Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted indenoindole

Article abstract of DOI:10.1016/j.cclet.2016.11.002

A nickel-based catalyst was employed for the first time in the crossing-coupling of indenoindoles with bromo-/iodoarenes. A simple and practical method was provided for the synthesis of N-aryl substituted indenoindole and the mechanism of this reaction was discussed.

Full text of DOI:10.1016/j.cclet.2016.11.002

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CCLET 3876 1–6
Chinese Chemical Letters xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
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Original article
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Nickel-catalyzed C-N crossing coupling reaction: The synthetic method
for N-aryl substituted indenoindole
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a
Xin-Le Lia, , Xiao-Mei Lang , Lian-Ming Yang , Sheng-Yuan Zhou , Hong-Fan Hu ,
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Q1
*
Shan Xuea, Xin Suna, Shi-Xuan Xina,
*
Polyolefin Research Department, Petrochina Petrochemical Research Institute, Beijing 102206, China
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Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Green Printing, Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Q2
A nickel-based catalyst was employed for the first time in the crossing-coupling of indenoindoles with
bromo-/iodoarenes. A simple and practical method was provided for the synthesis of N-aryl substituted
indenoindole and the mechanism of this reaction was discussed.
Received 22 September 2016
Received in revised form 19 October 2016
Accepted 25 October 2016
Available online xxx
ã 2016 Xin-Le Li and Shi-Xuan Xin. Chinese Chemical Society and Institute of Materia Medica, Chinese
Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Keywords:
Synthesis
Nickel
Crossing coupling
Indenoindole
Mechanism
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1. Introduction
ligand-promoted Cu-catalyzed chemistry [17–19] (so-called post-
Ullmann reaction) has also been developed. Compared to the
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N-Aryl substituted indenoindole compounds are attractive for
chemical synthesis because of their importance in preparation of
metallocene catalysts for the polymerization of ethylene and
propylene [1,2]. Metallocene catalyst has been modified world-
wide in industrial and academic areas to provide many different
catalyst-structures that can be used to synthesize highly isotactic,
syndiotactic, atactic, hemi-isotactic polyolefin with different
molecular weights and different degrees of tacticity [3–8]. N-Aryl
substituted indenoindole derivatives are important building block
for the ancillary ligands of metallocene catalyst owning to their
cyclopentadiene functional group. Until now, rare reports have
been found involving the synthesis of N-aryl substituted inden-
oindole [2], which also restrict the rational design of metallocene
catalyst structures.
corresponding Pd and Cu-catalyzed systems, the major advantages
of Ni-based catalysts are their much lower cost and potentially
high reactivity toward easily-available but relatively inert sub-
strates (e.g., aryl chlorides and aryl bromide) without the use of
specially tailored organic ligands. Some works on the synthesis of
N-aryl substituted indenoindole derivatives via cross coupling of
aromatic halogen and indenoindole under metal catalysis has been
done, the result disclosed the fact that little or none desired
product was received [20]. Yang and co-workers demonstrated a
number of nickel-catalyzed triarylamine synthesis via the amina-
tion of bromo-/iodoarene with metal diarylamides, in-situ
produced from a diarylamine and the Grignard reagent or sodium
hydride [21–25]. They proposed that simple anilines are not over
arylated and the reaction proceeds “selectively” to the mono-
substitution stage, even in the presence of excess aryl halides,
indicating that a diarylamine is not coupled with an aryl halide
under the “normal” conditions (i.e., typically a combination of free
amines and inorganic bases). Accordingly, the N-aryl substituted
indenoindole and the triarylamine have the similar conjugate
structure, therefore the synthesis of N-aryl substituted inden-
oindole is a challenging task. The reason was presumably that the
indenoindole is usually difficult to coordinate to the Ni center
due to its steric bulk and poor nucleophilicity against a relatively
small Ni center. For the metal-catalyzed coupling reaction, a
Nickel-catalyzed aromatic CÀÀN coupling reactions have
received intense investigations, and have become important and
powerful tools in organic syntheses during the past decade
[9–15]. The Ullmann reaction [16] is a classical method for the
Cu-mediated CÀÀN coupling and recently, the more practical
* Corresponding authors.
E-mail addresses: lixinle@petrochina.com.cn (X.-L. Li),
xinshixuan@petrochina.com.cn (S.-X. Xin).
http://dx.doi.org/10.1016/j.cclet.2016.11.002
1001-8417/ã 2016 Xin-Le Li and Shi-Xuan Xin. Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All
rights reserved.
Please cite this article in press as: X.-L. Li, et al., Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted
indenoindole, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.11.002

