Palladium-catalyzed Selective Amination of Aryl(haloaryl)amines with 9H-Carbazole Derivatives

Article abstract of DOI:10.1002/adsc.201701356

Palladium-catalyzed amination of aryl(haloaryl)amines with 9H-carbazole derivatives was investigated. In the amination of (4-bromophenyl)phenylamine with 9H-carbazole by the use of Pd₂(dba)₃/PtBu₃/NaOtBu catalyst, the main product was desired 9-[4-(phenylamino)phenyl]-9H-carbazole in 60% yield with conversion of (4-bromophenyl)phenylamine >99%, and the concomitant formation of 9-[4-[phenyl[4-(phenylamino)phenyl]amino]phenyl]-9H-carbazole (15% yield), which is the consecutive by-product, was observed. When XPhos was used instead of PtBu₃, the desired product was provided in 81% yield and the consecutive by-product was suppressed to 7.7%. The yield of the desired product reached 98% by the use of tBu-XPhos. Such excellent yields of the desired product were also obtained with other 2-di-tert-butyl- or 2-di(1-adamantyl)phosphino-1,1’-biaryls. Various 9-(arylamino)aryl-9H-carbazoles could be synthesized from aryl(haloaryl)amines and 9H-carbazole derivatives in high yields by the use of tBu-XPhos. The amination of 4-bromotoluene with a mixture of diphenylamine and 9H-carbazole gave only 9-o-tolyl-9H-carbazole with tBu-XPhos, while the use of PtBu₃ or XPhos afforded the mixture of 9-o-tolyl-9H-carbazole and diphenyl(o-tolyl)amine, indicating that Pd₂(dba)₃/tBu-XPhos/NaOtBu catalyst high selectively favors 9H-carbazole over diphenylamine as an amination substrate. (Figure presented.).

Full text of DOI:10.1002/adsc.201701356

Title: Palladium-catalyzed Selective Amination of Aryl(haloaryl)amines
with 9H-Carbazole Derivatives
Authors: Yuhki Otsuka, tetsuya yamamoto, Takanori Miyazaki, and
Tetsu Yamakawa
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201701356
Link to VoR: http://dx.doi.org/10.1002/adsc.201701356

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Palladium-catalyzed Selective Amination of
Aryl(haloaryl)amines with 9H-Carbazole Derivatives
Yuhki Ohtsuka,a Tetsuya Yamamoto,a,b Takanori Miyazaki,c Tetsu Yamakawaa*
a
Sagami Chemical Research Institute, Hayakawa 2743-1, Ayase, Kanagawa 252-1193, Japan
Fax: (+81)467-77-4113; phone: (+ 81)467-76-9268; e-mail address: t_yamakawa@sagami.or.jp
Present address: Tokyo Denki University, Senjyu Asahi-cho 5, Adachi-ku, Tokyo 120-8511, Japan
b
c
Tosoh Corporation, Kaisei-cho 4560, Shunan-shi, Yamaguchi 746-8501, Japan
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
Abstract:
aryl(haloaryl)amines with 9H-carbazole derivatives was
investigated. In the amination of (4-
bromophenyl)phenylamine with 9H-carbazole by the use of
Pd2(dba)3/PtBu3/NaOtBu catalyst, the main product was
desired 9-[4-(phenylamino)phenyl]-9H-carbazole in 60%
yield with conversion of (4-bromophenyl)phenylamine
>99%, and the concomitant formation of 9-[4-[phenyl[4-
Palladium-catalyzed
amination
of
tert-butyl- or 2-di(1-adamantyl)phosphino-1,1’-biaryls.
Various 9-(arylamino)aryl-9H-carbazoles could be
synthesized from aryl(haloaryl)amines and 9H-carbazole
derivatives in high yields by the use of tBu-XPhos. The
amination of 4-bromotoluene with
a
mixture of
diphenylamine and 9H-carbazole gave only 9-o-tolyl-9H-
carbazole with tBu-XPhos, while the use of PtBu3 or XPhos
afforded the mixture of 9-o-tolyl-9H-carbazole and
diphenyl(o-tolyl)amine, indicating that Pd2(dba)3/tBu-
XPhos/NaOtBu catalyst high selectively favors 9H-
carbazole over diphenylamine as an amination substrate.
(phenylamino)phenyl]amino]phenyl]-9H-carbazole
(15%
yield), which is the consecutive by-product, was observed.
When XPhos was used instead of PtBu3, the desired product
was provided in 81% yield and the consecutive by-product
was suppressed to 7.7%. The yield of the desired product
reached 98% by the use of tBu-XPhos. Such excellent yields
of the desired product were also obtained with other 2-di-
Keywords: 9H-carbazole; Buchwald-Hartwig amination;
palladium; Buchwald ligand
catalyst or peculiar apparatus, harsh condition and
limitation of a substrate.
Introduction
9-(Arylamino)aryl-9H-carbazoles
which
are
The Pd/phosphine/base-catalyzed amination of aryl
halides (or tosylates) with amines to form arylamines,
which is well known as the Buchwald-Hartwig
amination,[1] is powerful and versatile tool for the
formation of C-N bond and widely utilized in
medicinal chemistry and material chemistry.[1k]
Recently, the compounds having 9H-carbazole-9-yl
group have attracted much attention in organic
electronic materials[2] and have been synthesized
through the Buchwald-Hartwig amination with 9H-
carbazole derivatives using various phosphine ligands,
DPPF,[3] PtBu3,[4] tBu-XPhos,[5] JohnPhos,[6] SPhos,[7]
BippyPhos,[8] cBRIDP,[9] vBRIDP,[9] CMPhos[10] and
2-tBuPIndole[11] (with regard to the abbreviation of
the ligands, see Figure 1). In addition to the
Buchwald-Hartwig amination, the Cu-catalyzed
Ulmann reaction[12] or Ni-catalyzed amination[13] are
known for the syntheses of the compounds having
9H-carbazole-9-yl group from (hetero)aryl halides
with 9H-carbazole derivatives. However, they have
some disadvantage; the use of large amount of
diarylamines having 9H-carbazol-9-yl group(s) on
aryl group(s) are important building blocks in the
synthesis of organic semiconductors, i.e. hole
transport materials in OLEDs.[14,15] Although the
Buchwald-Hartwig amination using PtBu3 or XPhos
as a phosphine ligand is included in the syntheses of
these compounds, the substrate is not 9H-carbazole
derivatives but aniline or (9H-carbazole-9-yl)aniline
derivatives as depicted in Scheme 1(a)[14] or 1(b),[15]
respectively. Taking into account the use of the
Buchwald-Hartwig amination more effectively, one-
step amination of aryl(haloaryl)amines with 9H-
carbazole derivatives is one of promising and simple
route for the synthesis of 9-(arylamino)aryl-9H-
carbazoles (Scheme 1(c)). However, to the best of our
knowledge, the amination of aryl(haloaryl)amines
with 9H-carbazole derivatives has not been reported
at all. In use of this one-step route, the consecutive
amination of aryl(haloaryl)amine with the product of
9-(arylamino)aryl-9H-carbazole (side reaction A) or
intermolecular amination of aryl(haloaryl)amine (side
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
reaction B) should be suppressed for a satisfactory carbazoles were obtained in high yields by the use of
yield. In other words, palladium catalyst which Pd/tBu-XPhos/NaOtBu catalyst.
exhibits high chemoselectivity with 9H-carbazole
than with diarylamines in the amination should be
required.
Results and Discussion
At first, we examined the amination of (4-
bromophenyl)phenylamine 1a with 9H-carbazole 2a
by the use of Pd2(dba)3/PtBu3/NaOtBu catalyst.
(Scheme 2). The analysis by HPLC showed >99%
conversion of 1a and the formation of two kinds of
1
main products. H NMR characterization after the
isolation of these products revealed that one is desired
9-[4-(phenylamino)phenyl]-9H-carbazole 3a (48%
yield)
and
the
other
is
9-[4-[phenyl[4-
(phenylamino)phenyl]amino]phenyl]-9H-carbazole
4a (8% yield), respectively. Furthermore, we
ascertained that each HPLC yields were 60% and
15% by the use of authentic 3a and 4a synthesized
through the other method (see SI), respectively. As
depicted in Scheme 3, 4a might be formed by the
amination of 1a with 3a (path D). Another possible
route is the intermolecular amination between two
molecules of 1a to form (4-bromophenyl)phenyl[4-
(phenylamino)phenyl]amine 5a (path B) followed by
the amination of 5a with 2a (path C). However, we
did not detect 5a in the HPLC chromatogram. Taking
into consideration the reactivity of 1a-3a (vide infra),
we propose that 4a formation takes place via path D
where the amination with 9H-carbazole previously
occurs. In either path, two molecules of 1a should be
Scheme 1. Synthesis of 9-(arylamino)aryl-9H-carbazoles.
