagents were required to improve the
yields.
6
4
6
4
MeOC H MgBr. The reactions were performed in THF at 25
6
4
°
C in the presence of 1.5−2 mol % 2 or 4a and gave 85−93%
With the optimized conditions in hand, we surveyed the
scope of functionalized substrates (Table 6). p-ClC
displayed better results than p-ClC H COOEt in the reaction
H
COOBut
6 4
product yields (Table 4). The steric hindrance of the ortho
6
4
with p-MeC H MgBr catalyzed by 2 or 4a (entries 1 and 2,
Table 4. Reaction of 1-Chloro-2-methyl-1-propene with
Grignard Reagents Catalyzed by 2 and 4a
6
4
a
Table 6). A similar phenomenon was observed in the 2-
t
catalyzed reaction of p-ClC H COOBu and p-ClC H COOEt
6
4
6
4
with o-MeC H MgBr (entries 7 and 8, Table 6). p-ClC H C-
6
4
6
4
(
O)NEt is also a suitable electrophilic substrate in the reaction
2
with p-MeC H MgBr or p-MeOC H MgBr (entries 3, 4, and
6
4
6
4
1
0, Table 6). In the reaction of p-ClC H C(O)NEt with p-
6 4 2
MeC H MgBr, complex 4a showed a slightly higher catalytic
6
4
activity than 2. The reaction of p-ClC H COPh with p-
6
4
MeC H MgBr also proceeded in moderate yields in the
6
4
presence of 2 or 4a but required higher catalyst loading and
more ZnCl additives (10 mol %) (entries 5 and 6, Table 6).
2
This is probably because the ketone carbonyl group is more
reactive than those of esters and carboxamide. The reaction of
p-ClC H CHO with aryl Grignard reagents using 2 or 4a as a
6
4
catalyst can not generate cross-coupling products because of
the high reactivity of CHO group. Surprisingly, 2-(4-
chlorophenyl)-1,3-dioxolane can not catalytically couple with
aryl Grignard reagents in the absence of additives. In the
presence of LiCl (1 equiv) and ZnCl (10 mol %), the 2- or 4a-
2
catalyzed reaction of 2-(4-chlorophenyl)-1,3-dioxolane with p-
MeC H MgBr in a mixture of THF and NMP afforded cross-
coupling products in good yields (entries 11 and 12, Table 6).
a
6
4
Reactions were performed with 0.5 mmol vinyl chlorides and 0.75
b
mmol Grignard reagents in 2.5 mL of THF at 25 °C. Isolated product
yields.
The cross-coupling of p-ClC H CF with p-MeC H MgBr
6
4
3
6
4
catalyzed by 4a under the standard conditions gave excellent
1
0034
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The Journal of Organic Chemistry
Article
a
Table 5. Reaction of p-ClC H COOEt with p-MeC H MgBr Catalyzed by 2 and 4a
6
4
6
4
b
entry
catalyst (mol %)
additive
LiCl (1 equiv)
solvent
yield (%)
1
2
3
4
5
6
7
8
9
4a (2)
4a (2)
4a (2)
4a (2)
4a (2)
4a (2)
4a (1)
4a (2)
2 (2)
THF (3.7 mL)
trace
74
88
90
49
0
THF (2.2 mL) + NMP (1.5 mL)
THF (2.2 mL) + NMP (1.5 mL)
THF (2.2 mL) + NMP (1.5 mL)
THF (3.7 mL)
LiCl (2 equiv)
LiCl (3 equiv)
LiCl (3 equiv)
LiCl (3 equiv)
THF (2.2 mL) + DMA (1.5 mL)
THF (2.2 mL) + NMP (1.5 mL)
THF (2.2 mL) + NMP (1.5 mL)
THF (2.2 mL) + NMP (1.5 mL)
THF (2.2 mL) + NMP (1.5 mL)
LiCl (3 equiv)
79
90
76
85
LiCl (1 equiv), ZnCl (2 mol %)
LiCl (3 equiv)
10
2 (2)
LiCl (1 equiv), ZnCl (2 mol %)
a
Reactions were performed with 0.5 mmol p-ClC H COOEt and 1.1 mmol p-MeC H MgBr at 25 °C. After the mixture of p-ClC H COOEt,
6
4
6
4
6
4
additives, solvent, and 0.6 mmol p-MeC H MgBr in THF was stirred for 2 h, additional 0.5 mmol p-MeC H MgBr was injected, and stirring was
continued for an additional 2 h. Isolated product yields.
