Cu(II)-Catalyzed Ortho C(sp2)-H Diarylamination of Arylamines to Synthesize Triarylamines

Article abstract of DOI:10.1021/acs.orglett.0c00196

A copper-catalyzed, directed ortho C-H diarylamination of indoles, indolines, anilines, and N-aryl-7-azaindoles has been established. Only copper salt as the catalyst and oxygen as the terminal oxidant are used to synthesize triarylamines using various diarylamines including carbazole and phenothiazine. Mechanistic interrogation reveals that copper plays a dual role.

Full text of DOI:10.1021/acs.orglett.0c00196

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Letter
2
Cu(II)-Catalyzed Ortho C(sp )−H Diarylamination of Arylamines To
Synthesize Triarylamines
Mohit Kumar, Rishabh Sharma, Raziullah, Afsar Ali Khan, Ashfaq Ahmad, Himangsu Sekhar Dutta,
and Dipankar Koley*
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ABSTRACT: A copper-catalyzed, directed ortho C−H diarylamination of indoles, indolines, anilines, and N-aryl-7-azaindoles has
been established. Only copper salt as the catalyst and oxygen as the terminal oxidant are used to synthesize triarylamines using
various diarylamines including carbazole and phenothiazine. Mechanistic interrogation reveals that copper plays a dual role.
1
6
here has been a longstanding interest in the construction
amines, only a few reports have demonstrated C−H
2
2
T
of C(sp )−N bonds owing to the ubiquity of C(sp )−N
diarylamination to synthesize triarylamine derivatives (Scheme
1). In 2014, Patureau et al. reported ruthenium-catalyzed
diarylamination to afford anilines. However, only carbazole
17
bonds in natural products, pharmaceuticals, agrochemicals, and
1
−3
17g
multifunctional materials. The most accomplished method
to construct C−N bonds is the Pd-catalyzed Buchwald and
was effective as a diarylamine coupling partner. The same
group has also been able to devise a strategy to synthesize
4
,5
Hartwig amination to aryl halides/boronic acids. However,
in the past decade, considerable achievements have been made
phenothiazine- and carbazole-based triarylamines via oxidative
6
17a−f,h
in the direct C−H amination via oxidative coupling, metal-
coupling of diarylarylamines with arenes.
However, the
7
catalyzed directing group assisted cross-coupling, and radical
scope of the substrates was limited mostly to the phenol based
arenes. The Zhang group recently reported copper catalyzed
tandem reactions to synthesize indole and benzimidazole
8
induced coupling. In this regard, since the independent
7
f,g
seminal reports of Yu and Chatani, use of earth abundant,
inexpensive copper catalysts showed great progress, especially
on the directing group assisted C−H amination. Consequently,
several other groups have expanded the overall scope of this
strategy including the use of removable directing groups,
18
derivatives using diarylamines. Very recently, in 2019, Lei’s
group developed aryl C−H diarylamination to produce anilines
by utilizing electrochemical oxidation, albeit, furnishing the
1
7j
products exclusively in the para-selective manner.
We
3
c9
diverse aminating sources.
used bidentate directing groups that could be removed easily.
Yu et al. reported direct amination using carboxamides,
For examples, Daugulis et al.
considered whether directing group assisted C−H amination
using diarylamine could be an alternative strategy to synthesize
triarylamine. To the best of our knowledge, copper-catalyzed
9c
9d,g
sulfonamides, and anilines.
Recently, Chang et al. showed
2
ortho C(sp )−H diarylamination to arylamines has not been
that aqueous ammonia could directly be used as a C−H
reported. We have very recently demonstrated the use of
highly abundant, less toxic, and inexpensive copper salts to
9
f
aminating reagent.
