Effects of solvent and base on the palladium-catalyzed amination: PdCl 2(Ph3P)2/Ph3P-catalyzed selective arylation of primary anilines with aryl bromides

Article abstract of DOI:10.1016/j.tet.2014.05.048

A readily accessible catalytic system, PdCl₂(Ph ₃P)₂/Ph₃P, was developed for the selective arylation of primary anilines with aryl bromides. The strong influence of solvents and bases on the catalytic activity was observed. In refluxing o-xylene, triphenylphosphine shows high efficiency for Pd-catalyzed intermolecular amination reactions. By changing the bases, mono- and diarylation of primary amines could be selectively achieved in high yields. Moreover, the catalytic system showed good toleration for the steric hindrance of anilines. A series of N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′- diamines, important intermediates of OLED hole transport materials, were synthesized facilely via coupling reactions between 4,4′-diaminobiphenyls and aryl bromides.

Full text of DOI:10.1016/j.tet.2014.05.048

Accepted Manuscript
Effects of solvent and base on the palladium catalyzed amination: PdCl (Ph P) /
2
3 2
Ph P catalyzed selective arylation of primary anilines with aryl bromides
3
Liangzhen Cai , Xuanying Qian , Wenjing Song , Taoping Liu , Xiaochun Tao ,
Wanfang Li , Xiaomin Xie
PII:
S0040-4020(14)00728-5
10.1016/j.tet.2014.05.048
TET 25597
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 8 March 2014
Revised Date: 5 May 2014
Accepted Date: 15 May 2014
Please cite this article as: Cai L, Qian X, Song W, Liu T, Tao X, Li W, Xie X, Effects of solvent and base
on the palladium catalyzed amination: PdCl (Ph P) /Ph P catalyzed selective arylation of primary
2
3
2
3
anilines with aryl bromides, Tetrahedron (2014), doi: 10.1016/j.tet.2014.05.048.
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Effects of solvent and base on the palladium
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2
3
2
3
catalyzed selective arylation of primary
anilines with aryl bromides
a
a
a
a
a,
b
Liangzhen Cai , Xuanying Qian , Wenjing Song , Taoping Liu , Xiaochun Tao *, Wanfang Li ,
b,
Xiaomin Xie *
a
School of Chemistry and Molecular Engineering, East China University of Science and Technology,130
Meilong Road, Shanghai 200237, China
b
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road,
Shanghai 200240, China

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Effects of solvent and base on the palladium catalyzed amination: PdCl (Ph P) /Ph P
2
3
2
3
catalyzed selective arylation of primary anilines with aryl bromides
a
a
a
a
a,
b
Liangzhen Cai , Xuanying Qian , Wenjing Song , Taoping Liu , Xiaochun Tao *, Wanfang Li , and
b,
Xiaomin Xie *
a
School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
b
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
2 3 2 3
A readily accessible catalytic system, PdCl (Ph P) /Ph P, was developed for the selective
arylation of primary anilines with aryl bromides. The strong influence of solvents and bases on
the catalytic activity was observed. In refluxing o-xylene, triphenylphosphine shows high
efficiency for Pd-catalyzed intermolecular amination reactions. By changing the bases, mono-
and diarylation of primary amines could be selectively achieved in high yields. Moreover, the
catalytic system showed good toleration for the steric hindrance of anilines. A series of N, N, N’,
N’-tetraaryl-1,1’-biphenyl-4,4’-diamines, important intermediates of OLED hole transport
materials, were synthesized facilely via coupling reactions between 4, 4’-diaminobiphenyls and
aryl bromides.
Available online
Keywords:
Palladium
Amination
Triphenylphosphine
Diarylation
2
009 Elsevier Ltd. All rights reserved.
Monoarylation
1
. Introduction
2
. Results and Discussion
Palladium catalyzed arylation of amines constitutes a powerful
tool for synthetic chemists and has found widespread use in many
areas, such as the synthesis of important intermediates and
building blocks for fine chemicals, pharmaceuticals,
The structural blocks of di- and triarylamines are commonly
encountered in pharmaceuticals, xerographic and photographic
materials as well as conducting polymers. Therefore, the
1
coupling reaction of aniline (1) with 4-bromotoluene (2) was
1
photographic materials and conducting polymers. Improving the
chosen as the model reaction to test the feasibility of Pd/Ph P as a
3
efficiency and the substrate scope continues to fuel interest in the
catalyst system. Under the general reaction conditions for
2
3
design of new ligands. In this regard, many new bulky and
palladium-catalyzed amination , no coupling product was
3
4
electron-rich phosphine and N-heterocyclic carbene ligands
obtained when PdCl (Ph P) /Ph P was used as the catalyst and
2
3
2
3
t
have significantly contributed to the success of Pd-catalyzed
aminations. However, the synthesis of these ligands suffer from
tedious steps or expensive materials. Therefore, the development
BuONa was used as the base in refluxing toluene or dioxane
entries 1-2, Table 1).
(
Table 1. Screening conditions for PdCl (Ph P) /Ph P
of inexpensive and readily accessible catalytic systems is
2
3
2
3
a
5
catalyzed coupling reaction of 4-bromotoluene and aniline
attractive especially for industrial processes
.
Triphenylphosphine (Ph P),
a
simple and inexpensive
3
phosphine, has been applied extensively as a ligand in the Pd-
6
catalyzed coupling reactions. However, it is generally
considered less effective for the intermolecular amination
reaction, possibly due to its relative smaller steric hindrance and
7
less electron richness. Nevertheless, Ph P has still attracted the
b
3
b
Selectivity
Entry
Catalyst
Solvent
toluene
dioxane
Temp. Conv.
attention of researchers, because it is commercially available, air
stable, and inexpensive. Only recently has a Pd (dba) /Ph P
catalyzed coupling reaction of the anilines with aromatic halides
in refluxing aniline been reported. Herein, we report our results
on PdCl (Ph P) and Ph P catalyzed selective arylation reactions
3
a:4a
8
2
3
3
PdCl (Ph P)
2
3
3
3
3
2
2
2
2
1
2
110
110
0
0
-
3
/Ph P
8a,9
PdCl
Ph
PdCl (Ph
Ph
PdCl (Ph
2
(Ph
3
P
P)
P)
P)
-
/
2
3
2
3
2
between various aryl bromides and primary aryl amines.
