Cobalt(III)-Catalyzed, DMSO-Involved, and TFA-Controlled Regioselective C?H Functionalization of Anilines with Alkynes for Specific Assembly of 3-Arylquinolines

Article abstract of DOI:10.1002/adsc.201801709

Herein, a novel cobalt(III)-catalyzed and TFA-controlled [3+2+1] cyclization of diverse anilines and terminal alkynes has been realized by using DMSO as both the solvent and the C₁ source, which led to the specific synthesis of privileged 3-arylquinolines in one pot and regioselectively. Mechanistic investigations revealed that this versatile transformation might be initiated with a C?H activation process and with a 2-vinylbenzenamine species as the active intermediate. (Figure presented.).

Full text of DOI:10.1002/adsc.201801709

Title: Cobalt(III)-Catalyzed, DMSO-Involved, and TFA-Controlled
Regioselective C–H Functionalization of Anilines with Alkynes for
Specific Assembly of 3-Arylquinolines
Authors: Peiquan Zhang, Yurong Yang, Zhiyong Chen, Xu Zhang,
Feng Xu, Zhi Zhou, Xiyong Yu, and Wei Yi
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201801709
Link to VoR: http://dx.doi.org/10.1002/adsc.201801709

10.1002/adsc.201801709
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Cobalt(III)-Catalyzed, DMSO-Involved, and TFA-Controlled
Regioselective C–H Functionalization of Anilines with Alkynes
for Specific Assembly of 3-Arylquinolines
Peiquan Zhang,+a Yurong Yang,+a Zhiyong Chen,+c Zhang Xu,b Xuefeng Xu,b,* Zhi Zhou,a,* Xiyong
Yu,a and Wei Yia,*
a Key Laboratory of Molecular Target and Clinical Pharmacology & State Key Laboratory of Respiratory Disease, School
of Pharmaceutical Sciences & the Fifth Affiliated Hospital, Guangzhou Medical University, Guangzhou, Guangdong
511436, China
Fax: (+86)-20-37104196); phone: (+86)-20-37104196
E-mail: yiwei@gzhmu.edu.cn; zhouzhi@gzhmu.edu.cn
b Engineering Technology Research Center of Henan Province for Solar Catalysis, College of Chemistry and
Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, China
E-mail: xuxuefengedu@163.com
c Guangdong Provincial Public Laboratory of Analysis and Testing Technology, China National Analytical Center,
Guangzhou 510070, China
+These authors contributed equally to this work.
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######.((Please
delete if not appropriate))
Abstract: Herein, a novel cobalt(III)-catalyzed and TFA- recent work.[4] However, the reports in this regard
controlled [3+2+1] cyclization of diverse anilines and
terminal alkynes has been realized by using DMSO as both
the solvent and the C1 source, which led to the specific
synthesis of privileged 3-arylquinolines in one pot and
regioselectively. Mechanistic investigations revealed that
are still scarce, particularly in the context of
heterocycle synthesis.[5] The selective C
functionalization of arenes through the C
–
–
H
H
activation strategy without the assistance of a DG
for the construction of heterocyclic backbone is
highly challenging but synthetically demanding.
this versatile transformation might be initiated with a
C–H
activation process and with a 2-vinylbenzenamine species
as the active intermediate.
Keywords: cobalt(III) catalysis;
C–H functionalization;
anilines; alkynes; 3-arylquinolines.
Direct functionalization of inert C–H bonds is one
of the most efficient ways to access specific
molecules, as it provides a means for improving
the atom- and step-economy in current organic
synthesis, in which the regioselectivity is one
important issue.[1] So far, several versatile
strategies have been developed to control the
regioselectivity of the reaction. Among them, a
powerful method to obtain high regioselectivity
requires the assistance of a proximal directing
group (DG).[2] In most cases, the DG only
exhibits a ligating effect or acts as a simple
nucleophile in post coupling transformations.[3] In
general, the DG often leaves a chemical trace in
the products, thus limiting their structural
diversity. To overcome this drawback, Rh(III)-
catalyzed direct oxidative coupling between
simple arenes and activated alkynes via no DG-
Scheme 1. DMSO as one-carbon source for quinoline
synthesis.