As Buchwald pointed out, there are no
methodological papers focusing on the amination
using 9H-carbazole derivatives.[1k] In particular, the
investigation on chemoselectivity seems insufficient.
In the amination of chlorobenzene, Nakayama and co-
workers
vBRIDP/NaOtBu
diphenylamine
demonstrated
[PdCl(allyl)]2/Cy-
active with
9H-carbazole.[9b]
catalyst
and inactive
is
However, palladium catalyst and condition which is
more effective in the amination with 9H-carbazole
derivatives than with diarylamines have been not
reported so far to our best knowledge.
Scheme 2. Pd2(dba)3/PtBu3/NaOtBu catalyzed amination of
(4-bromophenyl)phenylamine 1a with 9H-carbazole 2a.
Herein we investigated the Buchwald-Hartwig
amination of aryl(haloaryl)amines with 9H-carbazole
derivatives to form 9-(arylamino)aryl-9H-carbazoles.
In the amination of (4-bromophenyl)phenylamine
with 9H-carbazole, we found that Buchwald ligands
having two tert-butyl or 1-adamantyl groups were
remarkably efficient for the synthesis of the desired
product 9-[4-(phenylamino)phenyl]-9H-carbazole in
an excellent yield and selectivity, while PtBu3 or
Buchwald ligands having two cyclohexyl groups
afforded the consecutive by-product 9-[4-[phenyl[4-
(phenylamino)phenyl]amino]phenyl]-9H-carbazole,
resulting in low selectivity of 9-(arylamino)aryl-9H-
carbazoles. Moreover, various 9-(arylamino)aryl-9H-
Scheme 3. Possible pathway for the formation of 4a.
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
consumed for the formation of 4a. The selectivity of (dicyclohexylphosphino)phenyl]pyrene
(PyrPhos)
possessing 1-pyrenyl group in the upper phenyl ring
at the ortho position to phosphino group and applied
it to the amination (run 7). This ligand also provided
3a in a similar yield, selectivity and mass balance to
those in runs 2-6 with >99% conversion of 1a. With
regard to Cy-JohnPhos, MePhos and BrettPhos, the
conversion of 1a was rather low, resulting in a low
yield of 3a (runs 8 - 10), while the selectivity and
mass balance were satisfactory. CMPhos was also
ineffective in the present amination (run 11). By the
use of PCy3, P(o-tolyl)3 and amideCMPhos, the
conversion of 1a was almost 0% and only a trace
amount of 3a was detected (runs 12-14).
Interestingly, the use of the Buchwald ligands with
two tBu groups instead of those with two Cy groups
in runs 2, 3, 5 and 7-9 improved the yield of 3a with
>99% conversion of 1a. Thus, tBu-Xphos (L1), tBu-
DavePhos (L2), tBu-Sphos (L3), tBu-PyrPhos (L4, 1-
[2-(di-tert-butylphosphino)phenyl]pyrene, justly new
compound), JohnPhos and tBu-MePhos provided 3a
in 93-98% yield (runs 15-20). Since the formation of
4a was considerably suppressed, 0.2-2.1%, the
selectivity reached over 96%. In these runs, the yield
and selectivity of 3a were high enough to isolate 3a
readily from the reaction mixture in an excellent
yield; e. g., the isolated yield of 3a was 97% in run 15
(see SI). The results in runs 15-20 motivated us to
examine other ligands possessing two tBu grouos.
The ligands listed in runs 21-23 also gave more than
90% yield of 3a with >99% conversion of 1a, and
excellent selectivity and mass balance. As expected,
the substitution of tBu groups with Cy groups in
cBRIDP (run 22) to Cy-cBRIDP (run 24) or vBRIDP
(run 23) to Cy-vBRIDP (run 25) afforded 4a in 10%
or 5.8% yields with decline of the yields of 3a to 74%
or 51%. Of the 2-di-tert-butylphosphino-1,1’-biaryls
in runs 15-23, the amination with 9H-carbazole using
L1,[5] JohnPhos,[6] BippyPhos,[8] cBRIDP[9] and
vBRIDP[9] have already been reported. Therefore, it
seems reasonable that the excellent 3a yields were
also obtained in the present amination with these
ligands.
3a calculated from (yield of 3a)/[yield of 3a + 2×
(yield of 4a)] and the mass balance calculated by
[yield of 3a + 2×(yield of 4a)]/(conversion of 1a)[16]
were 67% and 90%, respectively; the latter indicates
the formation of additional products other than 3a and
4a. Trace amounts of several products were found in
the HPLC, suggesting that the formation oligomeric
by-products with high molecular weight. These
products may be formed through further consecutive
amination, 4a and/or 5a with 1a (Scheme 3). In
addition, debromination of 1a also may occur.
Next we surveyed phosphine ligands in the
amination of 1a with 2a. The structures of the ligands
tested are illustrated in Figure 1. The results of
screening of phosphine ligands are listed in Table 1.
As shown in runs 2-6, 2-dicyclohexylphosphino-1,1’-
biaryls, XPhos, DavePhos, RuPhos, SPhos and CPhos
gave 3a in slightly higher HPLC yields (81-83%) than
PtBu3 (run 1) with >99% conversion of 1a. The
selectivity of 3a and the mass balance using these
ligands reached 82-91% and 96-99%, which are also
larger than those obtained with PtBu3, indicating that
other by-products were scarcely formed. Furthermore,
we synthesized a new Buchwald ligand, 1-[2-
The excellent yield and selectivity of 3a in runs
15-20 suggest that sterically hindered 2-di-tert-
butylphosphino-1,1’-biaryls are effective in this
amination. The 1,1’-biaryl-2-yl groups in these
phosphine ligands do not have any substituent in the
upper phosphorus-bound phenyl ring. TrixiePhos (run
26), the upper aryl group of which is naphthyl group,
behaved similarly to the above phosphines.
Contrastingly, Me4-tBu-XPhos (run 27) and tBu-
BrettPhos (run 28), which have methyl or methoxy
groups in the upper phenyl group of 1,1’-biaryl-2-yl
groups, afforded a trace amount of 3a; the former was
synthesized for the Pd-catalyzed aminations.[17] It is
somewhat interesting that BrettPhos, which has two
Figure 1. Structure of phosphine ligands tested in Table 1
(iPr = isopropyl, Cy = cyclohexyl, tBu = tert-butyl, Ad = 1-
adamantyl).
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
Table 1. Screening of phosphine ligands.
Cy groups (run 10), is more active than tBu-BrettPhos.
Probably tBu-BrettPhos is too crowded around the
phosphorus atom for the present amination. 2-
tBuPIndole was also ineffective in the present
amination (run 29). With regard to other phosphines
possessing two tBu groups, QPhos (run 30), which
was synthesized for the Pd-catalyzed aminations,[18]
and m-Crophos® (run 31) were examined. However,
conv. yield yield
sel.
3a
run
L
mbb)
1aa)
3aa]
4aa]
both phosphines afforded poor conversion and yield.