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coordination process, namely transmetalation, is one of the key
steps in a catalytic cycle. Based on the situation, butyl lithium was
selected as the base for a model reaction between bromobenzene
and indenoindole. Indenoindole is readily deprotonated by butyl
lithium and transformed to the more nucleophilic amide species,
which enhances its ability to bind Ni center, and in addition, the
use of highly air-sensitive nickel(0) precatalysts is avoided because
easy-to-handle nickel(II) compounds can be reduced to the low-
valent nickel species by butyl lithium agents in situ. Thus we
proposed to employ the butyl lithium as the strong base to
generate nucleophilic amides and as the reduction agent to
produce low-valent Ni species in situ.
2PPh3/nickel combination as the catalyst. Further increase the
PPh3/Ni ratio to 4/1 was detrimental (entry 9). However, excellent
coupling yield (82%, entry 10) was obtained when NiCl2(PPh3)2
complex was employed without any additional free triphenyl-
phosphine. Noted also that the use of additional free PPh3 dose not
help to enhance the catalytic efficiency (entry 11). Increasing the
NiCl2(PPh3)2 catalyst loading does not improve the coupling yield,
and evidenced dropping in coupling yield also occurred when the
catalyst loading was decreased (entries 12 and 15). Higher
temperature could not enhance the coupling reaction (entry 13)
though, the reaction at room temperature gave only a low product
yield of 15% (entry 14). Therefore the optimal conditions for this
coupling reaction were set as in entry 10 of Table 1.
The coupling reaction between the two representative
indeoindoles and a serial of aryl bromide under the above
optimized conditions was executed. Some aryl iodides were also
selected as electrophilic substrates where necessary. However,
aryl chlorides could not receive the target products under the
condition. The results were summarized in Table 2.
Generally, both aryl bromides and iodides are substrates
suitable for this reaction, and the iodides performed slightly
better than their bromide congeners (entry 1 vs. 2, entry 4 vs. 5,
entry 10 vs. 11, entry 12 vs. 15). Concerning the aryl bromide, both
their electronic and steric effect have considerable impacts on the
coupling reaction. The electron-neutral aryl bromide were
smoothly coupled with the indenoindole to give moderate to
excellent yields (entries 1, 3, 9 and 10, 16, 18), electron-deficient
aryl bromide also delivered good product yields (entries 12
and 19). Interestingly, the nitrile did not play a role in activating
the electrophilic substrate as usual, and instead, almost no
product was afforded (entry 7), presumably due to the strong
coordinating ability of the p-CN, while those bearing strong
electron-withdrawing groups seemed difficult to undergo the
crossing-coupling desired. For example, 4-nitrobromobenzene and
4-bromobenzene carboxylic acid (unlisted in Table 2) did not react
at all. Electron-donating groups gave a relatively low yield of the
desired product (entry 6). Furthermore, those containing the
carbonyl group, such as 4-bromobenzaldehyde (entry 8) provided
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2. Results and discussion
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The effect of the bases employed was evaluated first. Indeed,
those commonly used bases in metal-catalyzed CÀÀN coupling do
not work. For instance, no expected coupling product was observed
when sodium tert-butoxide, potassium tert-butoxide, or potassium
orthophosphate were used. Sodium hydride, although it is able to
convert indenoindole into the more nucleophilic amide species, is
also ineffective in facilitating the coupling reaction. In an exploring
model reaction, butyl lithium was used as the double function
reagent, i.e. as a strong base to generate the amide and also as a
reducing agent for the reduction of nickel salt to the low valent
species. In the model indenoindole/bromobenzene coupling
reaction, a brief set of screening experiments were focused on
different metal catalyst systems and the results are summarized in
Table 1. Several common transition metal(II) precatalysts were
surveyed, and it was found that only nickel showed the capability
of promoting the reaction compared to others, such as iron, copper
and palladium (entries 1–4). Toluene turned out to be the suitable
solvent for the model reaction compared with other solvents
tested. Nickel catalysts bearing phosphine ligands performed
better than those of other ligand types (entry 8 vs. entries 5–7), and
triphenylphosphine (PPh3) ligand offers relatively high activity
(entry 8). To our pleasure, successful coupling in the model
reaction resulted in 65% yield of the desired product when
Table 1
Q7
Screening of catalyst systems.a
Entry
[Metal(II)] (mol%)
Ligand (mol%)
T (ꢀC)
Isolated yield (%)
1
2
3
4
5
6
7
8
CuCl2 (5)
FeCl2 (5)
PdCl2 (5)
NiCl2 (5)
NiCl2 (5)
NiCl2 (5)
NiCl2 (5)
NiCl2 (5)
None
None
None
None
Ipr.HCl (10)
Bipyl (10)
Phen (10)
PPh3 (10)
PPh3 (20)
None
PPh3 (10)
None
None
90
90
90
90
90
90
90
90
90
90
90
90
110
30
90
Trace
0
Trace
25
20
21
22
65
40
82
9
NiCl2 (5)
10
11
12
13
14
15
NiCl2(PPh3)2 (5)
NiCl2(PPh3)2 (5)
NiCl2(PPh3)2 (10)
NiCl2(PPh3)2 (5)
NiCl2(PPh3)2 (5)
NiCl2(PPh3)2 (2)
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15
None
None
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a
Reactions performed on a 1-mmol scale and the solvent is toluene.
Please cite this article in press as: X.-L. Li, et al., Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted
indenoindole, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.11.002