6
4
6
4
b
results. However, the reaction catalyzed by 2 under the same
conditions led to a much lower yield (60%) (entries 13 and 14,
Table 6). In fact, in most cases complex 4a exhibited
comparable catalytic activity to 2, whereas complex 4a showed
higher catalytic activity than 2 in the reactions using p-
ClC H C(O)NEt and p-ClC H CF as electrophilic sub-
and purified by column chromatography (silica gel, eluted using
petroleum ether) to afford p-MeC H Ph (0.084 g, 99%).
6
4
The reactions in toluene or Et O followed the same procedure, only
2
THF was replaced with the required solvent.
(2). Representative Procedure for the Kumada Coupling of
Functionalized Aryl Chlorides. A Schlenk tube was charged with
nickel complex 4a (6.6 mg, 0.01 mmol), LiCl (21.2 mg, 0.5 mmol),
ZnCl (0.1 mL, a solution of 136 mg of ZnCl in 10 mL of THF, 0.01
6
4
2
6
4
3
strates.
2
2
In summary, we have described a broadly applicable nickel-
catalyzed Kumada reaction at room temperature. The P,N,O-
chelate nickel complexes showed high catalytic activity for the
coupling reactions of unactivated and deactivated aryl chlorides,
heteroaryl chlorides, and vinyl chlorides with aryl Grignard
mmol), NMP (1.5 mL), and p-ClC H COOEt (0.092 g, 0.5 mmol).
6
4
To the mixture was added slowly p-MeC H MgBr (1.2 mL, 0.5 M in
6
4
THF, 0.6 mmol) at 25 °C with stirring. After the resulting solution was
stirred at 25 °C for 2 h, a solution of p-MeC MgBr (1 mL, 0.5 M in
H
4
6
THF, 0.5 mmol) was slowly added again. After further stirring at 25 °C
for 2 h, the reaction mixture was quenched with water and extracted
with diethyl ether (3 × 10 mL). The combined organic phases were
dried over Na SO , concentrated by rotary evaporation, and purified
reagents. In the presence of LiCl and ZnCl additives, the
2
reactions tolerate a few types of functional groups such as ester,
ketone, carboxamide, and trifluoromethyl groups. In contrast,
P,N,S-chelate complexes 1 and 3 revealed a relatively low
catalytic activity. This work significantly expands the substrate
scopes of Kumada cross-coupling reactions.
2
4
by column chromatography (silica gel, eluted using 3% CH COOEt−
3
petroleum ether) to afford ethyl 4-(p-tolyl)benzoate (0.108 g, 90%).
Spectral Data of the Cross-Coupling Products. 4-Methyl-
3
6
1
biphenyl.
H NMR (CDCl ): δ 2.35 (s, 3H), 7.20 (d, J = 8.1 Hz,
3
2
H), 7.28 (d, J = 7.2 Hz, 1H), 7.37 (t, J = 7.4 Hz, 2H), 7.46 (d, J = 8.1
1
3
Hz, 2H), 7.54 (d, J = 7.5 Hz, 2H). C NMR (CDCl ): δ 21.2, 126.9,
EXPERIMENTAL SECTION
3
■
1
27.1, 127.3, 127.4, 128.8, 129.56, 129.61, 137.1, 138.5, 141.3.
All reactions were performed under a nitrogen atmosphere using
standard Schlenk and vacuum line techniques. Solvents were distilled
under nitrogen over sodium (toluene) or sodium/benzophenone
36
1
4
-Methoxy-4′-methylbiphenyl.
H NMR (CDCl ): δ 2.29 (s,
3
3
7
H), 3.74 (s, 3H), 6.87 (d, J = 9 Hz, 2H), 7.13 (d, J = 7.9 Hz, 2H),
.36 (d, J = 8.1 Hz, 2H), 7.43 (d, J = 8.8 Hz, 2H). C NMR (CDCl ):
13
3
(
THF and Et O) and degassed prior to use. NMP and DMA were
2
δ 21.1, 55.4, 114.3, 126.7, 128.0, 129.6, 133.9, 136.4, 138.1, 159.1.
dried over 4 Å molecular sieves, fractionally distilled under reduced
pressure, and stored under nitrogen atmosphere. All catalysts were
prepared according to the reported methods. The Grignard reagents
were prepared according to the procedure reported in literature. All
other chemicals and solvents were obtained from commercial vendors
and used as received. NMR spectra were recorded on a 300 MHz
53
1
4
′-Methyl-N,N-dimethylbiphenyl-4-amine.