Therefore, although tBu groups are indispensable for
a high selectivity of 3a, the other substituents in the
ligands also play an important role in the present
amination. Conversion, yield, selectivity and mass
balance were not affected by the substitution of the
tBu groups in JohnPhos and L2 with more sterically
hindered 1-adamantyl group (runs 32 and 33). None
of these ligands have been used in Pd-catalyzed
amination, however, Ad-JohnPhos has been used in
the Pd-catalyzed synthesis of diaryl ethers from aryl
halides and phenol derivatives.[19] On the other hand,
PAd2(nBu) showed poor yield and mass balance
despite the excellent conversion of 1a (run 34). The
poor mass balance obtained with PAd2(nBu) and m-
1
2
3
4
5
6
7
8
9
10
11
12c)
13c)
PtBu3
XPhos
DavePhos
RuPhos
SPhos
>99% 60% 15%
67% 90%
>99% 81% 7.7% 84% 96%
>99% 82% 8.2% 83% 98%
>99% 81% 8.9% 82% 99%
>99% 83% 7.0% 86% 97%
>99% 89% 4.2% 91% 97%
>99% 87% 3.9% 92% 95%
CPhos
PyrPhos
Cy-JohnPhos
MePhos
BrettPhos
CMPhos
PCy3
69%
68%
43%
38%
-
55% 4.4% 86% 92%
56% 3.8% 88% 94%
41% 0.3% 99% 97%
33% 2.2% 88% 98%
trace
trace
trace
nd
nd
nd
-
-
-
-
-
-
P(o-tolyl)3
-
-
14c) amideCMPhos
15
16
17
18
tBu-Xphos
(L1)
>99% 98% 0.6% 99% 99%
Crophos® were probably due to the debromination of
tBu-DavePhos >99% 98% 0.5% 99% 99%
(L2)
tBu-SPhos
(L3)
tBu-PyrPhos
(L4)
JohnPhos
tBu-MePhos
BippyPhos
cBRIDP
1a. Since bidentate ligands are frequently used in
Buchwald-Hartwig amination,[1k] DTBPF, DPPF, tBu-
Xantphos, Xantphos, BINAP and JosiPhos were
examined (runs 35-40). Of them, only DTBPF
provided moderate conversion and yield (run 35).
DPPF afforded only a trace amount of 3a, indicating
the definite necessity of two tBu groups for bidentate
ligands. Contrary to this, the xanthene back-bone with
either diphenylphosphino or di-tert-butylphosphino
groups afforded no desired product. BINAP was also
ineffective in the present amination. The results using
bidentate phosphines may suggest that flexible ligands
such as DTBPF act as monodentate ligands, which
coordinate to palladium only at one di-tert-
butylphosphino site. On the other hand, rigid ligands
such as tBu-Xantphos, Xantphos and BINAP
coordinate at two phosphino sites and the oxidative
addition of the C-Br bond may be difficult due to the
steric hindrance. JosiPhos, which has both
dicyclohexylphosphino and di-tert-butylphosphino
groups, afforded no product. We cannot explain the
reason for the inactivity of these ligands; however, we
speculate that the coordination to palladium in a
bidentate manner may retard the amination. Although
DTBPF afforded fairly poor selectivity and mass
>99% 98% 0.2% >99% 99%
>99% 98% 0.3% 99% 99%
19
20
21
22
23
24
25
26
27c)
>99% 93% 1.5% 97% 96%
>99% 95% 2.1% 96% 99%
>99% 90% 4.6% 91% 99%
>99% 95% 1.1% 98% 97%
>99% 98% 0.2% >99% 98%
>99% 74% 10%
72% 51% 5.8% 81% 87%
>99% 96% 1.4% 97% 99%
vBRIDP
Cy-cBRIDP
Cy-vBRDIP
TrixiePhos
Me4-tBu-
Xphos
tBu-BrettPhos
2-tBuPIndole
Qphos
m-Crophos®
79% 94%
-
trace
nd
-
-
28c)
29
30
31
32
33
34
-
trace
nd
-
-
46%
38%
22%
44% 0.3% 99% 97%
34% 1.0% 94% 95%
12% 1.8% 77% 71%
Ad-JohnPhos >99% 96% 1.4% 97% 99%
Ad-DavePhos >99% 96% 1.5% 97% 99%
PAd2Bu
DTBPF
DPPF
>99% 54% 16%
63% 86%
35c,d)
36c,d)
66%
41% 6.4% 76% 84%
-
-
-
-
-
trace
trace
trace
trace
trace
nd
nd
nd
nd
nd
-
-
-
-
-
-
-
-
-
-
37c,d) tBu-Xantphos
38c,d)
39c,d)
40c,d)
Xantphos
BINAP
JosiPhos
balance similarly to PAd2(nBu) and m-Crophos®, no
a) Determined by HPLC. b) When the conversion of 1a was
other amination products than 3a and 4a were
detected by the HPLC analysis. The debromination of
1a also seems to occur in this amination.
>99%, the mass balance (mb) was calculated by using
100% as conversion of 1a. c) Dash line (-) means that the
d)
conversion of 1a was almost 0%.
1.75 mol% of a
phosphine was used.
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
Furthermore, we examined the reaction in different
solvents at various reaction temperature using
Pd2(dba)3/L1/NaOtBu as shown in Table 3. The use
of toluene and 1,4-dioxane provided excellent
conversion of 1a, yield of 3a, selectivity of 3a and
mass balance (runs 1 and 2), despite that the reaction
was carried out at the lower temperature than 140 °C.
On the other hand, the reaction did not occur in DMF
or DMSO, which are solvents frequently used in
amination (runs 3 and 4). Surprisingly, the reaction in
xylene at 60 °C provided excellent conversion, yield,
selectivity and mass balance (run 5). Although the
conversion and the yield declined to 74% in the
reaction at 50 °C (run 6), both the selectivity and
mass balance were excellent, also suggesting that L1
essentially retards the consecutive amination of 1a
with 3a to form 4a. Furthermore, we examined the
reaction at 50 °C with L2, L3 and L4; these ligands
gave >99% conversion of 1a and the highest yield of
3a, 98% (see runs 17, 18 and 22 in Table 1). However,
only L4 provided the same conversion, yield and
selectivity as L1 (run 9). The amination did not
proceed with L2 and L3 (runs 7 and 8) suggesting
that not only two tert-butyl groups but also 1,1’-
biaryl-2-yl substituent is very important for the
present amination. 1-Pyrenyl group in the newly
synthesized L4 may be sterically similar to the 2,4,6-
triisopropylphenyl group in L1. In addition, vBRIDP
also afforded trace amount of 3a, though it revealed
excellent results in run 23 in Table 1.
Nakayama and co-workers reported the Pd-
catalyzed amination of chlorobenzene with 9H-
carbazole in the presence of the Grignard reagent
tBuMgCl as a base with just a little excess of
chlorobenzene ([chlorobenzene]/[9H-carbazole]
=
1.1).[9b] In this report, they compared the activity of
cBRIDP and vBRIDP, which were developed by
them, with other ligands. With regard to the ligands
possessing two tBu groups, the conversion of 9H-
carbazole decreased in the order of cBRDIP, L1 and
BippyPhos (>99%) > vBRIDP (63.8%) > JohnPhos
(35.9%) > L2 (31.2%) > PtBu3 (15.7%). The
phospine ligands which have two Cy groups, such as
Cy-vBRIDP, Cy-cBRIDP, DavePhos, XPhos and
SPhos, afforded the conversion in the range of 0.1-
3.4%. In addition, the amination did not occur with
the bidentate ligands, Xantphos, tBu-Xantphos and
DTBPF. Although the reaction conditions are
different in some respects from the present amination,
virtually the same trend in the yields was observed. It
seems that the character of the phosphine ligands
behaves similarly in the amination with 9H-carbazole.
Next, we examined the reactions with various
palladium precursors and bases using L1. The results
are shown in Table 2. With divalent palladium
precursors, PdCl2 and Pd(OAc)2, only a trace amount
of 3a was observed (runs 1 and 2). On the contrary,
[PdCl(-allyl)]2 gave an excellent result similar to
zero-valent Pd2(dba)3 (run 3). This might be due to
the generally accepted fact that Pd(II) in [PdCl(-
allyl)]2 is readily reduced to Pd(0). Both the
conversions and the yields were poor with inorganic
and organic bases other than NaOtBu (runs 4-7).
Noteworthy, the selectivity of 3a and mass balance in
runs 2, 4 and 5 are excellent despite the low
conversion of 1a and low yield of 3a. Thus, L1 may
essentially avoid formation of 4a presumably by the
amination of 1a with 3a.
Table 3. Screening of various solvents and reaction
temperature.
solvent
(T)
conv. yield yield
1aa] 3aa] 4aa]
sel.
3a
run
1
L
mb
toluene L1 >99% 98% 0.5% 99% 99%
Table 2. Screening of various Pd precursors and bases.