directed C
–H bond activation strategies (e.g.,
electrophilic metalation) has been reported in
1
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10.1002/adsc.201801709
Advanced Synthesis & Catalysis
the synthesis of 4-arylquinolines.[19] Compared to
On the other hand, quinolines are prevalent in the routine migratory 1,2-insertion of alkynes, of
natural products, biologically active molecules, note, the recently developed cobalt(III)-catalyzed
and pharmaceuticals.[6] Among quinoline
derivatives, 3-substituted quinoline scaffolds
C
–
H activation with alkynes in an acidic catalytic
system usually proceeds with a reverse selectivity,
have attracted considerable interest among in which an unusual 2,1-insertion was adopted for
chemists due to their broad range of biological
properties.[7] As a result, numerous synthetic
protocols to elaborate this molecular scaffold
the coupling of the alkynes.[20-21] Indeed, the
cobalt(III) species has emerged in the past few
years as one of widest-used catalysts due to its
have been developed over the years.[8-11] For unique
reactivity
in
the
site-selective
–
example, the groups of Wang,[8] Huang,[9] and functionalization of unactivated C
H bonds.[22]
Kwon[10] have independently demonstrated the
efficient and precise synthesis of 3-functionalized
quinolines from O-substituted anilines through
Especially, recently a seven membered cobalt(III)
-
alkenyl intermediate was isolated and identified by
the group of Sundararaju, which established a rational
foundation for understanding the cobalt(III)-
transition-metal-catalyzed
C
–
H
activation
strategy. Despite these significant progresses,
there is room for innovation. For example, most
catalyzed C
Inspired by these, we envisaged that, cobalt(III)-
–
H functionalization reaction mode.[23]
of these developments still suffer from difficult catalyzed electrophilic metalation of aniline could
operation, harsh reaction conditions, and
especially the need to use raw materials with
provide the ortho
intermediate, then, the acid was involved to affect
C
–
H
bond-activated
special types of substituents. Accordingly, the the coordination property of the cobalt(III)
development of mild, simple, highly efficient, catalyst, thus resulting in a regioselective
and economic synthetic processes for direct migratory 2,1-insertion of the alkynes, followed
preparation of 3-functionalized quinolines is still by the further reaction with DMSO to deliver the
highly desirable and presents an urgent need.
To address this issue,
recently a significant amount of attention has
been directed toward the development of
privileged 3-arylquinoline backbone (Scheme 1f).
Table 1 Optimization of reaction conditions.[a]
transition-metal-catalyzed C–H activation with
DMSO being a reactant due to its ready
availability.[12] Indeed, lots of versatile reactions
have been delivered by using DMSO as the
synthon for building the quinoline backbone.[13-19]
For example, Singh's group and Zhang's group
have independently revealed two beautiful
examples for the efficient synthesis of 4-
arylquinolines via a FeCl3 and CH3SO3H
promoted oxidative annulation of anilines and
aryl ketones, respectively, in which DMSO was
employed as a C1 source (Scheme 1a).[14]
Similarly, Tiwari[15] and Cheng[16] also
Yield[b](%)
Entry
catalyst
additive A
additive B
3a
12
0
3aa
34
0
1
2
3
4
5
6
7
8
9
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
Cp*Co(CO)I2
/
AgNTf2
AgNTf2
AgNTf2
AgNTf2
Ag2SO4
AgNO3
Ag2CO3
AgOAc
AgOTf
AgNTf2
AgNTf2
/
HOPiv
HOAc
TFA
HOTf
TFA
TFA
TFA
TFA
TFA
K2S2O8
/
TFA
TFA
TFA
TFA
TFA
81
0
0
0
0
0
0
0
46
32
77
0
0
0
0
10
11
12
13
14
15
16
8517
0
0
14
0
0
0
AgNTf2
/
AgNTf2
AgNTf2
/
0
0
independently
intermolecular three component reaction for the
construction of functionalized quinoline
demonstrated
a
prominent
Co(OAc)2
Co(acac)2
0
0
42
21
[a]
[b]
Reaction conditions: 1a (0.5 mmol), 2a (0.6 mmol),
Cp*Co(CO)I2 (5 mol %), additive (20 mol %), and
additive (1.5 equiv) in DMSO (2 mL) at 120 °C for 24 h
under air.
A
framework by using DMSO as the C1 source
(Scheme 1b and 1c). Interestingly, Guo and co-
workers demonstrated an elegant CuCl2-catalyzed
B
Isolated yields after chromatography.