H NMR (CDCl ):
3
δ 2.27 (s, 3H), 2.86 (s, 6H), 6.69 (d, J = 9 Hz, 2H), 7.10 (d, J = 8.1
Hz, 2H), 7.36 (d, J = 8.7 Hz, 2H), 7.39 (d, J = 9 Hz, 2H). C NMR
41
13
52
(CDCl ): δ 21.2, 40.8, 113.0, 126.3, 127.6, 129.5, 135.7, 138.4, 149.8.
3
54
1
4
-(Methoxymethoxy)-4′-methylbiphenyl.
.28 (s, 3H), 3.39 (s, 3H), 5.10 (s, 2H), 7.00 (d, J = 8.4 Hz, 2H), 7.11
H NMR (CDCl ): δ
3
2
1
spectrometer at ambient temperature. The chemical shifts of the H
and 13C NMR spectra were referenced to TMS or internal solvent
(d, J = 8.1 Hz, 2H), 7.34 (d, J = 7.8 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H).
1
3
C NMR (CDCl ): δ 21.2, 56.1, 94.6, 116.6, 126.8, 128.1, 129.6,
3
resonances.
1
35.1, 136.6, 138.0, 156.7.
General Procedure for the Cross-Coupling Reactions
Catalyzed by 1−4b. (1). Representative Procedure for the
Kumada Coupling of Aryl Chlorides. A Schlenk tube was charged
with nickel complex 2 (0.05 mL, 0.05 M solution in THF, 0.0025
mmol), THF (1.5 mL), and PhCl (0.056 g, 0.5 mmol). To the
solution was added dropwise a solution of p-MeC H MgBr (1.5 mL,
3
6
1
4
′-Methylbiphenyl-4-carbonitrile.
H NMR (CDCl ): δ 2.34 (s,
3
3H), 7.19 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 7.60 (d, J = 8.1
Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H). C NMR (CDCl
119.1, 127.2, 127.6, 130.0, 132.7, 136.4, 138.9, 145.7, 157.2.
1
3
): δ 21.3, 110.6,
3
3
6
1
2-Methoxy-4′-methylbiphenyl.
H NMR (CDCl ): δ 2.30 (s,
6
4
3
0
.5 M in THF, 0.75 mmol) at 25 °C with stirring. After stirring at this
3H), 3.71 (s, 3H), 6.88 (d, J = 8.6 Hz, 1H), 6.94 (d, J = 7.5 Hz, 1H),
7.12 (d, J = 7.9 Hz, 2H), 7.21 (d, J = 7.5 Hz, 2H), 7.34 (d, J = 7.9 Hz,
2H). C NMR (CDCl ): δ 21.3, 55.7, 111.4, 120.1, 120.9, 128.5,
temperature for 24 h, the reaction mixture was quenched with water
and extracted with diethyl ether (3 × 10 mL). The combined organic
phases were dried over Na SO , concentrated by rotary evaporation,
1
3
3
128.9, 129.6, 130.9, 135.8, 136.7, 156.7.
2
4
1
0035
dx.doi.org/10.1021/jo201821g | J. Org. Chem. 2011, 76, 10031−10038

The Journal of Organic Chemistry
Article
3
6
1
4
-Methoxybiphenyl.
H NMR (CDCl ): δ 3.82 (s, 3H), 6.96 (d,
3
Table 6. Reaction of Functionalized Aryl Chlorides with
Grignard Reagents Catalyzed by 2 and 4a
a
J = 8.7 Hz, 2H), 7.28 (t, J = 7.3 Hz, 1H), 7.39 (t, J = 7.5 Hz, 2H),
.49−7.55 (m, 4H). C NMR (CDCl ): δ 55.4, 114.3, 126.8, 128.3,
28.8, 133.9, 140.9, 159.3.
1
3
7
1
3
5
6
1
4
′-Methoxy-2,5-dimethylbiphenyl.
H NMR (CDCl ): δ 2.23
3
(
(
(
s, 3H), 2.33 (s, 3H), 3.84 (s, 3H), 6.94 (d, J = 8.7 Hz, 2H), 7.03−7.05
13
m, 2H), 7.14 (d, J = 8.1 Hz, 1H), 7.24 (d, J = 8.7 Hz, 2H). C NMR
CDCl ): δ 20.2, 21.0, 55.4, 113.6, 127.8, 130.4, 130.8, 132.4, 134.6,
3
1
35.3, 141.5, 158.6.