(110)
2
3
4
5
6
7
8
9
dioxane L1 >99% 96% 1.3% 98% 99%
(100)
DMF
(100)
DMSO L1
L1
-
-
trace
trace
nd
nd
-
-
-
-
(100)
xylene L1 >99% 98% 0.5% 99% >99%
(60)
conv. yield yield sel.
run
Pd
base
mb
-
1aa]
3aa]
4aa]
3a
xylene L1 74%- 73% 0.2% 99%
99%
1
2
3
PdCl2
NaOtBu
-
trace
nd
-
(50)
Pd(OAc)2 NaOtBu 35%
34% 0.1% 99% 98%
xylene L2
(50)
xylene L3
(50)
-
-
trace
trace
nd
nd
-
-
-
-
[PdCl(-
allyl)]2
Pd2(dba)3
Pd2(dba)3 Cs2CO3
Pd2(dba)3
Pd2(dba)3
NaOtBu >99% 97% 0.6% 99% 98%
4
5
6
7
K3PO4
71%
45%
70% 0.4% 99% >99%
44% 0.3% 99% >99%
xylene L4 75%
74% 0.1% >99% 99%
LiOH
NnPr3
-
-
trace
trace
nd
nd
-
-
-
-
(50)
a) Determined by HPLC.
a) Determined by HPLC.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
Table 4 lists the results of a detailed survey of the Table 5. Amination using various substrates with 9H-
experimental conditions using
by carbazole derivatives.a)
Pd2(dba)3/L1/NaOtBu in xylene at 140 °C. At first,
we examined the reaction using the same equivalents
of 2a and 1a. Although the conversion of 1a was
excellent, the yield of 3a slightly decline to 96% (run
1). Both the use of half the amount of Pd2(dba)3 and
shorter reaction time did not affect the conversion and
yield (runs 2 and 3). The selectivity of 3a and mass
balance were excellent in all entries.
run
1
2
3
yield
3b)
1
97%
(93%)
2a
3b
1b
1c
2
3
4
5
96%
(94%)
2a
2a
2a
2a
Table 4. Pd2(dba)3/L1/NaOtBu catalyzed amination under
various experimental conditions.
3c
3d
3e
97%
(94%)
1d
97%
(91%)
conv. yield
1aa] 3aa]
15 >99% 96%
yield
sel.
3a
run
1b)
Pd:1a:2a
t
mb
4aa]
1e
0.01:1:1.0
1.7% 97% >99%
0.6% 99% >99%
0.6% 99% 98%
2c) 0.005:1:1.05 15 >99% 98%
3b)
0.01:1:1.05
3
>99% 97%
97%
(93%)
a) Determined by HPLC. b) [P]/[Pd] = 3.5. c) [P]/[Pd] = 3.0.
1f
3f
Moreover, in the reaction by the use of (4-
6
7
98%
(95%)
2a
2a
2a
2a
2a
chlorophenyl)phenylamine (1a’) as
a substrate,
excellent conversion of 1a’ (>99%), yield of 3a
(98%), selectivity of 3a (99%) and mass balance
(>99%) were obtained as depicted in Scheme 4. We
believe that the Pd2(dba)3/L1/NaOtBu catalyst has
potential for industrial processes from the results in
Table 4 and Scheme 4.
3g
1g
96%
(90%)
1h
3h
3i
8
95%
(89%)
1i
1j
9
86%
(73%)
3j
10c)
Scheme 4. Pd2(dba)3/ L1/NaOtBu catalyzed amination of
(4-chlorophenyl)phenylamine (1a’) with 9H-carbazole.
95%
(90%)
1k
1l
3k
3l
Finally, we examined the amination of various
aryl(haloaryl)amines with 9H-carbazole derivatives
using Pd2(dba)3/L1/NaOtBu under basically the same
condition in run 15 in Table 1. Since the conversion
and selectivity were satisfactory for each substrates,
only the yield of the desired products are listed in
Table 5. The amination of meta-substituted, (3-
bromophenyl)phenylamine 1b (run 1), proceeded
smoothly as the amination of para-substituted 1a.
96%
(85%)
11
2a
2a
12d)
96%
(93%)
1m
1n
3m
3n
13d)
2a
90%
(80%)
However,
ortho-substituted
(2-
bromophenyl)phenylamine afforded no desired
product presumably due to the steric hindrance. The
present amination tolerated fluorine, methyl, methoxy
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
97%
(92%)
chlorophenyl)acetamide with 9H-carbazole using
cBRIDP as ligand and tBuMgCl as a base.[9b]
14
2a
2b
Of the products in Table 5, 3b,[14d] 3d,[14f] 3l[14g]
and 3m[15b] are reported as building blocks for the
synthesis of organic semiconductors. All of them
were synthesized through the routes in Scheme 1(a) or
(b) which afforded the lower yields than those in
Table 5. In addition, 3f was synthesized by the
Cu/K2CO3-catalyzed amination of (4’-iodo-1,1-
biphenyl-4-yl)phenylamine with 9H-carbazole at
rather high temperature, 230 °C.[20] Thus, the present
amination process is superior to these previous
methods in yield and reaction condition.
Along the study, we have been very interested in
the selectivity of 3a in Table 1. Thus, the yield of 3a
was remarkably higher when Buchwald ligands with
two tBu or Ad groups were used (runs 15-23, 25, 30
and 31) than when employing PtBu3 or Buchwald
ligands with two Cy groups (runs 1-11, 24 and 26).
We examined whether this difference occurs with
other substrate. 4-Bromotoluene and diphenylamine
1o
3o
3p
98%
(96%)
15
16
1a
98%
(96%)
1a
2c
3q
a)
1 (1.0 mmol), 2 (1.05 mmol), 0.5 mol% Pd2(dba)3, 3.5
mol% L1, NaOtBsu (1.5 mmol), xylene (3 mL), 140 °C, 15
b)
h. Determined by HPLC. The isolated yield was given in
parenthesis. c) JohnPhos was used instead of L1. d) 2a (2.10
mmol), 1.0 mol% Pd2(dba)3, 7.0 mol% L1, NaOtBu (3.0
mmol).
and phenyl groups on the phenyl or the 4-
bromophenyl group in 1a (runs 2-7). The substitution
of the phenyl group in 1a with 1-naphthyl group did
not affect the yield of desired product (run 8). On the
other hand, as shown in entry 9, the substitution of the
phenyl group with 3-pyridyl group, 1j, afforded a
slightly lower yield, 86%, than entry 8. It is
interesting that no desired product was obtained with
were chosen as
bromophenyl)phenylamine
a
simple analogue of (4-
1a and 9-[4-
(phenylamino)phenyl]-9H-carbazole 3a, respectively;
the substitution of phenylamino group in 1a with
methyl group or 9H-carbazole-9-yl group in 3a with
hydrogen atom turns to 4-bromotoluene or
diphenylamine. Therefore, the amination of 4-
bromotoluene with 2a or with diphenylamine can be
regarded as 3a formation from 1a and 2a or 4a
formation from 1a and 3a, respectively (see Scheme
3). The results of the amination using Pd2(dba)3/PtBu3,
XPhos or L1/NaOtBu are listed in Table 6. The
products were 9-p-tolyl-9H-carbazole 3r formed from
4-bromotoluene and 2a and diphenyl(p-tolyl)amine 4r
formed from 4-bromotoluene and diphenylamine in
all runs. The sum of the yield of these products was
96-97%, indicating that other reactions, such as the
debromination of 4-bromotoluene, scarcely occurred.
It is obvious that the yield of 3r was much larger than
that of 4r with any of the screened phosphines. This is
consistent with the results of runs 1, 2 and 15 in Table
1 where the yield of 3a is larger than that of 4a.
Interestingly, the selectivity of 3r calculated by (yield
of 3r)/(yield of 3r + yield of 4r) increased in the
order of PtBu3<XPhos<L1 and reached over 99%
with L1. This order is in excellent accordance with
the order of the 3a selectivity shown in runs 1, 2 and
15 in Table 1. Because the formation of 3r and 4r can
be regarded as the formation of 3a and 4a,
respectively, as mentioned above, the excellent yield
of 3a in Table 1 is presumably due to the observed
chemoselectivity in Table 6.