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Table 2
Substrate scope.a
Entry
1
Indenoindole lithium
Aryl halides
Product
Isolated yield (%)
79
1a
2
3
1a
1a
84
80
3aa
3ab
3ac
4
5
6
1a
1a
1a
35
63
21
3ad
7
1a
Trace
3ae
3af
8
9
1a
1a
None
55
3ag
3ah
10
11
1a
1a
78
84
12
13
1a
1a
79
85
3ai
Please cite this article in press as: X.-L. Li, et al., Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted
indenoindole, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.11.002

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X.-L. Li et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
Table 2 (Continued)
Entry
14
Indenoindole lithium
Aryl halides
Product
Isolated yield (%)
83
1b
15
16
1b
1b
83
85
3ba
3bb
3bc
17
18
1b
1b
38
79
3bh
19
1b
78
3bi
Reaction conditions: indenoindole lithium (1.0 mmol), aryl bromide or iodide (1.2 mmol), NiCl2(PPh3)2 (33 mg), toluene (10 mL).
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no desired product, although the starting bromide was found to be
consumed completely. This might be mainly due to the carbonyl
group being capable of capturing the nucleophile and leading to a
failure of the reduction of the Ni(II) into the catalytically active
low-valent species. The reaction is sensitive to the steric hindrance
of the aryl bromide. Thus the reaction of 2-bromotoluene and
3,4-dimethylbromobenzene with indenoindole gave low yield of
35% and 55%, respectively (entries 4 and 9), and ortho-substituted
aryl bromides were coupled with indenoindole (entry 4 and entry
17) in relatively low yields. The main reason is presumably that
the ortho-substituted aryl bromides were much more spatially
congested to coordinate to the nickel center which already bears a
bulky indenoindole amide species.
From the preliminary experimental observations, it is suggested
that the catalytically active species might involve the Ni(I)
phosphine complexes in this reaction, which is consistent with
our results: (1) very small amounts of biaryl by-products were
detected in almost all cases; (2) chloroarenes were inert in the
reaction, the conversion efficiency increases with the increasing of
bromoarene-/iodoarenes concentration and the iodoarenes have
higher reactivity; (3) the reaction proceeded only in the presence
of strong bases with reducing ability such as butyl lithium.
Arylnikel(II) halide complexes are readily available compounds
[26]. To discern the mechanism of the reaction, we conducted a
stoichiometric reaction of indenoindole lithium with Ni(II)-
(a-aryl) complexes which may be regarded as theoxidative
Furthermore, it is found that the indenoindole/heloarene
coupling reaction is quite different from most of the nickel-
catalyzed aromatic CÀÀN coupling reported previously [20–22].
adducts of haloarenes to the nickel(0) as shown in Eq. (1). As a
result, no N-aryl substituted indenoindole was received. This
experiment indicated that the arylnickel(II) complex is not the
Please cite this article in press as: X.-L. Li, et al., Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted
indenoindole, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.11.002