Triarylamines, with its unique structural and electronic
properties, are considered to be a promising building block for
2
19
functionalize the C(sp )−H of diverse arenes. The study
revealed that the reaction proceeds via disproportionation
reaction. Recently, Stahl et al. demonstrated that copper
catalyst can oxidatively dimerize diphenylamine to tetraarylhy-
10
novel optoelectronic devices. Derivatives of triarylamine have
11
shown enormous potential as photocatalysts and redox-
1
2
mediators. Especially, incorporation of carbazole and
phenothiazine moieties would be of immense importance
13
Received: January 14, 2020
owing to their proven character in organic materials. In
addition, triarylamine scaffolds are found to display anticancer
1
4
activity. However, the only available strategy for their
syntheses is the conventional cross-coupling method using
15
aryl halides and diarylamines. While a number of examples
are reported for the aryl C−H amination largely using dialkyl
©
XXXX American Chemical Society
https://dx.doi.org/10.1021/acs.orglett.0c00196
A
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Letter
a
Scheme 1. Amination to Anilines via C−H
Functionalization
Table 1. Reaction Optimization
b
2
a
Temp
(°C)
Yield
entry Cu-salt(mol %)
solvent
(equiv)
(%)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
Cu(OAc) (30)
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
DCB
DCE
DMF
DMSO
DCE
DCE
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.0
1.5
2.0
120
130
140
130
130
130
130
130
130
130
130
130
130
130
65%
69%
69%
66%
63%
nd
52%
54%
71%
traces
traces
65%
52%
46%
2
Cu(OAc) (30)
2
Cu(OAc) (30)
2
CuTc (30)
Cu(OBz) (30)
2
Cu(OTf) (30)
2
c
Cu O (30)
2
Cu(OAc) (30)
2
Cu(OAc) (30)
2
0
1
2
3
4
Cu(OAc) (30)
2
Cu(OAc) (30)
2
Cu(OAc) (30)
2
Cu(OAc) (30)
2
Cu(OAc) (30)
DCE
2
a
Reaction conditions: 1a (0.25 mmol), 2a (0.3 mmol), solvent (2.5
b
c
mL), O flush, 24 h. Isolated yield. With 60 mol % of BzOH
2
a
Scheme 2. Scope of Indolines and Diphenylamines
drazine under aerobic conditions via the generation of an
2
0
aminyl radical.
We argued that the in situ generated aminyl radical could
oxidize the cyclometalated Cu(II) intermediate I to II, which
should undergo reductive elimination to furnish the desired
product (Scheme 1). Herein, we disclose diarylamination to
synthesize indole, indoline, and aniline derivatives under
aerobic conditions using a copper catalyst via direct C−H
2
1
functionalization. Notably, this method showed very good
reactivity with not only various diarylamines including
carbazoles and phenothiazine but also various N-aryl-7-
azaindoles which were successfully aminated by diarylamines.
In addition, this simple and atom-economical protocol needs
only a copper catalyst and oxygen. While our work was in
progress, a similar strategy was reported by Miura et al. for the
diarylamination to phenols using a bidentate chelating ligand
17k
as a directing group. However, one of the major limitations
of this protocol was the formation of bis-aminated products.
In a pilot reaction, we used N-pyrimidyl indoline (1a) and
diphenylamine (2a) as the model substrates (Table 1).
Delightfully, when heated in toluene at 120 °C, 30 mol % of
Cu(OAc) furnished the desired product 3aa in 65% yield
2
(
entry 1). The same was isolated in 69% yield when the
temperature was further increased up to 140 °C (entries 2,3).
Next, various copper salts were tested (entries 4−7). However,
none of them provided a better yield. A solvent screening study
(
entries 8−11) revealed that polar solvents were not suitable
for this transformation, and dichloroethane (DCE) provided
1% of the desired product. 1.2 equiv of 2a furnished the
7
highest yield (entries 9, 12−14). Gratifyingly, no C5−H
aminated product was obtained under the optimized
conditions. No desired product was obtained in the absence
of a copper catalyst.
Next, the reaction scope was examined by treating a variety
of indoline derivatives (Scheme 2). The benzenoid moiety of
indoline bearing methyl (3ba), methoxy (3ca), fluoro (3da),
chloro (3ea), and iodo (3fa) functionality at the C5 position
a
Reaction conditions: 1a−1t (0.25 mmol), 2a−2j (1.2 equiv),
Cu(OAc) (30 mol %), DCE (2.5 mL), 130 °C, 24 h; isolated
yields. 1.0 mmol of 1g, 140 °C.
2
b
c
B
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proved to be compatible with the process. Furthermore,
indolines bearing substituents at the C2, C3, and C4 positions
also afforded the desired products (3ga−3ja) in good yields
Scheme 4. Control Experiments on Mechanistic Aspect
(
up to 81%). Notably, iodo- (3fa) and bromo- (3ja)
substituted derivatives preferentially underwent desired C−H
diarylamination over the Ullmann-type coupling. Indoline
bearing pyridine as a directing group also furnished the desired
product (3ka, 57%). Despite heating at elevated temperature
(
140 °C), hexahydrocarbazole (1l) and carbazole (1m)
furnished the products (3la, 3ma) in low yields. Our next
objective was to check the possibility of amination at the C2
position of indole. Delightfully, various indoles were aminated
to furnish the products (3na−3ra) in moderate yields. Aniline
derivatives were also aminated by diphenylamine to yield
products (3sa, 3ta) in low yields (up to 26% yield). We next
examined the scope of diarylamine substrates. Diarylamines
bearing methyl (3ac−3ae), methoxy (3ab), and nitro (3af)
efficiently furnished the products with yields up to 75%.