Pd2(dba)3/L1/NaOtBu from 1k, which has
a
bromopyridyl group. The excellent yield of 3k shown
in run 10 was obtained employing JohnPhos instead
of L1. The results in runs 9 and 10 suggest that
further investigation of phosphine ligand should be
required for the excellent yield from the substrates
having pyridyl groups. The amination of (4’-bromo-
1,1’-biphenyl-4-yl)phenylamine 1l with 9H-carbazole
also provided an excellent yield of 3l (run 11). The
amination of bis(4-bromophenyl)amine 1m with
twice amount of 2a and the catalyst gave 3m with an
excellent yield (run 12). As shown in run 13, 3n was
obtained from (3,5-dibromophenyl)phenylamine 1n in
a slightly lower yield, 90%, than the other products.
Since 3n was also obtained from (3,5-
dichlorophenyl)phenylamine in almost the same yield,
88%, as from 1n, this somewhat low yield is probably
due to not the reactivity of C-Br bond but steric
hindrance of 1n. The amination of (4-
bromophenyl)isopropylamine 1o, which is one of
alkyl(haloaryl)amines, provided excellent yield (run
14). The amination of 1a with fluoro- or methyl-
substituted 9H-carbazole proceeded smoothly with
excellent yields (runs 15 and 16).
On the other hand, the amination of N-(4-
bromophenyl)acetamide afforded no desired product
not only with L1 but also with PtBu3 or JohnPhos.
Nakamura and co-workers also failed to obtain any
The results in Table 6 seem to rule out the
formation of 4a via 5a in Scheme 3. Path B includes
product
from
the
amination
of
N-(4-
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
Experimental Section
Table 6. Amination of 4-bromotoluene with diphenylamine
and 9H-carbazole using PtBu3, XPhos and L1.
General techniques
HPLC analyses were performed using a Waters 2690
Separations Module up-grade with a ZORBAX
Eclipsa XDB-C18 column (Agilent Technologies, 5
m, 4.6 × 250 mm). A MeOH/THF (9/1) mixed
solution was used as eluent with a flow rate of 1.0
mL/min. The absorbance at 254 nm was monitored
25 °C. 3,6-Dibromo-9-phenyl-9H-carbazole or 9-p-
tolyl-9H-carbazole was used as internal standard.
When the peak of the starting amine overlapped with
the peak of 9H-carbazoles or xylene, the conversion
yield
3ra]
yield
4ra]
sel.
3r
run
L
1
2
3
PtBu3
XPhos
L1
83%
91%
97%
13%
5.1%
0.3%
86%
95%
>99%
a) Determined by HPLC.
1
of the amine was determined by H NMR. When the
peak of the desired product was overlapped with the
peak of xylene, HPLC analyses was carried out after
removal of xylene under vacuum. 1H, 13C, 19F and 31P
NMR spectra were recorded on a Bruker DRX-500
(1H 500 MHz, 13C 126 MHz, 19F 470 MHz, 31P 202
MHz) spectrometer and the chemical shifts are
the intermolecular amination of 1a which is one of
diphenylamine derivatives (vide supra), while path D
contains the amination of 1a with 2a. Taking into
account the reactivity of diphenylamine and 2a
observed in Table 6, 4a can be formed via path D
including the amination with 9H-carbazole 2a.
1
expressed in ppm (δ). H NMR was measured in
CDCl3 and DMSO-d6 with tetrametylsilane (0.00
ppm) and methyl proton in remained DMSO (2.49
ppm) as an internal reference, respectively. 13C NMR
was measured in CDCl3, DMSO-d6 and THF-d8 with
each carbons in the solvents, 77.0 ppm, 39.7 ppm and
25.2 ppm (3 or 4 position), were used as an internal
reference. 19F NMR was measured in DMSO-d6 with
benzotrifluoride (-63.72 ppm) as an internal reference.
31P NMR was measured in CDCl3 with 85% H3PO4
aq solution as an external reference (0.00 ppm). The
multiplicties are indicated by s (singlet), brs (broad
singlet), d (doublet), t (triplet), q (quartet), dt (doublet
of triplet), tt (triplet of triplet) and m (multiplet). IR
was measured using a HORIBA FT-720 in reflective
mode. High-resolution mass spectroscopy (HRMS)
was measured using a Jeol JMS-T100LP mass
spectrometer in ESI(+) mode. All commercially
available reagents were used without further
purification. Deoxidized xylene was purchased from
Wako Pure Chemicals Industries, Ltd.. 1c was
synthesized by SNAr with 4-bromoaniline and 1,4-
difluorobenzene following a literature procedure.[21]
1d, 1e, 1j and 1k were synthesized by the Pd-
Conclusion
In summary, we have developed the catalytic system
Pd2(dba)3/2-di-tert-butyl or (1-adamantyl)phosphino-
1,1’-biaryl/NaOtBu for the synthesis of 9-[4-
(phenylamino)phenyl]-9H-carbazole from (4-bromo
or chlorophenyl)phenylamine and 9H-carbazole in an
excellent yield with only a little amounts of by-
product, which was formed through the consecutive
amination of the desired product and the starting
material, resulting in a high selectivity. Employing
Pd2(dba)3/L1/NaOtBu, various 9-(arylamino)aryl-9H-
carbazoles were obtained from a wide range of
aryl(haloaryl)amines and 9H-carbazole derivatives as
substrates. The amination of 4-bromotoluene with the
mixture of diphenylamine and 9H-carbazole in the
presence of Pd2(dba)3/ L1/NaOtBu gave 9-p-tolyl-9H-
carbazole with >99% selectivity, indicating that
Pd2(dba)3/L1/NaOtBu catalyst selectively favors 9H-
carbazole over diphenylamine as a substrate for the
amination.
The present catalyst exhibits unique selectivity in
the amination with 9H-carbazole derivatives.
Therefore, the protection of nitrogen atom in
aryl(haloaryl)amines is unnecessary for the synthesis
catalyzed
amination
of
the
corresponding
bromoiodobenzenes with anilines.[22]
Syntheses of PyrPhos and tBu-PyrPhos (L4)
of
9-(arylamino)aryl-9H-carbazoles
(see
SI),
First 1-pyreneboronic acid (2.99 g, 12.1 mmol), (2-
bromo)iodobenzene (3.76 g, 13.3 mmol), Pd(PPh3)4
(0.70 g, 0.61 mmol), Na2CO3 aqueous solution (2.0
mol/L, 15 mL), toluene (20 mL) and EtOH (15 mL)
were added to a reaction vessel under an Ar
atmosphere. The mixture was heated at 90 °C for 9 h.
After cooling to room temperature, the solvent was
removed under vacuum. The residue was purified by
passing through a silica gel column (eluent: hexane)
suggesting that the present amination may be
practically predominant. Because the amination with
9H-carbazole derivatives will most certainly
contribute to the design of new organic
semiconductors, it seems very important to disclose
the origin of the selectivity. Not only rigorous steric
and electronic effects of the phosphine ligands but
also detailed investigation of the mechanism are
currently in progress.
8
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
and 1-(2-bromophenyl)pyrene was obtained as a mp 172.2-173.9 °C; 1H NMR (500 MHz, CDCl3) δ =
white solid (3.20 g, 9.0 mmol, 75% yield). 1.04 (d, JHP = 11.6 Hz, 9H), 1.21 (d, JHP = 11.6 Hz,
1-(2-Bromophenyl)pyrene (1.43 g, 4.0 mmol) and 9H), 7.35-7.42 (m, 1H), 7.44-7.51 (m, 2H), 7.67-7.72
THF (20 mL) were added to a reaction vessel under (m, 1H), 7.86-7.92 (m, 2H), 7.94-7.99 (m, 1H), 8.01-
an Ar atmosphere. After cooling to -78 °C, BuLi 8.12 (m, 4H), 8.13-8.19 (m, 2H); 13C NMR (126 MHz,
hexane solution (1.6 mL, 2.6 mol/L, BuLi 4.2 mmol)
was added to the reaction mixture and the obtained
CDCl3)  = 30.85, 30.88, 31.00, 31.02, 32.2, 32.4,
32.8, 33.1, 123.5, 124.6, 124.7, 124.8, 124.9, 125.7,
126.2, 126.5, 126.6, 127.0, 127.6, 128.2, 129.21,
129.22, 129.3, 129.4, 130.3, 131.0, 131.5, 132.0,
132.1, 135.58, 135.60, 137.3, 137.6, 139.0, 139.1,
149.3, 149.7; 31P NMR (202 MHz, CDCl3) δ = 19.3
(s); IR (neat) 2939, 1456, 1362, 1174, 843, 723 cm-1;
HR-MS: calcd for C30H32P (M+H+): 423.2236;
found:m/z 423.2230.
mixture
was
stirred
for
1
h.