3
4
p-xylene
o-xylene
140
145
57
92
85:15
97:3
/
3
P
2

2
Tetrahedron
/
Ph
PdCl (Ph
Ph
PdCl (Ph
Ph
PdCl (Ph
Ph
PdCl (Ph
PdCl
Pd(OAc)
Ph
PdCl
Pd(OAc)
PdCl (Ph
Ph
3
P
ACCEPTED MA
we w
N
U
er
S
e
C
su
R
rp
I
rised to find that the base played an important role
P
T
2
3
3
3
3
P)
P)
P)
P)
2
2
2
2
in determining mono arylation or diarylation of the amines
5
6
mesitylene
mesitylene
o-xylene
145
165
145
52
53
98
66:34
67:33
>99:1
/
3
P
(Table 3). When t-BuONa was replaced with t-BuOK, NaH,
KOH or K PO , both the catalytic activities and the selectivities
of diarylation decreased (entries 2-5, Table 2). Interestingly,
Cs CO provided exclusive formation of 4-methyldiphenylamine
4a) in a 95% yield after 8 hours (entries 6-7, Table 2). In the
cases of K CO or Na CO as the base, the conversion of aniline
2
3
4
/
3
P
c
2
7
2
3
/
3
P
(
8
9
2
o-xylene
o-xylene
145
145
85
77
95:5
95:5
2
3
2
3
2
/Ph
3
P
decreased, but the high selectivity for 4a remained (entries 8-9,
Table 2). Generally, it is quite difficult to tune the monoarylation
and diarylation of a primary amine in palladium-catalyzed
arylation reactions, because the monoarylation product, a
secondary amine, competes with the primary amine. In order to
achieve a selective monoarylation to give the diaryl amine, bulky
2
1
0
o-xylene
145
81
95:5
/
3
P
1
1
1
2
2
o-xylene
o-xylene
145
145
0
0
-
-
2
d
2
3
P)
2
1
3
o-xylene
145
21
41:59
/
3
P
a
2
Reaction conditions: aniline (1.0 mmol), 4-bromotoluene (2.5 mmol),
ligands are required in the amination. It is unusual that the base
t
BuONa (3.0 mmol), precatalyst (0.005 mmol, 0.5 mol%) and Ph
3
P (0.01
can be used to control the selectivity of a palladium catalyzed
arylation of primary amines, but monoarylated or diarylated can
be obtained with high selectivity in the PdCl (Ph P) /Ph P
b
mmol, 1.0 mol%), solvent (8.0 mL), reflux for 6 hrs under nitrogen;
c
d
conversion based on aniline measured by GC; reaction time: 12 hrs;
2
3
2
3
PdCl
2
(Ph
3
P)
2
(0.1 mol%) and Ph
3
P (0.2 mol%).
catalytic system described herein.
According to the proposed mechanism, four requisite
components influence the catalytic activity of the aminations
which are the palladium precursor, ligand, base, and solvent.
Table 2. The effect of base on the PdCl (Ph P) /Ph P
catalyzed amination between 4-bromotoluene and aniline
2
3
2
3
a
10
b
Selectivity
b
We focused on studying the effect of solvent and base to improve
the catalytic activity of PdCl (Ph P) /Ph P, so initiated our
Entry
Base
Conv.
3
a:4a
2
3
2
3
investigation by screening solvents. Generally, the role of
solvents is to dissolve the coupling partners as well as the base,
allow for a respective temperature window for the reaction, and
1
2
3
4
5
6
t-BuONa
t-BuOK
NaH
92
58
49
50
62
70
95
60
11
97:3
27:73
52:48
43:57
67:33
<1:99
<1:99
<1:99
<1:99
10
also stabilize intermediates in the catalytic cycle. In order to
elevate the reaction temperature, p-xylene, o-xylene, and
mesitylene were chosen as the solvent. After the reaction of
aniline and excessive 4-bromotoluene was carried out in p-xylene
KOH
3
o
K PO4
at 140 C for 6 hrs, 57% of aniline (1) was converted to an 85:15
mixture of 4,4’-dimethyltriphenylamine (3a) and 4-
methyldiphenylamine (4a) (entry 3, Table 1). Changing the
solvent with o-xylene increased the conversion of aniline to 92%
and the selectivity for triaryl amine (3a) increased to 97% (entry
Cs
2
2
CO
3
3
c
7
Cs
CO
c
8
K
2
CO
3
4
, Table 1). Prolonging the reaction time to 12 hours led to 98%
c
9
Na
2
CO
3
conversion of aniline and near exclusive formation of 3a (entry 7,
Table 1). When the coupling reaction was conducted in
mesitylene at 145 C, the conversion and selectivity were lower
than observed in o-xylene (entry 5, Table 1). No improvement in
a
o
Reaction conditions: aniline (1.0 mmol), 4-bromotoluene (2.5 mmol), base
3.0 mmol), PdCl (Ph P) (3.5 mg, 0.5 mol%) and Ph P (2.6 mg, 1.0 mol%),
(
2
3
2
3
b
o-xylene (8.0 mL), reflux for 6 hrs under nitrogen; conversion based on
yield or selectivity was observed when the reaction temperature
c
o
aniline measured by GC; reaction time: 8 hrs.
increased to 165 C (entry 6, Table 1). These results indicated that
the reaction temperature and the structure of solvent significantly
affect the activity of the PdCl (Ph P) /Ph P catalytic system. A
Under the optimized conditions, the scope and limitations of
the catalytic system (PdCl (Ph P) /Ph P) were explored. First, the
2
3
2
3
2
3
2
3
couple of reports have concerned o-xylene as a superior solvent
selective diarylation was investigated when t-BuONa was used as
base (Table 3). The steric hindrance of aryl bromides greatly
influenced the amination. Aryl bromides without ortho-
substituents cleanly provided triaryl products (3b – 3k Table 3).
However, when o-methyl bromobenzene reacted with aniline, the
mono arylated product, 2-methyldiphenylamine, was obtained in
in palladium-catalyzed coupling reactions, but the structural
11
influence of the solvent was not discussed. However, the effect
of the structure of solvents was found in metal catalyzed
asymmetric reactions, and was attributed to the participation of
12
the solvent in the reactions.
8
2% yield, and no diarylation product was detected (4b, Table 3).
Reducing the loading of Ph P led to a decrease in conversion
3
The catalyst system tolerated aryl chlorides by selectivity
performing the amination at the C-Br bond to yield triaryl amines
in excellent yields (3c, 3e and 3f, Table 3). In addition, the
catalytic system showed good toleration for the steric hindrance
of anilines. Bulky anilines, such as 2,4,6-trimethylaniline, were
biarylated in high yields (3i and 3j, Table 3). In the case of the
coupling of 2,6-dimethyl bromobenzene with 2,6-diisopropyl
aniline, the coupling reaction also worked well to give 4h in
and selectivity (entry 8, Table 1). When PdCl or Pd(dba) was
2
2
used as precatalyst instead of PdCl (PPh ) , the catalytic system
2
3 2
also displayed good activity and selectivity (entries 9-10, Table
). No coupling reaction occurred when PdCl or Pd(OAc) were
1
2
2
used as the precatalyst without Ph P (entries 11-12, Table 1).
3
These results demonstrate that Ph P is an effective ligand in the
3
amination of 4-bromotoluene. In addition, a remarkable decrease
of yield was observed when the catalyst loading was reduced to
.1 mol% (entry 13, Table 1).
9
4% yield (Table 3). The electronic factor of aryl bromides and
0
anilines had an impact on the amination. The reaction of electron-
rich m- and p-bromoanisoles gave the triaryl amines with
decreased yields (3d and 3k, Table 3). When p-fluoroaniline was
used only diaryl amines were formed regardless of the steric
Another crucial component of the reactive system was the
base which deprotonates the amine before or after coordination to
1,10
palladium. While screening bases with the model amination,

3
factors of the aryl bromide or if excess aryl b
4d, 4i, 4j and 4l, Table 3). Using p-trifluoromethyl aniline
resulted in no product formation.