C–H activation/cyclization of simple ketones and
anilines for the synthesis of 2-arylquinolines,
where DMSO was used as the C3 source (Scheme
1d).[17] Very recently, our group has also
To confirm the aforementioned hypothesis and
taking inspiration from Li group’s work on
cobalt(III)-catalyzed regioselective insertion of
terminal alkynes,21 we started our investigation
by using simple aniline (1a) and phenylacetylene
described a cobalt(III)-catalyzed C–H activation
strategy for one-pot construction of 4-
arylquinoline framework by using terminal
alkynes as the coupling partners (Scheme 1e).[18]
Almost simultaneously, Tiwari's group also reveal
an efficient and transition-metal-free approach for
(
2a) as model substrates and commenced this
study by testing different reaction conditions for
the desired synthesis of 3-phenylquinoline 3a
.
o
Initial reaction was run in DMSO at 120 C by
2
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10.1002/adsc.201801709
Advanced Synthesis & Catalysis
proceeded smoothly to give the desired products
in moderate to high yields, revealing that the
electronic and steric effects of the substituents
had no obvious influence on the efficiency of the
reaction. For example, substituted anilines
bearing the electron-neutral (H), electron-
donating (Me, OMe, SMe, Ph, N(CH3)2) or
electron-withdrawing (F, Cl, Br, CF3, CO2Me)
substituents at the para-position all showed good
employing Cp*Co(CO)I2, AgNTf2, and HOPiv as
the catalytic system (Table 1, entry 1). To our
delight, the anticipated reaction mode was
occurred even though the product 3a was
obtained as the by-product with an isolated yield
of 12%. Based on this encouraging finding, next
we were interested to examine the effect of the
acid for the optimization of the reaction.
Gratefully, switching the acid additive to TFA
gave an optimal results with an impressive yield
of 3a (81%), in which no 3aa was detected under
this condition (Table 1, entry 3). Subsequently,
the replacement of AgNTf2 by other silver salt
sources such as Ag2SO4, AgNO3, Ag2CO3,
AgOAc, and AgOTf, all gave an inefficient result
(Table 1, entries 5-9). The control experiments
demonstrated that the omission of either the
catalyst or co-catalytic additives led to a
significant decrease in the product yield (entries
11-14), indicating that the cobalt(III) catalyst and
AgNTf2/TFA additives were indispensable for the
compatibility, and the corresponding products 3a
-
k
were delivered efficiently in 70-87% yields.
Similarly, ortho- and meta-substituted anilines
also successfully afforded the corresponding
products 3l-s in good yields (up to 84%). It was
worth emphasizing that, for meta-substituted
anilines, the sole regioisomer was detected, in
which the C–H activation reaction exclusively
occurred at a less-hindered ortho-position. These
results were consistent with the reported cobalt-
catalyzed transformations.[24] The disubstituted
anilines also worked well under the optimized
conditions to afford the desired products (3t-w) in
excellent yields. Interestingly, this reaction also
tolerated well with the polyaromatic naphthalene
substrate, giving the corresponding product 3x in
reaction
outcome.
Finally,
changing
Cp*Co(CO)I2 to other well-known cobalt species
also obviously reduced the yield of the product or
completely inhibited the reaction (entries 15-16).
an
80%
yield.
Moreover,
and
large-size
4-
aminoglutethimide
morpholinobenzenamine were viable substrates
as they provided the desired products 3y and 3z
in 65% and 75%, respectively.
[a]Reaction conditions:
(5 mol %), AgNTf2 (20 mol %), and TFA (1.5 equiv) in DMSO (2
1 (0.5 mmol), 2a (0.6 mmol), Cp*Co(CO)I2
mL) at 120 °C for 24
chromatography.
h under air, isolated yields after
Scheme 2. Scope of anilines.[a]
[a]Reaction conditions: 1a (0.5 mmol),
(5 mol %), AgNTf2 (20 mol %), and TFA (1.5 equiv) in DMSO (2
2 (0.6 mmol), Cp*Co(CO)I2
mL) at 120 °C for 24
chromatography.
h under air, isolated yields after
With the optimized conditions in hand, we
proceeded to investigate the substrate scope of
this transformation with respect to the aniline
substrates (Scheme 2). Regarding the substituted
anilines, the results showed that both electron-
Scheme 3. Scope of alkynes.[a]
donating
and
-withdrawing
substituents
3
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10.1002/adsc.201801709
Advanced Synthesis & Catalysis
Subsequently, we evaluated the substrate scope
provided clear evidence that DMSO was not only
used as the solvent but also employed as the C1
source. Then, to define the role of acid in the
catalytic system, the deuterium labeling
with respect to the terminal alkynes (Scheme 3).