Then,
chlorodicyclohexylphosphine (1.10 g, 4.7 mmol) was
added and the mixture was stirred at room
temperature for 14 h. A saturated aq. solution of
NH4Cl (1.0 mL) was added and then the solvent was
removed under vacuum. The residue was purified by
passing through
hexane/chloroform
(dicyclohexylphosphino)phenyl]pyrene
a
silica gel column (eluent:
10/0-9/1) and 1-[2-
(PyrPhos)
=
Reaction procedures
The procedure of 1a and 2a to 3a and 4a using
Pd2(dba)3/PtBu3/NaOtBu shown in entry 1 in Table 1
is used as a representative example. 1a (248 mg, 1.0
mmol), 2a (176 mg, 1.05 mmol), Pd2(dba)3 (4.6 mg,
5.0 mol), PtBu3˖HBF4 (10.2 mg, 35 mol) and
NaOtBu (144 mg, 1.5 mmol) were added to a 10 mL
reaction vessel and Ar gas was thoroughly flashed.
After the addition of dehydrated and degassed xylene
(3 mL) in an Ar stream, the vessel was sealed and
heated at 140 °C for 15 h. After cooling to room
temperature, the reaction was quenched by the
addition of deionized water (25 mL) and the organic
compounds were completely dissolved by the
addition of ethyl acetate (HPLC grade, 20 mL) and
stirring. After adding 50 mg of 9H-9-(p-
tolyl)carbazole as internal standard to the obtained
water-ethyl acetate mixture, 0.1 mL of the ethyl
acetate phase was diluted with THF (HPLC grade, 3
mL). The analysis of 3 L of this THF solution by
HPLC revealed the formation of 3a in 60% and 4a in
15% to 1a, respectively. The isolation of 3a and 4a
was carried out as follows. The products were
extracted twice from the above water-ethyl acetate
mixture by adding ethyl acetate (20 mL). Then the
ethyl acetate layer was washed with sat. NaCl aq.
solution (20 mL) and dried over Na2SO4. The solvent
was removed under vacuum and the residue was
purified by passing through a silica gel column
was obtained as a pale yellow solid (1.34 g, 2.8 mmol,
71% yield).
mp 193.7-195.4 °C; 1H NMR (500 MHz, CDCl3) δ =
0.88-1.27 (m, 10H), 1.45-1.86 (m, 12H), 7.36-7.52 (m,
3H), 7.65 (d, J = 9.2 Hz, 1H), 7.74 (d, J = 6.9 Hz, 1H),
7.85 (d, J = 7.8 Hz, 1H), 7.93 (d, J = 9.2 Hz, 1H),
7.97 (dd, J = 7.8 Hz, 7.8 Hz, 1H), 8.06 (d, J = 8.9 Hz,
1H), 8.09 (d, J = 8.9 Hz, 1H), 8.12 (d, J = 7.8 Hz, 1H),
8.17 (dd, J = 7.8 Hz, 7.8 Hz, 2H); 13C NMR (126
MHz, CDCl3)  = 26.3, 26.4, 27.02, 27.14, 27.25,
27.33, 27.39, 27.44, 29.07, 29.14, 29.38, 29.49, 30.0,
30.1, 30.7, 30.8, 33.8, 34.0, 34.9, 35.1, 123.6, 124.5,
124.7, 124.87, 124.90, 125.7, 126.2, 126.7, 126.9,
127.1, 127.6, 128.1, 128.96, 129.00, 129.31, 129.32,
130.5, 131.0, 131.46, 131.47, 131.51, 132.87, 132.90,
135.9, 136.1, 138.3, 138.4, 148.9, 149.2; 31P NMR
(202 MHz, CDCl3) δ = –12.6 (s). IR (neat) 2925,
1442, 1182, 847, 721 cm-1; HR-MS: calcd for C34H36P
(M+H+): 475.2549; found:m/z 475.2511.
1-(2-Bromophenyl)pyrene (1.43 g, 4.0 mmol) and
THF (25 mL) were added to a reaction vessel under
an Ar atmosphere. After cooling to -78 °C, BuLi
hexane solution (1.8 mL, 2.7 mol/L, BuLi 4.8 mmol)
was added to the reaction mixture and the obtained
mixture was stirred for 1 h. CuCl (0.396 g, 4.0 mmol)
was added to the mixture, followed by the dropwise
addition of chlorodi-tert-butylphosphine (0.91 mL,
4.8 mmol). The resulting mixture was stirred at 70 °C
for 14 h. Ethyl acetate (150 mL) was added to the
mixture after cooling to room temperature. After
washing with a mixed solution of sat. NH4Cl aq.
solution (40 mL) and H2O (10 mL), 12% NH3 aq.
solution (3 x 50 mL) and sat. NaCl aq. solution (50
mL), the organic layer was dried over Na2SO4. Then,
the solvent was removed under vacuum. The residue
was purified by passing through a silica gel column
(eluent: hexane/chloroform = 9/1-5/5) and 1-[2-(di-
1
(eluent: hexane/ethyl acetate = 9/1). The H NMR
spectrum indicated that the obtained solid (254 mg)
was mixture of 3a (194 mg, 58%) and 4a (60 mg,
13%). The mixture was further purified with silica gel
preparative TLC (eluent hexane/CH2Cl2 = 8/1, four
times), providing 3a as a white solid (161 mg, 48%
1
yield) and 4a as a white solid (40 mg, 8% yield). H
NMR of 3a agreed with the reported data. Because 4a
is a new compound, it was fully characterized (see
below).
tert-butylphosphino)phenyl]pyrene
(tBu-PyrPhos)
[4-(9H-carbazol-9-yl)phenyl]phenylamine (3a):
1H NMR (500 MHz, DMSO-d6) δ 5.88 (brs, 1H),
was obtained as a pale yellow solid (0.51 g, 1.2 mmol,
30% yield).
9
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
6.98-7.04 (m, 1H), 7.17-7.22 (m, 2H), 7.23-7.30 (m, cm-1; HR-MS: calcd for C36H26N3 (M+H+): 500.2121;
4H), 7.31-7.44 (m, 8H), 8.12-8.17 (m, 2H).
found: m/z 500.2090.
Characterization of products
9-(4-isopropylaminophenyl)-9H-carbazole (3o):
1
The following eight products are new. Their melting white solid. mp 119.6-121.0 °C; H NMR (500 MHz,
point, NMR (1H, 13C and 19F), IR and HR-MS data are DMSO-d6) δ = 1.19 (d, J = 6.3 Hz, 6H), 3.54-3.67 (m,
shown below. The charts of NMR are included in SI. 1H), 5.80 (d, J = 7.8 Hz, 1H), 6.77 (d, J = 8.8 Hz, 2H),
The other compounds are known and NMR spectra 7.19-7.28 (m, 6H), 7.35-7.41 (m, 2H), 8.17-8.22 (m,
agreed with the reported data.
9-[3-methyl-4-(phenylamino)phenyl]-9H-
2H); 13C NMR (126 Mz, CDCl3)  = 22.9, 44.2, 109.8,
113.6, 119.3, 120.1, 122.9, 125.6, 126.3, 128.4, 141.6,
146.9; IR (neat) 3400, 1520, 1450, 1315, 1232, 822,
750, 723 cm-1. HR-MS: calcd for C21H21N3 (M+H+):
301.1699; found: m/z 301.1681.