′-Methoxy-N,N-dimethylbiphenyl-4-amine. 1H NMR
CDCl ): δ 2.96 (s, 6H), 3.82 (s, 3H), 6.78 (d, J = 8.8 Hz, 2H),
4
1
4
(
3
1
3
6
.93 (d, J = 8.7 Hz, 2H), 7.45 (t, J = 8.4 Hz, 4H). C NMR (CDCl ):
3
δ 40.8, 55.5, 113.1, 114.3, 127.5, 129.4, 134.1, 149.7, 158.4.
1
4
-(Methoxymethoxy)-4′-methoxybiphenyl. H NMR (CDCl ): δ
3
3
(
.49 (s, 3H), 3.81 (s, 3H), 5.19 (s, 3H), 6.94 (d, J = 8.8 Hz, 2H), 7.08
1
3
d, J = 8.7 Hz, 2H), 7.46 (d, J = 8.4 Hz, 4H). C NMR (CDCl ): δ
3
5
5.4, 56.1, 94.6, 114.3, 116.7, 127.9, 127.9, 133.5, 134.8, 156.5, 158.9.
+
HR-MS (EI): m/z 244.1102 [M] , calcd for C H O 244.1099.
1
5
16
3
3
6
1
2
-p-Tolylpyridine.
H NMR (CDCl ): δ 2.37 (s, 3H), 7.10−7.27
3
(
m, 1H), 7.25 (d, J = 7.9 Hz, 2H), 7.65−7.67 (m, 2H), 7.88 (d, J = 8.1
1
3
Hz, 2H), 8.64−8.66 (m, 1H). C NMR (CDCl ): δ 21.38, 120.2,
1
3
21.8, 126.8, 129.5, 136.7, 139.0, 149.6, 157.5.
14
1
2
-o-Tolylpyridine.
H NMR (CDCl ): δ 2.36 (s, 3H), 7.19−7.29
3
(
=
m, 4H), 7.36−7.41 (m, 2H), 7.71 (dt, J = 1.8, 7.8 Hz, 1H), 8.68 (d, J
1
3
4.2 Hz, 1H). C NMR (CDCl ): δ 20.3, 121.7, 124.1, 125.9, 128.3,
3
1
29.7, 130.8, 135.8, 136.2, 140.5, 149.2, 160.1.
14
1
2
-(p-Methoxyphenyl)pyridine.
H NMR (CDCl ): δ 3.82 (s,
3
3
2
H ), 6.98 (d, J = 8.7 Hz, 2H), 7.11−7.15 (m, 1H), 7.61−7.69 (m,
3
1
3
H), 7.94 (d, J = 8.7 Hz, 2H), 8.63 (d, J = 4.5 Hz, 1H). C NMR
(CDCl ): δ 55.3, 114.2, 119.8, 121.4, 128.2, 132.1, 136.7, 149.6, 157.1,
3
1
60.5.
-(p-N,N-Dimethylaminophenyl)pyridine.
.96 (s, 6H), 6.76 (d, J = 8.9 Hz, 2H), 7.05 (d, J = 4.5 Hz, 1H), 7.59−
5
7
1
2
H NMR (CDCl ): δ
3
2
7
1
3
.61 (m, 2H), 7.91 (d, J = 8.9 Hz, 2H), 8.60 (d, J = 4.7 Hz, 1H).
C
NMR (CDCl ): δ 40.3, 112.2, 119.1, 120.6, 127.7, 136.5, 149.4, 151.2,
3
1
57.6.
-Methoxy-6-(4′-methylphenyl)pyridine.
.31 (s, 3H), 3.94 (s, 3H), 6.56 (d, J = 8.4 Hz, 1H), 7.15−7.22 (m,
5
8
1
2
H NMR (CDCl ): δ
3
2
3
1
3
H), 7.50 (t, J = 7.8 Hz, 1H), 7.85 (d, J = 8.4 Hz, 2H). C NMR
(
1
CDCl ): δ 21.4, 53.3, 108.9, 112.5, 118.1, 126.7, 127.0, 129.4, 136.5,
3
38.9, 139.2, 154.9, 163.8.
5
9
1
2
-Methoxy-6-(4′-methoxyphenyl)pyridine.