A
ro
C
m
C
ide
E
w
P
a
T
s
E
us
D
ed MAan
N
d
U
typ
S
ic
C
al
R
ly
I
utilize expensive reagents or ligands. Inspired by
P
T
(
the above results, we explored the synthesis of these compounds
by the coupling reaction of 4,4’-diaminobiphenyl and aryl
bromides with our catalytic system. When the loading of
precatalyst and ligand increased to 5 mol% and 10 mol%, the
coupling reaction of 4,4’-diaminobiphenyl and 4-bromotoluene
gave the tetraaryl product in a 93% yield under the optimized
condition. We then examined the scope of the tetraarylation of
Table 3. Arylation of primary anilines with aryl bromides
t
a
catalyzed by PdCl (Ph P) /Ph P using BuONa as base
2
3
2
3
4
,4’-diaminobiphenyl (Table 5). The catalyst system,
PdCl (PPh) /Ph P, allowed for the synthesis of N,N,N’,N’-
2
3
3
tetraaryl-1,1’-biphenyl-4,4’-diamines in moderate to excellent
yields. Both electron-neutral and deficient aryl bromides worked
well to provide the corresponding products in excellent yields.
Tetra p-fluoro and p-chloride substituted N,N,N’,N’-tetraphenyl-
1
,1’-biphenyl-4,4’-diamines (6d and 6e, Table 5) were obtained
in over 90% yields. The amination also proceeded smoothly
when 2-bromonaphthalene was used to give the desired product
(6h) in 73% yield. The electron-rich aryl bromides, p- or m-
bromoanisole, provided the tetraarylated products with slightly
diminished yields of 76% and 82% respectively. In addition,
when 4-bromo-N,N-diphenylaniline was used as the substrate, the
corresponding product (6i) with six triaryl amine blocks was
successfully obtained in a 60% yield.
Table 5.Tetraarylation of 4,4’-diaminobiphenyl with aryl
bromides catalyzed by PdCl (Ph P) /Ph P
2
3
2
3
a
Reaction conditions: aniline (1.0 mmol), aryl bromide (2.5mmol),
BuONa (3.0 mmol), PdCl (Ph P) (3.5 mg, 0.5mol%) and Ph P (2.6 mg,
.0mol%), o-xylene (8.0 mL), reflux for 12 hrs under nitrogen, isolated yields.
t
2
3
2
3
1
Table 4. Mono-arylation of primary anilines with aryal
bromides catalyzed by PdCl (Ph P) / Ph P using Cs CO as base
2
3
2
3
2
3
a
Reaction conditions: 4,4’-diaminobiphenyl (1.0 mmol), aryl bromide (6.0
mmol), t-BuONa (6.0 mmol), PdCl
2
(Ph
3
P)
2
(5 mol%) and Ph
3
P (10 mol%), o-
a
Reaction conditions: aniline (1.0 mmol), aryl bromide (1.25 mmol),
CO (3.0 mmol), PdCl (Ph P) (3.5 mg, 0.5mol%) and Ph P (2.6 mg,
.0mol%), o-xylene (8.0 mL), reflux for 8 hrs under nitrogen, isolated yields.
o
xylene (12.0 mL), 144 C, 48 h.
Cs
1
2
3
2
3
2
3
3
. Conclusions
Next,
the
monoarylating
catalytic
system
of
In summary, we have found that Ph P exhibited high activity
3
PdCl (Ph P) /Ph P and Cs CO as a base was explored further
2
3
2
3
2
3
in the Pd-catalyzed coupling reaction of aryl bromides with
anilines in refluxing o-xylene to selectively provide triarylamines
or diarylamines. The reaction is strongly influenced by choice of
solvent, base, and structure of substrates: diarylamines were
achieved selectively when cesium carbonate was used as base;
(
Table 4). Electron-deficient and electron-neutral aryl bromides
reacted with primary amines to afford diaryl amines in very good
yields. o-Methyl bromobenzene reacted with p-fluoro aniline to
yield the diaryl amine (4d) in 83% of yield; and 2,4,6-trimethyl
aniline was monoarylated with p-chloro bromobenzene in 94% of
yield (4t, Table 4). However, the coupling reaction of p-
bromoanisole, an electron-rich aryl bromide, with aniline did not
occur. Methyl 4-aminobenzoate, which bears a base-sensitive
functional group, was also coupled to give the mono-arylated
product (4u) in 83% yield.
t
while the use of BuONa selectively afforded triarylamines. In
addition, diarylamines were obtained when p-fluroaniline or o-
substituted arylbromide were used. Moreover, the catalytic
system tolerates sterically hindered anilines. The catalytic system
efficiently catalyzed the multiple arylation of 1,1’-biphenyl-4,4’-
diamines to afford N,N,N’,N’-tetraaryl-1,1’-biphenyl-4,4’-
diamines which are important intermediates of OLED hole
transport materials.
N,N,N’,N’-tetraaryl-1,1’-biphenyl-4,4’-diamines are important
intermediates of the hole transport materials of organic light
emitting diode (OLED).
synthesized by the Cu or Pd catalyzed coupling reactions of
,4’-diiodobiphenyl or 4,4’-dibromobiphenyl with diarylamines
13
These compounds are usually
14
15
4. Experimental section
4
4
.1. General information and materials

4
Tetrahedron
2
0
All reagents and solvents were obtained
A
fro
C
m
C
c
E
om
P
m
T
e
E
rc
D
ial MA4.
NU
2.9
2
S
,4
C
,6
R
-Tr
I
i
P
m
T
ethyltriphenylamine (3i). Solid (Yield: 96%),
o
1
sources. Anhydrous dioxane and toluene were pre-dried over
sodium wire prior to continuous distillation over sodium-
benzophenone. Xylene and mesitylene were pre-dried over
sodium wire and freshly distilled. Reactions were routinely
carried out under an atmosphere of nitrogen with magnetic
stirring. The crude products were purified by flash column
chromatography on silica gel. H and C NMR spectra were
recorded on a AVANCE DMX-500 spectrometer operating at 500
and at 125 MHz, respectively.Chemical shifts (δ) are reported in
parts per million (ppm) and the coupling constants (J) are given
in hertz (Hz). High resolution mass spectra (HRMS) were
measured with a mass spectrometer Bruker Bio-TOF IIIQ.
m.p.: 138-140 C; H NMR (500 MHz, CDCl ): δ 7.22 (t, J = 7.5
3
Hz, 4H), 7.01 (d, J = 7.5 Hz, 4H), 6.97 (s, 2H), 6.90 (t, J = 7.5
Hz, 2H), 2.36 (s, 3H), 2.03 (s, 6H).
21
4
.2.10
2,4,4’,4’’,6-Pentamethyltriphenylamine(3j).
Solid
o
1
(Yield: 95%), m.p.: 139-141 C; H NMR (500 MHz, CDCl ): δ
3
1
13
7.00 (d, J = 8.3 Hz, 4H), 6.94 (s, 2H), 6.87 (d, J = 8.3 Hz, 4H),
.34 (s, 3H), 2.29 (s, 6H), 2.01 (s, 6H).
2
4.2.11 2,4,6-Trimethyl-3’,3’’-dimethoxytriphenylamine (3k).
Solid (Yield: 66%), m.p.: 108-110 C; H NMR (500 MHz,
CDCl ): δ 7.08 (t, J = 8.1 Hz, 2H), 6.90 (s, 2H), 6.55-6.58 (m,
o
1
3
4H), 6.43 (d, J = 8.1 Hz, 2H), 3.71 (s, 6H), 2.30 (s, 3H), 1.99 (s,
1
3
6
1
H); C NMR (125 MHz, CDCl ): δ 18.68, 21.23, 55.38, 105.96,
3
4
.2 General Procedure for Catalytic Amination of Aryl
06.24, 112.82, 129.81, 130.08, 136.95, 137.75, 147.49, 160.58;
Bromide. In a Schlenk tube with a magnetic bar, base (3.0
mmol), PdCl (Ph P) (3.5 mg, 0.5 mol%), and Ph P (2.6 mg, 1.0
+
HRMS (m/z): Calcd for C H NO (M +H): 348.1185, found:
23
25
2
2
3
2
3
3
48.1971.
mol%), aryl amine (1.0 mmol) and aryl bromide (2.5 mmol) in o-
xylene (8.0 mL) were placed under nitrogen. The resulting
mixture was stirred at reflux for 8 hrs (or 12 hrs) under nitrogen.