1
carbazole (3g): white solid. mp 50.6-53.7 °C; H
NMR (500 MHz, DMSO-d6) δ = 2.32 (s, 3H), 6.81-
6.87 (m, 1H), 7.07 (dd, J = 1.0, 8.6 Hz, 2H), 7.22-
7.32 (m, 5H), 7.34-7.45 (m, 6H), 7.57 (brs, 1H), 8.22
3-methyl-9-(4-phenylamino)phenyl-9H-carbazole
13
1
(d, J = 7.7 Hz, 2H); C NMR (126 MHz, DMSO-d6)
(3p): white solid. mp 49.6-52.3 °C; H NMR (500
 = 17.9, 109.8, 118.3, 118.4, 119.5, 120.2, 121.2, MHz, DMSO-d6) δ = 2.48 (s, 3H), 6.86-6.92 (m, 1H),
123.1, 125.5, 125.7, 128.7, 129.4, 129.5, 130.6, 140.9, 7.16-7.25 (m, 5H), 7.26-7.34 (m, 5H), 7.36-7.42 (m,
141.2, 143.2; IR (neat) 3388, 3047, 1595, 1493, 1450, 3H), 8.01 (d, J = 0.8 Hz, 1H), 8.16 (d, J = 7.7 Hz, 1H),
1309, 1228, 742, 721 cm-1; HR-MS: calcd for
C25H21N2 (M+H+): 349.1699; found:m/z 349.1708.
9-[3-fluoro-4-(m-tolyl)aminophenyl]-9H-
8.46 (brs, 1H); 13C NMR (126 MHz, DMSO-d6)  =
21.2, 109.5, 109.7, 117.3, 117.7, 119.6, 120.3, 120.4,
120.5, 122.5, 122.7, 126.0, 127.5, 127.8, 128.4, 128.6,
129.4, 139.2, 141.0, 143.1, 143.3; IR (neat) 3388,
1597, 1512, 1456, 1309, 1230, 798, 742, 696 cm-1;
HR-MS: calcd for C25H21N2 (M+H+): 349.1699;
found: m/z 349.1708.
1
carbazole (3h): white solid. mp 40.2-43.6 °C; H
NMR (500 MHz, DMSO-d6) δ = 2.28 (s, 3H), 6.74 (d,
J = 7.4 Hz, 1H), 6.92-7.00 (m, 2H), 7.17 (t, J = 7.7 Hz,
1H), 7.25-7.33 (m, 3H), 7.37-7.54 (m, 6H), 8.13 (brs,
1H), 8.23 (d, J = 7.7 Hz, 2H); 13C NMR (126 MHz,
CDCl3)  = 21.4, 109.6, 114.5, 114.7, 116.47, 116.56, (3q): white solid. mp 43.6-46.6 °C; H NMR (500
116.59, 119.8, 120.18, 120.24, 123.15, 123.23, 123.26, MHz, DMSO-d6) δ = 6.87-6.93 (m, 1H), 7.02-7.13 (m,
123.41, 125.9, 129.05, 129.14, 129.26, 131.64, 131.75, 2H), 7.18-7.23 (m, 2H), 7.24-7.34 (m, 6H), 7.37-7.45
139.4, 141.02, 141.08, 151.2, 153.6; 19F NMR (470 (m, 3H), 8.18-8.27 (m, 2H), 8.50 (brs, 1H); 13C NMR
2-fluoro-9-(4-phenylamino)phenyl-9H-carbazole
1
(126 MHz, CDCl3) δ = 96.5, 96.8, 107.6, 107.8, 109.8,
117.8, 118.8, 119.4, 119.8, 120.0, 121.1, 121.2, 121.9,
122.7, 125.4, 128.0, 129.3, 129.4, 141.79, 141.81,
141.90, 142.0, 142.2, 143.1, 160.9, 163.3; 19F NMR
(202 MHz, DMSO-d6) δ = -117.3; IR (neat) 3394,
1597, 1514, 1456, 1309, 1225, 1140, 742, 690 cm-1;
HR-MS: calcd for C24H18N2F (M+H+): 353.1449;
found: m/z 353.1440.
9-[4-[phenyl[4-(phenylamino)phenyl]amino]-
phenyl]-9H-carbazole (4a): white solid. mp 182.3-
184.3 °C; 1H NMR (500 MHz, DMSO-d6) δ = 6.78-
6.84 (m, 1H), 7.02-7.10 (m, 3H), 7.11-7.18 (m, 8H),
7.19-7.29 (m, 4H), 7.31-7.39 (m, 4H), 7.40-7.47 (m,
4H), 8.20-8.24 (m, 3H); 13C NMR (126 MHz, THF-
d8)  = 110.4, 117.9, 119.0, 120.3, 120.70, 120.73,
123.27, 123.30, 124.1, 124.5, 126.4, 128.2, 128.5,
129.7, 129.9, 131.3, 140.5, 141.8, 142.0, 144.7, 148.6,
148.8; IR (neat) 3381, 1601, 1504, 1450, 1308, 1274,
1227, 835, 750, 725, 694 cm-1; HR-MS: calcd for
C36H28N3 (M+H+): 502.2278; found: m/z 502.2253.
MHz, DMSO-d6)  = -127.1; IR (neat) 3396, 3049,
1593, 1618, 1450, 1313, 1228, 746, 723 cm-1; HR-
MS: calcd for C25H20N2F (M+H+): 367.1605; found:
m/z 367.1623.
9-[5-(m-tolyl)aminopyridin-2-yl]-9H-carbazole
1
(3k): white solid. mp 129.0-130.4 °C; H NMR (500
MHz, DMSO-d6) δ = 2.29 (s, 3H), 6.76 (d, J = 7.5 Hz,
1H), 6.98-7.04 (m, 2H), 7.20 (t, J = 7.7 Hz, 1H), 7.26-
7.32 (m, 2H), 7.40-7.47 (m, 2H), 7.57 (d, J = 8.6 Hz,
1H), 7.65 (d, J = 8.3 Hz, 2H), 7.76 (dd, J = 2.9, 8.7
Hz, 1H), 8.22 (d, J = 7.4 Hz, 2H), 8.44 (d, J = 2.7 Hz,
1H), 8.56 (brs, 1H); 13C NMR (126 MHz, CDCl3)
21.4, 110.7, 115.5, 119.1, 119.7, 120.1, 120.3,
123.7, 125.8, 126.0, 129.3, 138.4, 138.7, 139.4, 140.0,
141.6, 143.8; IR (neat) 3348, 1514, 1473, 1448, 1371,
1309, 1227, 748, 725 cm-1; HR-MS: calcd for
C24H20N3 (M+H+): 350.1652; found:m/z 350.1655.
[3,5-di(9H-carbazole-1-yl)phenyl]phenylamine
1
(3n): white solid. mp 111.2-114.2 °C; H NMR (500
MHz, DMSO-d6) δ = 6.89-6.95 (m, 1H), 7.18 (t, J =
1.8 Hz, 1H), 7.24-7.34 (m, 10H), 7.45-7.51 (m, 4H),
7.64 (d, J = 8.3 Hz, 4H), 8.24 (d, J = 7.4 Hz, 4H),
8.83 (brs, 1H). 13C NMR (126 MHz, CDCl3)  =
109.9, 113.1, 116.4, 119.8, 120.2, 120.4, 122.8, 123.5,
126.1, 129.6, 140.0, 140.5, 141.1, 146.6; IR (neat)
3388, 3047, 1587, 1444, 1311, 1227, 1155, 744, 694
References
[1] a) J. P. Wolfe, S. Wagaw, J.-F. Marcoux, S. L.
Buchwald, Acc. Chem. Res. 1998, 31, 805-818; b) J. F.
Hartwig, Acc. Chem. Res. 1998, 31, 852-860; c) J. F.
Hartwig, Angew. Chem. Int. Ed. 1998, 37, 2046-2067;
10
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
d) D. Prim, J.-M. Campagne, D. Joseph, B. Andrioletti, [11] F. Rataboul, A. Zapf, R. Jackstell, S. Harkal, T.
Tetrahedron 2002, 58, 2041-2075; e) B. Schlummer, U.
Scholz, Adv. Synth. Catal. 2004, 346, 1599-1626; f) J. F.
Riermeier, A. Monsees, U. Dingerdissen, M. Beller,
Chem. Eur. J. 2004, 10, 2983-2990.
Hartwig, Synlett 2006, 1283-1294; g) D. S. Surry, S. L. [12] a) N. D. McClenaghan, R. Passalacqua, F. Loiseau, S.
Buchwald, Angew. Chem. Int. Ed. 2008, 47, 6338-6361;
h) J. F. Hartwig, Acc. Chem. Res. 2008, 41, 1534-1544;
i) D. S. Surry, S. L. Buchwald, Chem. Sci. 2011, 2, 27-
50; j) R. J. Lundgren, M. Stradiotto, Aldrichimica Acta
2012, 45, 59-65; k) P. Ruiz-Castillo, S. L. Buchwald,
Chem. Rev. 2016, 116, 12564-12649.