H NMR (CDCl ):
3
δ 3.72 (s, 3H), 3.91 (s, 3H), 6.51 (d, J = 8.1 Hz, 1H), 6.86 (d, J = 8.7
Hz, 2H), 7.13 (d, J = 7.5 Hz, 1H), 7.45 (t, J = 7.8 Hz, 1H), 7.89 (d, J =
8
a
Unless otherwise stated, the reactions were carried out as the
1
3
.7 Hz, 2H). C NMR (CDCl ): δ 53.2, 55.4, 108.4, 112.0, 114.0,
3
following procedure: a mixture of 0.5 mmol aryl chloride, 1 equiv of
1
14.2, 127.8, 128.0, 131.8, 139.2, 154.5, 160.4, 163.7.
LiCl, 2 mol % ZnCl , 1.5 mL of NMP, required catalyst, and 0.6 mmol
2
58
1
4
-Methyl-2-(4′-methylphenyl)quinoline.
H NMR (CDCl ): δ
3
Grignard reagent in THF was stirred at 25 °C for 2 h. Then, additional
2
.26 (s, 3H), 2.50 (s, 3H), 7.11−7.16 (m, 2H), 7.25−7.34 (m, 1H),
0
.5 mmol Grignard reagent in THF was injected, and stirring was
b c
7.40−7.55 (m, 2H), 7.70−7.76 (m, 1H), 7.85−7.92 (m, 2H), 8.00−
continued for an additional 2 h. Isolated product yields. 10 mol %
1
3
8
1
.04 (m, 1H). C NMR (CDCl ): δ 18.9, 21.3, 119.5, 123.6, 125.8,
3
ZnCl was used.
2
27.1, 127.4, 129.2, 129.5, 130.2, 136.9, 139.2, 144.6, 148.1, 156.9.
6
0
1
5
5
1
4-Methyl-2-(2′-methylphenyl)quinoline.
H NMR (CDCl ): δ
3
2
-Methylbiphenyl.
H NMR (CDCl ): δ 2.26 (s, 3H), 7.20−7.26
13
3
2
2
.40 (s, 3H), 2.69 (s, 3H), 7.30 (s, 3H), 7.34 (s, 4H), 7.45−7.56 (m,
H), 7.69 (t, J = 7.2 Hz, 1H), 7.98 (d, J = 8.1 Hz, 1H), 8.16 (d, J = 8.4
(
(
m, 4H), 7.28−7.34 (m, 3H), 7.36−7.42 (m, 2H). C NMR
CDCl ): δ 20.6, 125.7, 125.9, 126.9, 127.3, 127.4, 128.29, 129.3,
13
3
Hz, 1H). C NMR (CDCl ): δ 18.9, 20.4, 123.1, 123.6, 126.0, 126.2,
1
160.1.
3
1
29.9, 130.4, 135.5, 142.09, 142.13.
26.8, 128.4, 129.3, 129.6, 130.2, 130.8, 136.0, 140.9, 144.2, 147.7,
4
1
1
4
′-Methoxy-2-methylbiphenyl.
H NMR (CDCl ): δ 2.24 (s,
3
1
3
61
1
3H), 3.80 (s, 3H), 6.94 (d, J = 8.7 Hz, 2H), 7.17−7.22 (m, 6H).
C
4-Methyl-2-(4′-methoxyphenyl)quinoline.
H NMR (CDCl ): δ
3
NMR (CDCl ): δ 20.7, 55.4, 113.6, 125.9, 127.1, 130.0, 130.37,
2.68 (s, 3H), 3.85 (s, 3H), 7.04 (d, J = 8.7 Hz, 2H), 7.49 (t, J = 7.3 Hz,
3
1
30.41, 134.5, 135.6, 141.7, 158.7.
1H), 7.63 (s, 1H), 7.70 (t, J = 7.5 Hz, 1H), 7.92 (d, J = 8.1 Hz, 1H),
1
3
5
3
1
8
1
.10−8.19 (m, 3H). C NMR (CDCl ): δ 19.0, 55.3, 114.1, 119.2,
2
′-Methyl-N,N-dimethylbiphenyl-4-amine.
H NMR (CDCl ):
3
3
23.6, 125.6, 127.0, 128.8, 129.2, 130.0, 132.3, 144.5, 148.1, 156.5,
δ 2.21 (s, 3H), 2.86 (s, 6H), 6.67 (d, J = 8.4 Hz, 2H), 7.05−7.15 (m,
H). 1 C NMR (CDCl ): δ 20.8, 40.7, 112.3, 125.8, 126.6, 130.1,
3
160.7.