The solvent was evaporated in vacuo, and the residue was
purified by flash column chromatography (petroleum ether–
EtOAc) to give the product.
22
4.2.12 4-Methyldiphenylamine (4a). Solid (Yield: 91%), m.p.:
84-87 C; H NMR (500 MHz, CDCl ): δ 7.24 (d, J = 8.3 Hz, 2H),
7.08 (d, J = 8.3 Hz, 2H), 6.99-7.01 (m, 4H), 6.88 (t, J = 7.3 Hz,
1H), 5.67 (br, 1H), 2.30 (s, 3H).
o
1
3
23
4
.2.13 2-Methyldiphenylamine (4b). Solid (Yield: 82%), m.p.:
16
o
1
4
.2.1 4,4’-Dimethyltriphenylamine (3a). Solid (yield: 98%),
108-110 C; H NMR (500 MHz, CDCl ): δ 7.22-7.24 (m, 3H),
7.19 (d, J = 7.5 Hz, 1H), 7.13 (t, J = 7.2 Hz, 1H), 6.88-.6.96 (m,
4H), 5.40 (br, 1H), 2.25 (s, 3H).
3
o
1
m.p.: 105-107 C; H NMR (500 MHz, CDCl ): δ 7.22 (t, J = 7.5
Hz, 2H), 7.07-7.11 (m, 6H), 7.02 (d, J = 8.4 Hz, 4H), 6.98 (t, J =
3
7
.5 Hz, 1H), 2.35 (s, 6H).
2
4
4
.2.14 2,4’-Dimethyldiphenylamine (4c). Solid (Yield: 80%),
16
o
1
4
9
.2.2 4,4’,4’’-Trimethyltriphenylamine (3b).
Solid (Yield:
m.p.: 51-53 C; H NMR (500 MHz, CDCl ): δ 7.16 (d, J = 8.2
Hz, 2H), 7.11 (d, J = 7.8 Hz, 1H), 7.07 (d, J = 8.2 Hz, 2H), 6.86-
3
o
1
3%), m.p.: 112-115 C; H NMR (500 MHz, CDCl ): δ 7.08 (d, J
3
=
8.3 Hz, 6H), 7.01 (d, J = 8.3 Hz, 6H), 2.35 (s, 9H).
6.91 (m, 3H), 5.30 (br, 1H), 2.30 (s, 3H), 2.24 (s, 3H).
1
7
4
(
(
2
.2.3 4,4’-Dichloro-4’’-methyltriphenylamine (3c).
Solid
4.2.15 4-Fluro-2’-methyldiphenylamine (4d). Oil (Yield: 78%);
o
1
1
Yield: 95%), m.p.: 92-95 C; H NMR (500 MHz, CDCl ): δ 7.20
d, J = 8.8 Hz, 4H), 7.11 (d, J = 8.3 Hz, 2H), 6.98-6.70 (m, 6H),
H NMR (500 MHz, CDCl ): δ 7.17 (d, J = 7.4 Hz, 1H), 7.06-
3
3
13
7.12 (m, 2H), 6.87-6.97 (m, 5H), 5.26 (br, 1H), 2.23 (s, 3H) ; C
.34 (s, 3H).
NMR (125 MHz, CDCl ): δ 18.01, 115.97, 116.19, 117.59,
3
1
8
120.31, 121.68, 127.06, 127.43, 131.16, 140.01, 142.28, 156.87,
4
(
6
4
.2.4 4,4’-Dimethoxy-4’’-methyltriphenylamine (3d).
Solid
+
o
1
159.25; HRMS(m/z): Calcd for C13
found: 202.1031.
H12FN (M +H): 202.0954,
Yield: 76%), m.p.: 127-129 C; H NMR (500 MHz, CDCl ): δ
.98-7.00 (m, 6H), 6.87 (d, J = 8.2 Hz, 2H), 6.78 (d, J = 8.9 Hz,
3
2
5
H), 3.76 (s, 6H), 2.26 (s, 3H).
4.2.16 4-Chloro-2’-methyldiphenylamine (4e).
Oil (Yield:
): δ 7.12-7.21 (m, 5H), 6.96 (t,
J = 7.3 Hz, 1H), 6.84 (d, J = 8.7 Hz, 2H), 5.35 (br, 1H), 2.23 (s,
H).
1
19
79%); H NMR (500 MHz, CDCl
3
4
(
7
.2.5 4-Chloro-4’,4’’-dimethyltriphenylamine (3e).
Solid
o
1
Yield: 90%), m.p.: 98-100 C; H NMR (500 MHz, CDCl ): δ
.13 (d, J = 8.4 Hz, 2H), 7.05 (d, J = 8.4 Hz, 4H), 6.96 (d, J = 8.4
3
3
26
Hz, 4H), 6.93 (d, J = 8.4 Hz, 2H), 2.30 (s, 6H).
4.2.17 2,2’,6,6’-Tetramethyldiphenylamine (4f). Solid (Yield:
o
1
17
89%), m.p.: 96-98 C; H NMR (500 MHz, CDCl
3
): δ 7.01 (d, J =
4
.2.6 4,4’,4’’-Trichlorotriphenylamine (3f). Solid (Yield: 91%),
m.p.: 145-147 C; H NMR (500 MHz, CDCl ): δ 7.20 (d, J = 8.8
o
1
7.4 Hz, 4H), 6.87 (t, J = 7.4 Hz, 2H), 4.83 (br, 1H), 2.04 (s, 12H).
3
2
7
Hz, 6H), 6.97 (d, J = 8.8 Hz, 6H).
4.2.18 2,6-Diethyl-2’,6’-dimethyldiphenylamine (4g).
(
Solid
o
1
Yield: 93%), m.p.: 96-98 C; H NMR (500 MHz, CDCl ): δ
3
4
9
7
6
2
2
1
.2.7 2,3,4’,4’’-Tetramethyltriphenylamine (3g). Solid (Yield:
5%), m.p.: 59-61 C; H NMR (500 MHz, CDCl ) δ 7.07 (t, J =
.5 Hz, 1H), 7.03 (d, J = 7.5 Hz, 1H), 6.98 (d, J = 8.3 Hz, 4H),
.96 (d, J = 7.5 Hz, 1H), 6.83 (d, J = 8.3 Hz, 4H), 2.27 (s, 3H),
.26 (s, 6H), 1.98 (s, 3H); C NMR (125 MHz, CDCl ): δ 14.78,
o
1
7.00-7.07 (m, 3H), 6.97 (d, J = 7.4 Hz, 2H), 6.79 (t, J = 7.4 Hz,
H), 4.90 (br, 1H), 2.45 (q, J = 7.5 Hz, 4H), 2.00 (s, 6H), 1.14 (t,
J = 7.5 Hz, 6H).