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potential intermediate on the catalytic pathway. Thus, it should be
reasonable to rule out the mechanism to follow an usual Ni(0)–Ni
(II) cycle for this nickel-catalyzed N-aryl substituted indenoindole
derivatives synthesis.
synthesis, efficient production of the nickel(I) species would be the
key step for the coupling reaction, and we are currently more
inclined to consider the oxidative addition as the rate determining
step. This conclusion may partly explain the reasons why aryl
(1)
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It was presumed that the catalytically active species might
involve the Ni(I) species in this reaction. Kochi and Tsou [27] has
carefully investigated the oxidative addition of the nickel(0) on aryl
halidesand proposed a route to in-situ forming the Ni(I) species via
a one-electron transfer of the in situ-generated Ni(0) species to the
haloarene. Based on their studies, we proposed a route to
generating the nickel(I) intermediate as shown in Scheme 1.
Firstly, the nickel(II) compound was reduced to the nickel(0)
species by butyl lithium agents, then the nickel(I) species were
formed via a single-electron transfer from nickel(0) to an aryl
halide and the crossing reaction of the indenoindole derivatives
with bromo-/iodoarenes was initiated.
Based on our experimental investigation, and combining
previous studies [19,28]. We propose a plausible mechanism that
might follow a catalytic cycle of the Ni(I)–Ni(III) shuttle involving
sequential oxidative addition, transmetallation and reductive
elimination as shown in Scheme 2. For this nickel-catalyzed
chlorides do not react under the condition and there always existed
a little biaryl by-product.
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3. Conclusion
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In summary, we have for the first time demonstrated the
feasibility for Ni-catalyzed arylation of indenoindoles with
bromo-/iodoarenes. A simple and practical method was provided
for the synthesis of N-aryl substituted indenoindole. A preliminary
investigation suggested that the mechanism of this reaction might
be different from that of the normal Ni(0)–Ni(II) shuttle. Further
work to expand the scope of substrates and elucidate the
mechanistic details is ongoing in our laboratory.
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4. Experimental
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All the chemicals were purchased commercially and used
without any further treatment, unless otherwise stated. 1H NMR
spectra were recorded on a BRUKER AVANCE 400 spectrometer.
Mass spectra were obtained on a Bruker Daltonics Inc. APEXII
FT-ICR. Melting points were measured with an X-4 micro melting-
point apparatus and uncorrected. All reactions were carried out
under nitrogen atmosphere with oven-dried glassware and heated
in an oil bath. Dioxane and toluene were distilled from sodium/
benzophenone before use. Grignard reagents and n-butyl lithium
were purchased from commercial sources. All amines and
haloarenes were available commercially and used without further
purification. Column chromatography was performed on silica gel
(200–300 mesh). All yields refer to isolated yields (average of two
run) of compounds estimated to be >95% pure as determined by
1H NMR. The known compounds were partly characterized by
melting points, MS,1H NMR, and compared to authentic samples or
the literature data.
Typical procedure for the N-aryl substituted indenoindole
synthesis: An oven-dried 50 mL three-necked flask was charged
with NiCl2(PPh3)2 (5 mol% relative to the indenoindole lithium,
33 mg) and 1 mmol indenoindole lithium. The flask was evacuated
and backfilled with nitrogen, with the operation being repeated
twice. Dried toluene (10 mL) was added via syringe. The resulted
mixture was stirred for 5 min, a bromoarene (1.2 mmol) was added
via syringe. The mixture was stirred for 10 min at room
temperature and then heated at an oil bath of 85 ꢀC for 12 h.
The reaction mixture is allowed to cool to room temperature and
added to 20 mL saturated ammonium chloride solution, then
extracted with ethyl acetate (20 mL Â 3). The combined organic
phases were evaporated under reduced pressure and the residue
purified by column chromatography. The detail information about
experimental procedures, the data of NMR and spectroscopy are
deposited in Supporting information.
Scheme 1. A plausible route to in-situ generating the nickel(I) species.
Scheme 2. A proposed mechanism for the arylation of indenoindole with bromo-/
iodoarenes catalyzed by NiCl2(PPh3)2.
Please cite this article in press as: X.-L. Li, et al., Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted
indenoindole, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.11.002

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id. 1H NMR (400 MHz, CDCl3):
d 7.92 (d, 1H, J = 7.6 Hz), 7.69 (d, 1H,
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J = 7.6 Hz), 7.57-7.52 (m, 5H), 7.43-7.35 (m, 3H), 7.30-7.21 (m, 4H),
7.11-7.05 (m, 2H), 3.80 (s, 2H). MS (EI): m/z 281 (M+).
5-Phenyl-5,10-dihydroindeno[1,2-b]indole (3ba): Pale yellow
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solid. 1H NMR (400 MHz, CDCl3):
d 7.68 (d, 1H, J = 8.0 Hz), 7.58-7.54
(m, 4H), 7.48 (t, 1H, J = 3.2 Hz), 7.39 (d, 1H, J = 6.4 Hz), 7.18-7.16
(m, 4H), 7.07 (d, 1H, J = 7.2 Hz), 3.79 (s, 2H). MS (EI): m/z 281 (M+).
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Appendix A. Supplementary data
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Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cclet.2016.11.002.
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Please cite this article in press as: X.-L. Li, et al., Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted
indenoindole, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.11.002