The substituted aryl alkynes bearing various
steric and electronic functional groups either at
the ortho-, meta-, or para- position on the experiment was also performed in the presence of
benzene ring all gave the corresponding products CF3CO2D by using p-toluidine and
4a with excellent regioselectivity and in phenylacetylene as the model substrates (Scheme
moderate to excellent yields (70-85%). 4b). H NMR analysis demonstrated that the 2-
Interestingly, the phenyl group could also be position and 8-position of the quinoline were
extended to the heteroaryl moiety, such as 2- substantially deuterated, hinting that the C–H
ethynylthiophene and 2-ethynylpyridine, bond cleavage at both DMSO and ortho-position
delivering the corresponding quinoline products of the amino group might be occurred, which also
-j
1
in good yield (for 4k, 74%; and for 4l, 70%). further revealed the vital role of the TFA in the
Moreover, the electron-withdrawing alkynes, catalytic cycle. Subsequently, two independent,
such as methyl propiolate, could be compatible
well in the transformation with excellent
side-by-side experiments were also carried out to
probe the C–H activation process, and a relatively
regioselectivity, delivering 4m in acceptable large KIE value (kH/kD = 2.33) was detected. The
yields. Finally, it should be noted that the reaction result revealed that the C–H cleavage could
also worked well with polyaromatic 2- potentially be involved in the rate-limiting step
ethynylnaphthalene to produce the product 4n in (Scheme 4c). Moreover, 2-styrylaniline was
83% yield.
prepared and designated as a substrate to react
with DMSO under the standard conditions. The
result showed that 89% of quinoline 3a was
obtained (Scheme 4d, eq (1)). On the other hand,
the reaction of 2-styrylaniline with DMSO-d6
gave the C1-90% deuterated product 3a in 82%
yield (Scheme 4d, eq (2)), and no deuterium
scrambling in 8-position of the quinoline was
observed. Taken together, the results not only
confirmed the participation of DMSO in the
annulation reaction but also indicated that the
cleavage of C–H bond occurred before the
annulation reaction. Finally, the kinetic isotope
effect was measured to shed more light on the
annulation process, and a small value for the
kinetic isotope effect (KIE = 1.32) was monitored
from two independent, side-by-side experiments
(Scheme 4d, eq (3)), suggesting that the cleavage
of the C–H bond in DMSO might not be the rate-
determining step.
Scheme 4. Mechanistic studies.
Based on the remarkable substrate scope as
shown in above and to obtain a better insight into
the reaction mechanism, especially to give an
overall understanding on how the TFA to control
the selectivity of alkyne insertion, a set of
additional experiments were carried out in
Scheme 4. Firstly, when DMSO-d6 was used to
replace DMSO, the deuterated product [d1]-3g
was formed in 79% yield with almost 100%
incorporation of deuterium (Scheme 4a), which
Scheme 5. Proposed catalytic cycles.
4
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10.1002/adsc.201801709
Advanced Synthesis & Catalysis
Acknowledgements
On the basis of these experimental results and
We thank the National Natural Science Foundation of
China (81330007, U1601227, 21502100, 81502909
and 21877020), the Science and Technology Programs
of Guangdong Province (2015B020225006), Natural
Science Funds for Distinguished Young Scholar
(2017A030306031), Medical Scientific Research
Foundation of Guangdong Province (A2018421), and
Natural Science Foundation Research Team of
Guangdong Province (2018B030312001) for financial
support on this study.
literature precedents, a plausible catalytic cycle is
depicted in Scheme 5. The reaction starts from a
cationic cobalt complex
with aniline, followed by an ortho-metalation
process to afford the intermediate via a
A, which coordinates
B
reversible C–H bond cleavage process, which
further coordinates with the alkyne 2a to generate
intermediate
2,1-insertion of alkyne is occurred to provide a
vinylcobalt intermediate . It is known that the
DMSO is activated by TFA to give E [13f,14b,17]
which then couples with to produce the
intermediate . Subsequently, gives an imine
species with the elimination of HSMe,
followed by Co–C migratory insertion to provide
the intermediate . Finally, protonolysis of
C. Then, TFA-controlled selective
D
,
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10.1002/adsc.201801709
Advanced Synthesis & Catalysis
COMMUNICATION
Cobalt(III)-Catalyzed, DMSO-Involved, and TFA-
Controlled Regioselective C–H Functionalization
of Anilines with Alkynes for Specific Assembly of
3-Arylquinolines
Adv. Synth. Catal. Year, Volume, Page – Page
Peiquan Zhang, Yurong Yang, Zhiyong Chen,
Xu Zhang, Xuefeng Xu,* Zhi Zhou,* Xiyong Yu
and Wei Yi*
7
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