3
1
13
28
3
4.2.19 2,6-Dimethyl-2’,6’-diisopropyldiphenylamine (4h). Oil
1
0.76, 20.88, 121.54, 126.72, 127.50, 129.75, 130.56, 135.36,
38.06, 138.79, 145.82, 145.96; HRMS(m/z): Calcd for
(Yield: 94%); H NMR (500 MHz, CDCl ): δ 7.11-7.16 (m, 3H),
3
6.95 (d, J = 7.4 Hz, 2H), 6.73 (t, J = 7.4 Hz, 1H), 4.81 (br, 1H),
3.15 (hept, J = 6.9 Hz, 2H), 1.99 (s, 6H), 1.13 (d, J = 6.9 Hz,
+
C H N(M +H): 302.1830, found : 302.1889.
22
23
1
2H).
4
.2.8 2,3-Dimethyl-4’,4’’-dichlorotriphenylamine (3h). Solid
o 1
29
1
(Yield: 96%), m.p.: 101-103 C; H NMR (500 MHz, CDCl ): δ
4.2.20 4-Flurodiphenylamine (4i). Oil (Yield: 91%); H NMR
(500 MHz, CDCl ): δ 7.22-7.25 (m, 2H), 7.02-7.05 (m, 2H),
6.95-6.98 (m, 4H), 6.91 (t, J = 7.4 Hz, 1H), 5.55 (br, 1H).
3
7
1
.17 (d, J = 8.8 Hz, 4H), 7.10-7.14 (m, 2H), 6.98 (d, J = 8.4 Hz,
3
13
H), 6.92 (d, J = 8.8 Hz, 4H), 2.34 (s, 3H), 2.02 (s, 3H);
C
NMR (125 MHz, CDCl ): δ 14.70, 20.73, 122.64, 126.59,
1
HRMS (m/z): Calcd for C H Cl N (M +H): 342.0738, found:
3
3
30
4
.2.21 4-Fluro-4’-methyldiphenylamine (4j). Solid (Yield:
27.12, 127.36, 128.41, 129.35, 135.26, 139.29, 144.78, 146.18;
o
1
35 +
91%), m.p.: 43-45 C; H NMR (500 MHz, CDCl ): δ 7.05 (d, J =
8
3
20
17
2
.4 Hz, 2H), 6.93-6.96 (m, 4H), 6.89 (d, J = 8.4 Hz, 2H), 5.45
42.0791.
(br, 1H), 2.28 (s, 3H).

5
3
1
4
.2.22 2,4,6-Trimethyldiphenylamine (4k). So
A
lid
C
(
C
Yi
E
el
P
d:
T
8
E
6%
D
), MAso
N
lve
U
nt
S
w
C
as
R
e
I
vaporated in vacuo, and the residue was purified
P
T
o
1
m.p.：50-52 C; H NMR (500 MHz, CDCl ): δ 7.13 (t, J = 7.5
Hz, 2H), 6.93 (s, 2H), 6.72 (t, J = 7.5 Hz, 1H), 6.48 (d, J = 7.5
by flash column chromatography (petroleum ether–EtOAc) to
give the product.
3
Hz, 2H), 5.07 (br, 1H), 2.30 (s, 3H), 2.17 (s, 6H).
4
4
4' 4'
4
.3.112b
(6a).
CDCl ): δ 7.48 (d, J = 8.4 Hz, 4H), 7.27-7.30 (m, 8H), 7.14-7.16
N ,N ,N ,N -tetraphenyl-[1,1'-biphenyl]-4,4'-diamine
3
2
o 1
4
.2.23 4-Fluro-2’,4’,6’-trimethyldiphenylamine (4l).
Solid
Solid (93%); m.p.: 222-224 C; H NMR (500 MHz,
o
1
(
(
(
Yield: 71%), m.p.: 86-88 C; H NMR (500 MHz, CDCl ): δ 6.93
s, 2H), 6.83 (t, J = 8.7 Hz, 2H), 6.41 (m, 2H), 5.01 (br, 1H), 2.29
s, 3H), 2.15 (s, 6H).
3
3
13
(m, 12H), 7.05 (t, J = 7.6 Hz, 4H), C NMR (125 MHz, CDCl3):
δ 122.84, 124.12, 124.34, 127.32, 129.27, 134.79, 146.79,
+
3
3
147.77. HRMS (m/z): Calcd for C36
found: 489.2347.
H
28
N
2
(M +H): 489.2252,
4
.2.24 4,4’-Dimethyldiphenylamine (4m). Solid (Yield: 90%),
o
1
m.p.: 77-79 C; H NMR (CDCl , 500 MHz): δ 7.06 (d, J = 8.2
4
4
4' 4'
3
4
(
.3.2
N ,N ,N ,N -tetra-p-tolyl-[1,1'-biphenyl]-4,4'-diamine
Hz, 4H), 6.95 (d, J = 8.2 Hz, 4H), 5.69(br, 1H), 2.29 (s, 6H).
37
o 1
6b). Solid (93.%); m.p.: 213-215 C; H NMR (500 MHz,
CDCl ): δ 7.38 (d, J = 8.3 Hz, 4H), 7.04-7.06 (m, 12H), 7.01 (d, J
= 8.3 Hz, 8H), 2.30 (s, 12H); C NMR (125 MHz, CDCl
20.83, 122.98, 124.55, 127.09, 129.88, 132.41, 134.03, 145.37,
147.05. HRMS (m/z): Calcd for C40
found: 545.2969.
4
.2.25 4-Fluro-4’-chlorodiphenylamine (4n). Oil (Yield: 82%);
3
1
13
H NMR (500 MHz, CDCl ): δ 7.18 (d, J = 8.8 Hz, 2H), 6.98-
): δ
3
3
13
7
.02 (m, 4H), 6.87 (d, J = 8.8 Hz, 2H), 5.54 (br, 1H); C NMR
+
(
125 MHz, CDCl ): δ 116.18, 116.41, 118.03, 121.15, 121.23,
H N (M +H): 545.2878,
36 2
3
1
25.32, 129.53, 138.70, 142.93, 159.74; HRMS(m/z): Calcd for
35 +
4
4
4' 4'
C H ClFN (M +H): 222.0408, found: 222.0485.
4.3.3
6c). Solid (90%); m.p.: 166-169 C; H NMR (500 MHz,
CDCl ): δ 7.47 (d, J = 8.3 Hz, 4H), 7.18 (t, J = 8.3 Hz, 4H), 7.12
N ,N ,N ,N -tetra-m-tolyl-[1,1'-biphenyl]-4,4'-diamine
12
9
o 1
(
3
4
4
8
8
6
.2.26 4-Chloro-4’-methyldiphenylamine (4o). Solid (Yield:
o
1
3
6%), m.p.: 81-83 C; H NMR (500 MHz, CDCl ): δ 7.16 (d, J =
.7 Hz, 2H), 7.08 (d, J = 8.2 Hz, 2H), 6.95 (d, J = 8.2 Hz, 2H),
.89 (d, J = 8.7 Hz, 2H), 5.54 (br, 1H), 2.30 (s, 3H).
3
(
(
d, J = 8.3 Hz, 4H) , 6.97 (s, 4H), 6.95 (d, J = 8.3 Hz, 4H), 6.87
d, J = 8.3 Hz, 4H), 2.30 (s, 12H); C NMR (125 MHz, CDCl3):
δ 21.44, 121.61, 123.68, 124.00, 125.04, 127.18, 129.02, 134.49,
39.07, 146.94,147.78. HRMS (m/z): Calcd for C H N
M +H): 545.2878, found: 545.2963.