-(4′-Methylphenyl)benzothiazole.
s, 3H), 7.11 (d, J = 7.8 Hz, 2H), 7.17−7.22 (m, 1H), 7.30−7.35 (m,
H), 7.70 (d, J = 7.8 Hz, 1H), 7.83 (d, J = 8.1 Hz, 2H), 7.93 (d, J = 8.1
6
1
3
62
1
2
H NMR (CDCl ): δ 2.24
3
30.4, 135.5, 142.1, 149.5.
(
1
4
-(Methoxymethoxy)-2′-methylbiphenyl. H NMR (CDCl ): δ
3
1
2
7
1
.17 (s, 3H), 3.40 (s, 3H), 5.10 (s, 2H), 6.97 (d, J = 8.6 Hz, 2H),
.08−7.15 (m, 6H). C NMR (CDCl ): δ 20.6, 56.1, 94.6, 115.9,
25.9, 127.2, 130.0, 130.4, 135.5, 135.7, 141.6, 156.3. HR-MS (EI): m/
13
Hz, 2H). C NMR (CDCl ): δ 21.5, 121.6, 123.1, 125.0, 126.2, 127.5,
3
13
3
128.9, 129.7, 135.0, 141.4, 154.3, 168.2.
2-(4′-Methoxyphenyl)benzothiazole.
(s, 3H), 6.97 (d, J = 9 Hz, 2H), 7.31−7.36 (m, 1H), 7.44−7.49 (m,
6
2
1
H NMR (CDCl ): δ 3.83
3
+
z 228.1152 [M] , calcd for C H O 228.1150.
15
16
2
1
0036
dx.doi.org/10.1021/jo201821g | J. Org. Chem. 2011, 76, 10031−10038

The Journal of Organic Chemistry
Article
1
1
H), 7.85 (d, J = 8.1 Hz, 1H), 8.03 (t, J = 8.2 Hz, 1H). 13C NMR
CDCl ): δ 55.5, 114.4, 121.6, 122.9, 124.8, 126.2, 126.5, 129.1, 134.9,
tert-Butyl 2-(o-Tolyl)benzoate. H NMR (CDCl ): δ 1.51 (s, 9H),
3
(
1
2.14 (s, 3H), 7.09−7.15 (m, 4H), 7.26 (d, J = 8.1 Hz, 2H), 7.94 (d, J =
8.1 Hz, 2H). C NMR (CDCl ): δ 20.5, 28.3, 81.0, 126.0, 127.8,
129.2, 129.4, 129.6, 130.5, 135.2, 141.1, 146.3, 165.8. HR-MS (EI): m/
z 268.1459 [M] , calcd for C H O 268.1463.
3
1
3
54.3, 162.0, 167.9.
3
6
3
1
2
-(4′-Methylphenyl)benzoxazole.
H NMR (CDCl ): δ 2.26 (s,
3
+
3
8
1
H), 7.11−7.22 (m, 4H), 7.39−7.42 (m, 1H), 7.59−7.66 (m, 1H),
1
8
20
2
.00 (d, J = 8.1 Hz, 2H). 13C NMR (CDCl ): δ 21.6, 110.5, 119.9,
Ethyl 4′-Methoxybiphenyl-4-carboxylate.
36
1
H NMR (CDCl ): δ
3
3
24.5, 124.9, 127.6, 128.9, 129.6, 130.2, 142.0, 142.3, 150.7, 163.4.
1.39 (t, J = 7.2 Hz, 3H), 3.82 (s, 3H), 4.38 (q, J = 7.2 Hz, 2H), 6.97 (d,
J = 8.8 Hz, 2H), 7.54 (d, J = 8.8 Hz, 2H), 7.59 (d, J = 8.4 Hz, 2H),
6
3
1
2
-(2′-Methylphenyl)benzoxazole.
H NMR (CDCl ): δ 2.68 (s,
3
1
3
3
8
1
H), 7.13−7.9 (m, 5H), 7.40−7.46 (m, 1H), 7.66−7.69 (m, 1H),
8.07 (d, J = 8.5 Hz, 2H). C NMR (CDCl ): δ 14.4, 55.4, 60.9, 114.5,
3
13
.03−8.06 (m, 1H). C NMR (CDCl ): δ 22.3, 110.5, 120.2, 124.4,
126.5, 128.4, 128.7, 130.1, 132.5, 145.2, 159.9, 166.6.
3
N,N-Diethyl-4′-methoxybiphenyl-4-carboxamide. 1H NMR
6
9
25.1, 126.1, 130.0, 130.9, 131.8, 138.9, 142.3, 150.4, 163.4.