Campagna, B. Verheyde, A. Hameurlaine, W. Dehaen,
J. Am. Chem. Soc. 2003, 125, 5356-5365; b) J. K.
Kwon, J. H. Cho, Y.-S. Ryu, S. H. Oh, E. K. Yum,
Tetrahedron 2011, 67, 4820-4825; c) C. Börger, O.
Kataeva, H.-J. Knölker, Org. Biomol. Chem. 2012, 10,
7269-7273; d) W.-J. Yoo, T. Tsukamoto, S.
Kobayashi, Org. Lett. 2015, 17, 3640-3642; e) X.
Zhao, Y. She, K. Fang, G. Li, J. Org. Chem. 2017, 82,
1024-1033.
[2] a) Y. Shirota, H. Kageyama, Chem. Rev. 2007, 107,
953-1010; b) K. Albrecht, K. Matsuoka, K. Fujita, K.
Yamamoto, Angew. Chem. Int. Ed. 2015, 54, 5677-
5682; c) S. Tanimoto, T. Suzuki, H. Nakanotani, C.
Adachi, Chem. Lett. 2016, 45, 770-772; d) O. Y. Kim,
B. S. Kim, J. Y. Lee, Synth. Metals 2015, 201, 49-53; e)
J.-R. Cha, C. W. Lee, J. Y. Lee, M.-S. Gong, Dyes
Pigment. 2016, 134, 562-568; f) M. Godumala, S. Choi,
M. J. Cho, D. H. Choi, J. Mater. Chem. C 2016, 4,
11355-11381; g) B. Wex, B. R. Kaafarani, J. Mater.
Chem. C 2017, 5, 8622-8653.
[3] G. Mann, J. F. Hartwig, M. S. Driver, C. Fernandez-
Rivas, C. J. Am. Chem. Soc. 1998, 120, 827-828.
[4] a) M. Watanabe, S. Nishiyama, T. Yamamoto (Tosoh
Corporation) JP2001 011046; b) M. Watanabe, M.
Nishiyama, T. Yamamoto, Y. Koie, Tetrahedron Lett.
2000, 41, 481-483; c) M. Soh, S. A. G. Santamaria, E.
L. Williams, M. Pérez-Morales, H. J. Bolink, A.
Sellinger, J. Polym. Sic., Part B: Polym. Phys. 2011, 49,
531-539; d) Y. Zou, T. Ye, D. Ma, J. Qin, C. Yang, J.
Mater. Chem. 2012, 22, 23485-23491; e) M. Ouyang, Z.
Fu, X. Lv, B. Hu, P. Wang, S. Huang, Y. Dai, C. Zhang,
J. Electrochem. Soc. 2013, 160, H787-792; f) Y.-X.
Zhang, L. Zhang, L.-S. Cui, C.-H. Gao, H. Chen, Q. Li,
Z.-Q. Jiang, L.-S. Liao, Org. Lett., 2014, 16, 3748-
3751; g) I. Neogi, S. Jhulki, A. Ghosh, T. J. Chow, J. N.
Moorthy, ACS Appl. Mater. Interfaces 2015, 7, 3298-
3305; h) C. M. So, Z. Zhou, C. P. Lau, F. Y. Kwong,
Angew. Chem. Int., Ed. 2008, 47, 6402-6406; i) A. Y.
Lebedev, V. V. Imer, A. F. Asachenko, A. A. Trarev, D.
V. Uborsky, Y. A. Homutova, E. R. Shperber, J. A. M.
Canich, A. Z. Voskoboynikov, Organometallics 2009,
28, 1800-1816.
[13] a) S. G. Rull, J. F. Blandez, M. R. Fructos, T. R.
Belderrain, M. C. Nicasio, Adv. Synth. Catal. 2015,
357, 907-911; b) Y. Minami, T. Komiyama, K.
Shimizu, S. Uno, T. Hiyama, O. Goto, H. Ikehara,
Synlett 2017, 28, 2407-2410.
[14] a) M. Egawa, T. Seo (Semiconductor Energy
Laboratory), JP2008-088083; b) T. Q. Huang, N. N.
Thang, D. H. Hoang, T. T. Dang, A. Villinger, P.
Langer, Org. Biomol. Chem. 2014, 12, 2596-2605; c)
V. V. Diev, J. D. Allen, K. D. Dobbs, W. Gao, M. H.
Howard Jr., M. R. Moseley, W. Wu (E. I. du Pont de
Nemours Company), WO2016 126423; d) M. Okabe,
M. Yabe, K. Okabe, K. Iida (Mitsubishi Chemical
Corporation) JP2008 031068; e) Y. Qiu, J. Li, Y. Li
(Beijing Visionox Technology Co., Ltd., Kunshan
Visionox Display Technology Co., Ltd., Tsinghua
University), CN101987822. f) T. Miyazaki, N.
Matsumoto, H. Araya (Tosoh Corporation) JP2017-
095429.
[15] a) S. Iwamoto, H. Ikeda, M. Matsuura, T. Maeda
(Idemitsu Kosan Co.) JP2009-177125; b) K.-T. Wong,
Y.-H. Lin, H.-H. Wu, F. Fungo, Org. Lett., 2007, 9,
4531-4534.
[16] Since the conversion of 1a was >99%, the mass
balance was calculated by using 100% as conversion
of 1a.
[17] K. W. Anderson, R. E. Tundel, T. Ikawa, R. A.
Altman, S. L. Buchwald, Angew. Chem., Int. Ed. 2006,
45, 6523-6527.
[18] N. Kataoka, Q. Shelby, J. P. Stambuli, J. F. Hartwig, J.
Org. Chem. 2002, 67, 5553-5566.
[19] A. Aranyos, D. W. Old, A. Kiyomori, J. P. Wolfe, J. P.
Sadighi, S. L. Buchwald, J. Am. Chem. Soc. 1999,
121, 4369-4378.
[20] J. Kido, T. Uchida, T. Yamada, T. Suzuki (Chemipro
Kasei Ltd.) JP2001 098023.
[5] A. V. Aggarwal, A. Thiesses, A. Idelson, D. Kalle, D.
Würsch, T. Stangl, F. Steiner, S.-S. Jester, J. Vogelsang,
S. Höger, J. M. Lupton, Nat. Chem. 2013, 5, 964-970.
[6] a) S. B. Lee, S. N. Park, C. Kim, H. W. Lee, H. W. Lee,
Y. K. Kim, S. S. Yoon, Synth. Metals 2015, 203, 174-
179; b) T. Fleetham, G. Li, J. LI, ACS Appl. Mater.
Interfaces 2015, 7, 16240-16246.
[7] C. W. Lee, J.-K. Kim, S. H. Joo, J. Y. Lee, J. Y. ACS
Appl. Mater. Interfaces 2013, 5, 2169-2173.
[8] S. M. Crawford, C. B. Lavery, M. Stradiotto, M. Chem.
Eur. J. 2013, 19, 16760-16771.
[21] X. Kong, H. Zhang, Y. Xiao, C. Cao, Y. Shi, G. Pang,
RSC Advances 2015, 15, 7035-7048.
[22] R. Lindner, B. van den Bosch, M. Lutz, J. N. H. Reek,
J. I. van der Vlugt, Organometallics 2011, 30, 499-
510.
[9] a) K. Suzuki, Y. Hori, T. Kobayashi, T. Adv. Synth.
Catal. 2008, 350, 652-656; b) Y. Nakayama, N.
Yokoyama, H. Nara, T. Kobayashi, M. Fujiwara, Adv.
Synth. Catal. 2015, 357, 2322-2330.
[10] C. M. So, Z. Zhou, C. P. Lau, F. Y. Kwong, Angew.
Chem. Int., Ed. 2008, 47, 6402-6406.
11
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701356
Advanced Synthesis & Catalysis
FULL PAPER
Palladium-catalyzed Selective Amination of
Aryl(haloaryl)amines with 9H-Carbazole
Derivatives
Adv. Synth. Catal. Year, Volume, Page – Page
Yuhki Ohtsuka, Tetsuya Yamamoto, Takanori
Miyazaki, Tetsu Yamakawa*
12
This article is protected by copyright. All rights reserved.