.3.4 N ,N ,N ,N -tetrakis(4-fluorophenyl)-[1,1'-biphenyl]-4,4'-
diamine (6d). Solid (95%); m.p.: 170-175 C; H NMR (500
MHz, CDCl ): δ 7.44 (d, J = 8.3 Hz, 4H), 7.08-7.10 (m, 8H) ,
7.05 (d, J = 8.2 Hz, 4H) , 7.00 (t, J = 8.3 Hz, 8H); C NMR (125
MHz, CDCl ):δ 116.09, 116.27, 122.82, 126.00, 126.07, 127.34,
134.37, 143.79, 146.93, 157.96, 159.89; HRMS (m/z): Calcd for
C H F N (M +H): 561.1876, found: 561.1966.
4.3.5 N ,N ,N ,N -tetrakis(4-chlorophenyl)-[1,1'-biphenyl]-4,4'-
13
2
a
1
(
4
4
.2.27 4,4’-Dichlorodiphenylamine (4p). Solid (Yield: 89%),
40 36
2
+
o
1
m.p.: 76-78 C; H NMR (500 MHz, CDCl ): δ 7.21 (d, J = 8.9
3
4
4
4' 4'
Hz, 4H), 6.95 (d, J = 8.9 Hz, 4H), 5.62 (br, 1H).
o 1
1
4
.2.28 2,3,4’-Trimethyldiphenylamine (4q). Oil (Yield: 89%); H
3
13
NMR (400 MHz, CDCl ): δ 6.98-7.05 (m, 4H), 6.79-6.84 (m,
3
13
3
H), 5.27 (br, 1H), 2.30 (s, 3H), 2.27 (s, 3H), 2.14 (s, 3H);
C
3
NMR (125 MHz, CDCl ): δ 13.75, 20.83, 20.89, 117.56, 117.96,
3
+
1
24.11, 126.15, 127.54, 129.92, 130.01, 137.92, 141.94, 142.37;
36
24
4
2
+
4
4
4' 4'
HRMS (m/z): Calcd for C H N (M +H): 212.1361, found:
15
17
o 1
2
12.1449.
diamine (6e). Solid (93%); m.p.: 164-170 C; H NMR (500 MHz,
CDCl ): δ 7.47 (d, J = 8.3 Hz, 4H), 7.24 (d, J = 8.3 Hz, 8H) ,
4
9
7
2
.2.29 4-Chloro-2’,3’-dimethyldiphenylamine (4r). Oil (Yield:
3
13
1
7
.11 (d, J = 8.3 Hz, 4H), 7.05 (d, J = 8.3 Hz, 8H); C NMR (125
0%); H NMR (500 MHz, CDCl ): δ 7.14 (d, J = 8.8 Hz, 2H),
3
MHz, CDCl ): δ 124.33, 125.28, 127.64, 128.18, 129.50, 135.37,
.02-7.06 (m, 2H), 6.92 (d, J = 8.1 Hz, 1H), 6.71 (d, J = 8.8 Hz,
3
35
+
13
1
6
4
4
45.97, 146.18; HRMS (m/z): Calcd for C H Cl N (M +H):
36 24 4 2
H), 5.34 (br, 1H), 2.31 (s, 3H), 2.13 (s, 3H); C NMR (125
25.0694, found: 625.0792.
MHz, CDCl ): δ 14.05, 21.00, 117.68, 119.76, 124.43, 125.68,
1
Calcd for C H ClN (M +H): 232.0815; found: 232.0910.
3
4
4
4' 4'
.3.6
N ,N ,N ,N -tetrakis(4-methoxyphenyl)-[1,1'-biphenyl]-
26.43, 129.46, 129.63, 138.40, 140.64, 144.19; HRMS (m/z):
12b o 1
35 +
,4'-diamine (6f). Solid (76%); m.p.: 177-180 C, H NMR (500
14
14
MHz, DMSO-d ): δ 7.38 (d, J = 8.3 Hz, 4H), 7.01 (d, J = 8.3 Hz,
6
35
4
9
8
2
.2.30 2,4,4’,6-Tetramethyldiphenylamine (4s). Solid (Yield:
8
H), 6.89 (d, J = 8.3 Hz, 8H), 6.80 (d, J = 8.3 Hz, 4H), 3.73 (s,
o
1
13
0%), m.p.: 64-66 C; H NMR (500 MHz, CDCl ): δ 6.95 (d, J =
3
12H); C NMR (125 MHz, DMSO-d ): δ 55.70, 115.40, 120.48,
6
.3 Hz, 2H), 6.92 (s, 2H), 6.41 (d, J = 8.3 Hz, 2H), 4.98 (br, 1H),
.29 (s, 3H), 2.23 (s, 3H), 2.16 (s, 6H).
1
26.92, 127.06, 132.27, 140.68, 147.59, 156.10. HRMS (m/z):
+
Calcd for C H N O (M +H): 609.2675, found: 609.2740.
4
4,4'-diamine (6g). Solid (82%); m.p.: 146-148 C; H NMR (500
40
36
2
4
4
4
4' 4'
.3.7
N ,N ,N ,N -tetrakis(3-methoxyphenyl)-[1,1'-biphenyl]-
4
.2.31 2,4,6-Trimethyl-4’-chlorodiphenylamine (4t). Solid
o 1
o
1
(
(
(
Yield: 94%), m.p.: 88-89 C; H NMR (500 MHz, CDCl ): δ 7.07
d, J = 8.8 Hz, 2H), 6.93 (s, 2H), 6.39 (d, J = 8.8 Hz, 2H), 5.06
br, 1H), 2.30 (s, 3H), 2.15 (s, 6H); C NMR (125 MHz, CDCl3):
3
MHz, CDCl ): δ 7.48 (d, J = 8.3 Hz, 4H), 7.16-7.19 (m, 8H),
3
1
3
13
6.73-6.74 (m, 8H), 6.61 (d, J = 8.3 Hz, 4H), 3.75 (s, 12H); C
NMR (125 MHz, CDCl ): δ 55.27, 108.38, 110.19, 116.87,
3
δ 18.38, 21.14, 114.48, 122.56, 129.30, 129.53, 135.29, 136.01,
1
2
35
+
124.59, 127.31, 129.82, 135.04, 146.53, 148.87, 160.51; HRMS
36.19, 145.54; HRMS (m/z): Calcd for C H ClN (M +H):
15 16
+
(
m/z): Calcd for C H N O (M +H): 609.2675, found:
40
36
2
4
46.0971, found: 246.1053.
.2.32 Methyl 4-(p-tolylamino)benzoate (4u). Solid (Yield:
6
09.2764. 4
36
4
4' 4'
4
8
=
4.3.8
N ,N ,N ,N -tetra(naphthalen-2-yl)-[1,1'-biphenyl]-4,4'-
o
1
o 1
3%), m.p.: 105-107 C; H NMR (500 MHz, CDCl ): δ 7.89 (d, J
diamine (6h). Solid (73%); m.p.: 122-124 C; H NMR (500
3
7.5 Hz, 2H), 7.15 (d, J = 7.4 Hz, 2H), 7.08 (d, J = 7.4 Hz, 2H),
MHz, CDCl ): δ 7.77-7.81 (m, 8H), 7.63 (d, J = 8.3 Hz, 4H),
3
6
.91 (d, J = 7.5 Hz, 2H), 5.95 (br, 1H), 3.87 (s, 3H), 2.34 (s, 3H).