6
3
1
2
-(4′-Methoxyphenyl)benzoxazole.
H NMR (CDCl ): δ 3.80
(CDCl
): δ 1.14 (b, 3H), 1.23 (b, 3H), 3.31 (b, 2H), 3.54 (b, 2H),
3
3
(
1
(
s, 3H), 6.97 (d, J = 8.7 Hz, 2H), 7.24−7.32 (m, 2H), 7.47−7.52 (m,
3.81 (s, 3H), 6.96 (d, J = 8.7 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H), 7.52
(d, J = 8.8 Hz, 2H), 7.56 (d, J = 8.1 Hz, 2H). C NMR (CDCl ): δ
3
1
3
13
H), 7.70−7.75 (m, 1H), 8.15 (d, J = 8.8 Hz, 2H). C NMR
CDCl ): δ 55.4, 110.4, 114.3, 119.6, 124.4, 124.6, 129.4, 142.3, 150.7,
12.9, 14.2, 39.2, 43.3, 55.3, 114.2, 126.5, 126.8, 128.1, 132.7, 135.4,
141.5, 159.4, 171.1.
3
162.3, 163.2.
6
4
1
70
2-(4′-Methyl[1,1′-biphenyl]-4-yl)-1,3-dioxolane. 1H NMR
2
-(2′,4′,6′-Trimethylphenyl)benzoxazole.
H NMR (CDCl ): δ
3
2
7
1
.17 (s, 6H), 2.21 (s, 3H), 6.84 (s, 2H), 7.20−7.27 (m, 2H), 7.42−
(CDCl ): δ 2.29 (s, 3H), 3.88−4.08 (m, 4H), 5.75 (s, 1H), 7.14 (d,
3
13
.46 (m, 1H), 7.69−7.72 (m, 1H). C NMR (CDCl ): δ 20.4, 21.3,
J = 7.9 Hz, 2H), 7.39 (d, J = 8.1 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H),
3
1
3
10.6, 120.2, 124.3, 124.9, 128.7, 138.5, 140.3, 141.7, 150.7, 163.3.
7.50 (d, J = 8.4 Hz, 4H). C NMR (CDCl
126.9, 127.0, 127.1, 129.6, 136.7, 137.3, 138.0, 142.1.
3
): δ 21.2, 65.4, 103.7,
6
5
1
p-Methyl-β,β-dimethylstyrene.
H NMR (CDCl ): δ 1.84 (s,
3
1
3
41
1
3
H), 1.88 (s, 3H), 2.32 (s, 3H), 6.23 (s, 1H), 7.11 (s, 4H). C NMR
4-Methyl-4′-(trifluoromethyl)biphenyl.
H NMR (CDCl ): δ
3
(
CDCl ): δ 19.5, 21.2, 27.0, 125.2, 128.8, 128.9, 134.8, 135.4, 136.0.
3
66
2.39 (s, 3H), 7.26 (d, J = 8.1 Hz, 2H), 7.48 (d, J = 8.1 Hz, 2H),
1
13
o-Methyl-β,β-dimethylstyrene.
H NMR (CDCl ): δ 1.72 (s,
7.65 (s, 4H). C NMR (CDCl
): δ 21.3, 125.8 (q, J = 3.5 Hz), 127.2,
3
3
1
3
3H), 1.92 (s, 3H), 2.25 (s, 3H), 6.25 (s, 1H), 7.14 (s, 4H). C NMR
127.3, 129.9, 137.0, 138.3, 144.8.
(
1
CDCl ): δ 19.3, 20.0, 26.2, 124.3, 125.4, 127.4, 129.6, 129.8, 135.0,
3
36.4, 138.0.
ASSOCIATED CONTENT
6
7
1
■
* Supporting Information
1
p-Methoxy-β,β-dimethylstyrene.
H NMR (CDCl ): δ 1.83 (s,
3
S
3
7
1
H), 1.87 (s, 3H), 3.76 (s, 3H), 6.20 (s, 1H), 6.83 (d, J = 8.7 Hz, 2H),
.14 (d, J = 8.7 Hz, 2H). 13C NMR (CDCl ): δ 19.3, 26.8, 55.2, 113.5,
H and 13C NMR spectra of all products. This material is
3
24.7, 129.9, 131.4, 133.9, 157.8.
available free of charge via the Internet at http://pubs.acs.org.