22
Notably, phenothiazine, a privileged heterocycle not only in
medicinal chemistry but also in photoredox catalysis, has been
coupled with 1a to synthesize N-arylphenothiazine 3ag in 48%
yield. Gratifyingly, carbazoles, another important class of
2
3
medicinally relevant scaffold, were successful coupling
partner as diarylamine to furnish 3ah−3aj. Gratifyingly, the
reaction was also tolerated on a larger scale setup as 1.0 mmol
of 1g yielded 78% of 3ga.
2
4
We next argued whether 7-azaindole, a promising
privileged scaffold in medicinal chemistry, could be used as a
directing group for the diarylamination to produce arene
substrates (Scheme 3). Thus, various N-aryl-7-azaindoles were
a
Scheme 3. Scope of Azaindoles
radical mechanism was supported by the radical trap
experiment (Scheme 4a), as the formation of 3aa was
suppressed by both 2,2,6,6-tetra-methylpiperidine-1-oxyl
(
TEMPO) and butylated hydroxytoluene (BHT). As described
by Stahl et al., in the presence of a copper salt under O , the
2
diarylamine exists in equilibrium with its tetraarylhydrazine
derivative; thus, we wondered whether tetraarylhydrazine
might serve as the source of the diarylaminyl radical. To our
delight, under the optimized conditions, tetraphenylhydrazine
provided 41% of 3aa (Scheme 4b). As expected, no product
was obtained when the same reaction was performed in the
absence of a copper catalyst (Scheme 4c). On the contrary,
upon heating, tetraphenylhydrazine undergoes smooth decom-
position to diphenylamine without any copper catalyst
(Scheme 4d). These results together suggest that the aminyl
radical is the key intermediate in this reaction and copper is
necessary to generate this radical. As observed previously by
a
Reaction conditions: 4a−4i (0.25 mmol), 2a (0.3 mmol), Cu(OAc)
2
(
30 mol %), Toluene (2.5 mL), 140 °C, 24 h; isolated yields.
subjected to the optimized reaction conditions. To our delight,
various N-aryl-7-azaindoles were tolerated by the method and
the aminated products (5aa−5ia) were obtained in good to
very good yields (53−70%). Arenes bearing an alkyl (5ba, 5ca,
5
fa), alkoxyl (5da, 5ga), and halogen (5ea, 5ha) were well
tolerated. Hetereoarene (5ia, 59%) also participated in the
reaction. Interestingly, unlike the Miura report, in most of the
cases only trace amount of bisaminated product was identified
via mass spectroscopic analysis of the crude reaction mixture.
We next focused our attention toward understanding the
mechanism of this reaction (Scheme 4). Our hypothesis of a
19c−e
us,
the results of deuterium scrambling experiments
(Scheme 4e, 4f) suggest that the C−H metalation step is
reversible. However, the primary kinetic isotope study revealed
(k /k = 0.92) that the rate of the reaction does not depend on
H
d
the C−H metalation step (Scheme 4g). We have also observed
C
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(
Scheme 4h, 4i) that electronically rich indolines as well as
Afsar Ali Khan − Academy of Scientific and Innovative Research,
New Delhi 110001, India
Ashfaq Ahmad − Medicinal and Process Chemistry Division,
CSIR-Central Drug Research Institute, Lucknow 226031, India
Himangsu Sekhar Dutta − Academy of Scientific and
Innovative Research, New Delhi 110001, India
electronically rich diarylamines react preferentially over the
electronically neutral or electronically deficient substrates.
On the basis of the preliminary experimental results and
previous reports,
reaction is outlined in Scheme 5. First, 1a chelates with Cu(II)
1
7k,19c,d,20,25
a plausible mechanism for this
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c00196
Scheme 5. Plausible Reaction Mechanism
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from DST-SERB (EMR/2016/000613),
UGC-New Delhi (R. and M.K.), CSIR-New Delhi (A.A.K.,
A.A., H.S.D.), and Ministry of Chemicals and Fertilizers (R.S.)
is gratefully acknowledged. We thank the CDRI SAIF division
for analytical support. CDRI communication number 10045.
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https://dx.doi.org/10.1021/acs.orglett.0c00196
Org. Lett. XXXX, XXX, XXX−XXX