7.54-7.56 (m, 8H) 7.38-7.45 (m, 12H), 7.26 (d, J = 8.3 Hz, 4H);
13
C NMR (125 MHz, CDCl ): δ 120.76, 124.56, 124.63, 124.67,
3
4
.3 General Procedure for tetraarylation of 4,4’-
1
1
6
4
26.36, 127.02, 127.49, 127.62, 129.04, 130.28, 134.48, 135.17,
diaminobiphenyl Catalyzed by PdCl (Ph P)/Ph P. In
Schlenk tube with a magnetic bar, t-BuONa (6.0 mmol),
PdCl (Ph P) (35.0 mg, 5 mol%), and Ph P (26.0 mg, 10mol%),
4
o-xylene (8.0 mL) were placed under nitrogen. The resulting
mixture was stirred at reflux for 48 hrs under nitrogen. The
a
+
2
3
3
45.33, 146.73; HRMS (m/z): Calcd for C H N (M +H):
52
36
2
89.2878, found: 689.2953.
2
3
2
3
1
1'
1
.3.9 N ,N -([1,1'-biphenyl]-4,4'-diyl)bis(N -(4-(diphenylamino)
,4’-diaminobiphenyl (1.0 mmol) and aryl bromide (6.0 mmol) in
4
4
phenyl)-N ,N -diphenylbenzene-1,4-diamine) (6i). Solid (60%);
m.p.: 213-215 C; H NMR (500 MHz, C D ): δ 7.37 (d, J = 8.3
o
1
6
6

6
Tetrahedron
Cheng, Q.; Song, W.; Cai, L.; Tao, X. Synlett 2012, 2333; (d) Okamoto,
Hz, 4H), 7.19 (d, J = 8.3 Hz, 4H), 7.11-7.1
A
4 (
C
m
C
, 1
E
6H
P
)
TED
2- MANUSCRIPT
, 7
.0
T.; Terada, E.; Kozaki, M.; Uchida, M.; Kikukawa, S.; Okada, K. Org.
Lett. 2003, 5, 373; (e) Monguchi, Y.; Kitamoto, K.;Ikawa,T.; Maegawa,
T. H. S. Adv. Synth. Catal. 2008, 350, 2767; (f) Heichert, C.;
Wrackmeyer, M.; Hartmann, H. Synthesis 2011, 3375; (g) Ye, S.;
Liu,Y.;Lu, K.; Wu, W.; Du, C.; Liu, Y.; Liu, H.; Wu, T.; Yu, G. Adv.
Funct. Mater. 2010, 20, 3125.
7
.05 (m, 24H), 6.97 (d, J = 8.3 Hz, 8H), 6.81 (t, J = 8.3 Hz, 8H);
C NMR (125 MHz, C D ): δ 122.49, 123.58, 123.94, 125.35,
1
3
6
6
1
25.59, 127.97, 129.26, 134.65, 142.96, 143.11, 146.93, 148.11;
+
HRMS (m/z): Calcd for C H N (M +H):1157.5192, found:
84
64
6
1
157.5297.
1
1
2. Zhou, J.; Ye, M.; Huang, Z.; Tang, Y. J. Org. Chem. 2004, 69, 1309.
3. (a) Stolka, M.; Yanus, J. F.; Pai, D. M. J. Phys. Chem. 1984, 88, 4707;
Acknowledgments
(
b) Saragi, T. P. I.; Fuhrmann-Lieker, T.; Salbeck, J. Adv. Funct. Mater.
2
006, 16, 966; (c) Shizu, K.; Sato, T.; Ito, A.; Tanaka, K.; Kaji, H. J.
We thank the National Natural Science Foundation of China
and Shanghai Key Laboratory of Molecular Catalysts and
Innovative Materials (2012MCIMKF01) for financial support.
Mater. Chem. 2011, 21, 6375; (d) Kamino, B. A.; Morse, G. E.; Bender,
T. P. J. Phys. Chem. C. 2011, 115, 20716.
1
1
4. (a) Low, P. J.; Paterson, M. A. J.; Goeta, A. E.; Yufit, D. S.; Howard, J.
A. K.; Cherryman, J. C.; Tackley, D. R.; Brown, B. J. Mater. Chem.
2004, 14, 2516; (b) Zhao, Y.; Wang, Y.; Sun, H.; Li, L.; Zhang, H.;
Chem. Commun. 2007, 3186; (c) Cheng, Y.; Liao, M.; Shih, H.; Shih, P.;
Hsu, C. Macromolecules 2011, 44, 5968; (d) Yuan, W. Z. ; Gong, Y.;
Chen, S.; Shen, X. Y.; Lam, J. W. Y.; Lu, P.; Lu, Y.; Wang, Z.; Hu, R.;
Xie, N.; Kwok, H. S.; Zhang, Y.; Sun, J. Z.; Tang, B. Z. Chem. Mater.
2012, 24, 1518.
Supplementary Data
1
13
These data include H NMR and C NMR spectra for all
products (3a-6i) described in this article. Supplementary data
related to this article can be found at
5. (a) Yamrmoto, T.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1998, 39,
2367; (b) Franz, A. W.; Rominger, F.; Müler, T. J. J. J. Org. Chem.
References and notes
2
008, 73, 1795; (c) Monguchi, Y.; Kitamoto, K.; Ikawa, T.; Maegawa,
1
2
.
.
(a) Riermeier, T. H.; Zapf, A.; Beller, M. Top. Catal. 1998, 4, 301; (b)
Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131; (c)
Lakshman, M. K. Curr. Org. Synth. 2005, 2, 83; (d) Sadig, J. E. R.;
Willis, M. C. Synthesis 2011, 1.
(a)Surry, D. S.; Buchwald, S. L. Chem. Sci. 2011, 2, 27; (b) Klinkenberg,
J. L.; Hartwig J. F. Angew. Chem. Int. Ed. 2011, 50, 86; (d) Hicks, J. D.;
Hyde, A. M.; Alberto Martinez, C.; Buchwald, S. L. J. Am. Chem. Soc.
T.; Sajiki, H. Adv. Synth. Catal. 2008, 350, 2767; (d) Lim, Y.; Park, Y.;
Kang, Y.; Jang, D. Y.; Kim, J. H.; Kim, J.; Sellinger, A.; Yoon, D. Y. J.
Am. Chem. Soc. 2011, 133, 1375; (e) Kamino, B. A.; Mills, B.; Reali, C.;
Gretton, M. J.; Brook, M. A. ; Bender, T. P. J. Org. Chem.2012, 77,
1663.
16. Goodbrand, H. B.; Hu, N. J. Org. Chem. 1999, 64, 670.
17. R. I. Walter, J. Am. Chem. Soc. 1955, 77, 5999.
18. Bushby, R. J.; McGill, D. R.; Ng, K. M.; Taylor, N. J. Chem. Soc.,
Perkin Trans. 2 1997, 1405.
19. Amthor, S.; Noller, B. Chem. Phys. 2005, 1-3, 141.
20. Yamamoto, M.; Matsubara, S. Chem. Lett. 2007, 1, 172.
21. Matsuo, K.; Shichida, Y.; Nishida, H.; Nakata, S.; Okubo, M. J. Phys.
Org. Chem. 1994, 1, 9.
2
2
2
009, 131, 16720; (e)Littke, A. F.; Fu, G. C. Angew. Chem. Int. Ed.
002, 41, 4176; (f) Christmann, U.; Vilar, R. Angew. Chem., Int. Ed.
005, 44, 366.
3
.