6
8
1
1
-Cyclopentenyl-4-methylbenzene.
H NMR (CDCl ): δ 1.95−
3
2
6
.05 (m, 2H), 2.33 (s, 3H), 2.48−2.55 (m, 2H), 2.65−2.72 (m, 2H),
AUTHOR INFORMATION
■
.11−6.14 (m, 1H), 7.11 (d, J = 7.8 Hz, 2H), 7.33 (d, J = 7.8 Hz, 2H).
13
C NMR (CDCl ): δ 21.3, 23.2, 33.37, 33.44, 125.2, 125.6, 129.1,
Corresponding Author
*E-mail: zxwang@ustc.edu.cn.
3
134.2, 136.6, 142.4.
1
6
1
1
-Cyclopentenyl-2-methylbenzene.
H NMR (CDCl ): δ 1.94−
3
2
5
2
.05 (m, 2H), 2.35 (s, 3H), 2.49−2.56 (m, 2H), 2.62−2.70 (m, 2H),
ACKNOWLEDGMENTS
1
3
■
.75−5.78 (m, 1H), 7.12−7.21 (m, 4H). C NMR (CDCl ): δ 21.3,
3
This research was supported by National Basic Research
Program of China (Grant No. 2009CB825300) and the
National Natural Science Foundation of China (Grant No.
20772119).
3.9, 33.7, 36.8, 125.7, 126.7, 128.1, 129.5, 130.6, 135.6, 138.4, 143.4.
1
6
1
1
-Cyclopentenyl-4-methoxybenzene.
H NMR (CDCl ): δ
3
1
.95−2.05 (m, 2H), 2.47−2.55 (m, 2H), 2.64−2.71 (m, 2H), 3.80
(
s, 3H), 6.03−6.06 (m, 1H), 6.85 (d, J = 8.7 Hz, 2H), 7.37 (d, J = 8.7
13
Hz, 2H). C NMR (CDCl ): δ 23.5, 33.4, 55.4, 113.8, 124.1, 126.8,
3
1
29.9, 142.0, 158.7.
3
6
1
REFERENCES
■
Ethyl 4′-Methylbiphenyl-4-carboxylate.
H NMR (CDCl ): δ
3
(
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.30 (t, J = 7.2 Hz, 3H), 2.29 (s, 3H), 4.29 (q, J = 7.1 Hz, 2H), 7.15 (d,
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(
1
d, 2H, J = 8.3 Hz). 13C NMR (CDCl ): δ 14.5, 21.2, 61.0, 126.8,
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tert-Butyl 4-(p-Tolyl)benzoate.
H NMR (CDCl ): δ 1.50 (s,
3
9
7
H), 2.27 (s, 3H), 7.12 (d, J = 7.8 Hz, 2H), 7.38 (d, J = 8.1 Hz, 2H),
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3
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CDCl ): δ 1.19 (b, 6H), 2.38 (s, 3H), 3.32 (b, 2H), 3.53 (b, 2H),
1
3
6
(
3
7
2
3
.23 (d, J = 7.8 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H), 7.48 (d, J = 8.1 Hz,
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3
9.3, 43.3, 126.77, 126.80, 126.90, 129.5, 135.7, 137.4, 141.9, 171.1.
3
6
1
(
4′-Methylbiphenyl-4-yl)(phenyl)methanone.
H NMR
(
5
(
CDCl ): δ 2.30 (s, 3H), 7.17 (d, J = 8.1 Hz, 2H), 7.36−7.51 (m,
3
1
3
H), 7.58 (d, J = 8.4 Hz, 2H), 7.71−7.79 (m, 4H). C NMR
CDCl ): δ 21.3, 126.8, 127.2, 128.4, 129.8, 130.1, 130.8, 132.4, 136.0,
3
137.1, 137.9, 138.2, 145.2, 196.4.
3
6
1
Ethyl 2′-Methylbiphenyl-4-carboxylate.
H NMR (CDCl ): δ
3
1
7
.30 (t, J = 7.1 Hz, 3H), 2.15 (s, 3H), 4.28 (q, J = 7.1 Hz, 2H), 7.08−
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1
3
.16 (m, 4H), 7.27 (d, J = 8.7 Hz, 2H), 7.99 (d, J = 8.4 Hz, 2H).
C
NMR (CDCl ): δ 14.4, 20.4, 61.0, 126.0, 127.9, 129.3, 129.5, 129.6,
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3
130.6, 135.2, 141.0, 146.7, 166.6.
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1
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