For selected references, see (a) Hartwig, J. F. Acc. Chem. Res. 1998, 31,
8
6
52. (b) Surry, D. S.; Buchwald, S. L. Angew. Chem. Int. Ed., 2008, 47,
338; (c) Rataboul, F.; Zapf, A.; Jackstell, R.; Harkal, S.; Riermeier, T.;
Monsees, A.; Dingerdissen, U.; Beller, M. Chem. Eur. J. 2004, 10, 2983;
d) Dai, Q.; Gao, W.; Liu, D.; Kapes, L. M.; Zhang, X. J. Org. Chem.
006, 71, 3928; (e) Lundgren, R. J.; Peters, B. D. Alsabeh, P. G.;
Stradiotto, M. Angew. Chem. Int. Ed., 2010, 49, 4071; (f) Kwong, F. Y.;
Chan, A. S. C. Synlett 2008, 1440; (g) Doherty, S.; Knight, J. G.;
McGrady, J. P.; Ferguson, A. M.; Ward, N. A. B.; Harrington, R. W.;
Clegg, W. Adv. Synth. Catal. 2010, 352, 201.
For selected references, see (a) Kantchev, E. A. B.; O’Brien, C. J.;
Organ, M. G. Angew. Chem. Int. Ed. 2007, 46, 2768; (b) Marion, N.;
Nolan, S. P. Acc. Chem. Res. 2008, 41, 1440; (c) Glorius, F. Top.
Organomet. Chem. 2007, 21, 1; (d) Valente, C.; Çalimsiz, S.; Hoi, K.
H.; Mallik, D.; Sayah, M.; Organ, M. Angew. Chem. Int. Ed. 2012, 51,
22. Park, S.; Kang, S. B.; Jung, K.; Won, J.; Yoon, Y.; Lee, S. Synthesis
2009, 815.
23. Kidwai, M.; Mishra, N. K.; Bhardwaj, S.; Jahan, A.; Kumar A.;
Mozumdar, S. ChemCatChem, 2010, 2, 1312.
(
2
24. Law, H. D. J. Chem. Soc. Trans. 1912, 101, 154.
25. Spagnolo, P.; Zanirato, P. Tetrahedron Lett. 1987, 9, 961.
26. Li, J.; Cui, M.; Yu, A.; Wu, Y. J. Organomet. Chem. 2007, 692, 3732.
27. Li, Y.; Zhang, J.; Li, X.; Geng, Y.; Xu, X.; Jin, Z. J. Organomet. Chem.,
2013, 737, 12.
28. Marion, N.; Navarro, O.; Mei, J. G. J. Am. Chem. Soc. 2006, 128, 4101.
29. Carroll, M. A.; Wood, R. A. Tetrahedron 2007, 63, 11349.
30. Zhang, L.; Wang, W.; Fan, R. Org. Lett. 2013, 15, 2018.
31. Reddy, B. V. S.; Reddy, N. S.; Reddy, Y. J.; Reddy, Y. V. Tetrahedron
Lett. 2011, 52, 2547.
4
.
3
2
314; (e) Chartoire, A.; Frogneux, X.; Nolan, S. P. Adv. Synth. Catal.
012, 354, 1897; (f) Organ, M. G.; Chass, G. A. ; Fang, D. C.;
Hopkinson, A. C.; Valente, C. Synthesis 2008, 2776; (g) Fang, W.;
Jiang, J.; Xu, Y.; Zhou, J.; Tu, T. Tetrahedron 2013, 69, 673; (h) Tu, T.;
Fang, W.; Jiang, J. Chem. Commun. 2011, 47, 12358; (i) Zhu, L.; Ye,
Y.; Shao, L. Tetrahedron 2012, 68, 2414.
32. Kobayashi, O.; Mori, Y.; Naito, T.; Enatsu, H.; Okumura, Y.; Igarashi, T.
Jpn. Kokai Tokkyo Koho. 2011, JP2011020949A20110203.
33. Chiang, G. C. H.; Olsson, T. Org. Lett. 2004, 6, 3079.
34. Kyo, A.; Masakatsu, T.; Akira, K. Chem. Express. 1990, 6, 385.
35. Ackermann, L.; Spatz, J. H.; Gschrei, C. J.; Born, R.; Althammer, A.
Angew. Chem. Int. Ed. 2006, 45, 7627.
36. Zhang, H.; Cai, Q.; Ma, D. J. Org. Chem.2005, 13, 5164.
37. Sreenath, K.; Suneesh, C. V.; Kumar, V. K. R.; Gopidas, K. R. J. Org.
Chem. 2008, 73, 3245.
5
6
.
.
Torborg, C.; Beller, M. Adv. Synth. Catal .2009, 351, 3027.
For selected references, see (a) Fresneau, N.; Hiebel, M.; Agrofoglio, L.
A.; Berteina-Raboin, S. Molecules 2012, 17,14409; (b) Chen, C.;
Huang, Yu; Su, W.; Kaneko, K.; Kimura, M.; Takayama, H.; Wong F.
F. J. Heterocycl. Chem. 2012, 49, 183; (c) Saleh, S.; Picquet, M.;
Meunier, P.; Hierso, J. Synlett 2011, 2844; (d) Leonori, D.; Coldham, I.
Adv. Synth. Catal. 2009, 351, 2619. (e) Doucet, H.; Hierso, J. Curr.
Opin. Drug Discov. Devel. 2007, 10, 672; (f) Manabe, K.; Nakada, K.
J.; Aoyama, N.; Kobayashi, S.Adv. Synth. Catal.2005, 347, 1499; (g)
Ali, B. E.; Fettouhi, M. J. Mol. Catal. A: Chem. 2002, 182-183, 195; (h)
Mowery, M. E.; DeShong, P. Org. Lett. 1999, 1 ,2137; (i) O'Keefe, D.
F.; Dannock, M. C.; Marcuccio, S. M. Tetrahedron Lett. 1992, 33,
6
679.
(a) Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901;
b) Hartwig, J. F.; Richards, S.; Barañano, D.; Paul, F. J. Am. Chem.
Soc. 1996, 118, 3626.
(a) Scholz, U.; Schlummer, B. Tetrahedron 2005, 61, 6379; (b)
Ehrentraut, A.; Zapf, A.; Beller, M. J. Mol. Catal. A: Chem. 2002, 182-
7
8
9
.
.
.
(
1
83, 515.
Buchwald, S. L.; Mauger, C.; Mignani, G.; Scholz, U. Adv. Synth. Catal.
006, 348, 23.
2
1
1
0. Schlummer, B.; Scholz, U. Adv. Synth. Catal. 2004, 346, 1599.
1. (a) Clark, J. H.; Paul, S. Green Chem. 2003, 5, 635; (b) Yamamoto, T.;
Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1998, 39, 2367; (c) Liu, T.;

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Supplementary Data
Effect of Solvent and Base on the Palladium Catalyzed Amination:
PPh /Pd Catalyzed Selectively Arylation of Primary Anilines with Aryl Bromides
3
a
a
a
a
a,
b
b,
Liangzhen Cai , Xuanying Qian , Wenjing Song , Taoping Liu , Xiaochun Tao *, Wanfang Li , Xiaomin Xie *
a
School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
b
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
1
13
H and C NMR spectra of triaryl amines (3a-3k) ................................................................................................................................ P2-P15
1
13
H and C NMR spectra of diaryl amines (4a-4u) ................................................................................................................................ P16-P41
1
13
4
4
4' 4'
H and C NMR spectra of N ,N ,N ,N -tetraaryl-[1,1'-biphenyl]-4,4'-diamines (6a-6i) ................................................................... P42-P59

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