Palladium-Catalyzed One-Pot Synthesis of C2-Quaternary Indolin-3-ones via 1H-indole-3-sulfonates Generated in Situ from 2-Alkynyl Arylazides and Sulfonic Acids

Article abstract of DOI:10.1002/adsc.201700838

A novel method for the synthesis of C2-quaternary indole-3-ones via palladium-catalyzed one-pot transformation of 2-alkynyl arylazides is described. The reaction produced in moderate to excellent yields under mild conditions. This novel rearrangement of 1-H-indole-3-sulfonates represents an important contribution to the application of aryl sulfonates. (Figure presented.).

Full text of DOI:10.1002/adsc.201700838

Title: Palladium-Catalyzed One-Pot Synthesis of C2-Quaternary
Indolin-3-ones via 1H-indole-3-sulfonates Generated in Situ from
2-Alkynyl Arylazides and Sulfonic Acids
Authors: Xiaoxiang Zhang, Ping Li, Chang Lyu, Wanxiong Yong, Jing
Li, Xingyu Pan, Xinbao Zhu, and Weidong Rao
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700838
Link to VoR: http://dx.doi.org/10.1002/adsc.201700838

Advanced Synthesis & Catalysis
10.1002/adsc.201700838
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Palladium-Catalyzed One-Pot Synthesis of C2-Quaternary
Indolin-3-ones via 1H-indole-3-sulfonates Generated in Situ
from 2-Alkynyl Arylazides and Sulfonic Acids
,
†
†
†
†
Xiaoxiang Zhang,* Ping Li, Chang Lyu, Wanxiong Yong, Jing
†
‡
†
,†
Li, Xinyu Pan, Xinbao Zhu, and Weidong Rao*
†
[Jiangsu key lab of Biomass-based Green Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry
University, Nanjing 210037, China. Te l： (+86) 25-854270；Fax: (+86) 25-85427024; E-mail: zhangxiaoxiang@njfu.edu.cn
X. Zhang); weidong@njfu.edu.cn (W. Rao)]
(
‡
[
Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China]
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.
A
novel method for the synthesis of
C2-quaternary indole-3-ones via palladium-catalyzed
one-pot transformation of 2-alkynyl arylazides is described.
The reaction produced in moderate to excellent yields
under mild conditions. This novel rearrangement of
1
-H-indole-3-sulfonates
represents
an
important
contribution to the application of aryl sulfonates.
Keywords: palladium-catalyzed; indole derivatives;
-alkynyl arylazides; N-containing heterocycles.
2
Aryl sulfonates are very important coupling reagents
used in transition metal-catalyzed cross-coupling
[1]
reactions. Compared with aryl halides and triflates,
aryl sulfonates are much easier to handle. Although
they have been regarded as relatively unreactive
coupling reagents, some very important and
successful work has been reported, such as
Scheme 1 Transformation of aryl sulfonates.
However, the unexpected C2-quaternary indolin-3-
one 4aa was obtained in 50% yield instead of the
desired coupling product under Buchwald's cross
coupling reaction conditions, and such molecules are
important core structures found in many natural
[1a]
palladium-catalyzed Hiyama cross-coupling
and
palladium[ or nickel -catalyzed Suzuki-Miyaura
reactions. In those reported coupling reactions,
various aryl and hetero aryl sulfonates were
employed. To our surprise, the application of
1c]
[1d]
[2]
products and bioactive compounds (Scheme 2).
1
H-indole-3-sulfonates, as important group of aryl
sulfonates, has not been reported. We envisioned that
1
2
H-indole-3-sulfonates generated in situ from
-alkynyl arylazides 1 and sulfonic acids 2 might also
act as efficient coupling reagents in carbonyl enolate
coupling reactions using Buchwald's reaction
conditions (Scheme 1).[
1i]
Scheme
2
Selected natural products containing
C2-quaternary indolin-3-ones.
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201700838
Therefore, many methods have been established for
[3]
the synthesis of C2-quaternary indolin-3-ones, such
as Pd-catalyzed C-H oxygenation,[ the oxidative
3a]
[
3p]
rearrangement of α-imino gold carbenes,
and
[
3f]
rhodium(III)-catalyzed multisite cyclization. To the
best of our knowledge, reactions for the synthesis of
2
-(2-oxo-2-phenylethyl)-2-phenylindolin-3-ones
4
have remained sparse. This compound is the only
member of the C2-quaternary indolin-3-one family of
compounds to also act as a valuable synthetic
precursor for various N-hetero cycles,[
3d]
and its
preparation has been reported by Ru-catalyzed
redox-neutral cleavage of the N-O bond in
Scheme 3 Control experiments on converting Ⅰto 4aa.
[3g]
isoxazolidines
2
or base-catalyzed reactions of
-oxindoles with enones.[ However, the reported
3d]
Upon decreasing the temperature to room
temperature or 60 ℃, either intermediate Ⅰor a low
product yield was obtained (entries 2-3). Different
reactions suffer from multi-step preparation of
starting materials or low product yields. Hence, mild
and efficient methods for the synthesis of 2-(2-oxo-2-
bases were also examined. K
be an efficient base and provided 4aa in a 72% yield
entry 4). Repeating this reaction with K PO and
2
CO
3
was also shown to
phenylethyl)-2-phenylindolin-3-ones
process are desirable.
in
one-pot
(
3
4
t-BuOK as the base also produced 4aa in similar
yields of 44 and 54%, respectively (entries 5-6).
Interestingly, the reaction was found to proceed fast
and generate many unknown compounds when the
organic base DBU was employed, and it produced a
Recently, we reported the transformation of
[
4]
2
-alkynyl arylazides 1 catalyzed by gold , which
[5]
generated α-imino gold carbenes in situ followed by
the unexpected trapping of 1,4-dioxane instead of
MsOH.[
4a]
Later, we found that Pd(OAc) was an
2
1
7% yield of the desired product 4aa (entry 7).
efficient catalyst for the tandem reaction of
1
-azido-2-(phenylethynyl)benzene 1a with MsOH 2a,
which gave 96% yield of
-phenyl-4H-benzo[d][1,3]oxazin-4-one Ⅰ in 3 min.
Table 1 Optimization of the reaction conditions.[a]
a
2
Due to its high efficiency in preparing Ⅰ, we decided
to transform the 2-alkynyl arylazides 1 into
2
-(2-oxo-2-phenylethyl)-2-phenylindolin-3-ones
4
using a one-pot method. As far as we know, there has
been no previous report on this transformation of
Entry base
T (
℃
)
t (h)
Yield(%)[b]
74%
2
2
-alkynyl arylazides 1 to 2-(2-oxo-2-phenylethyl)-
-phenylindolin-3-ones 4 via 1H-indole-3-sulfonates
1
2
3
4
5
6
7
8
9
1
1
Cs
Cs
Cs
2
2
2
CO
CO
CO
3
3
3
90
rt
23
24
23
23
23
23
5.5
23
23
23
23
[6,7]
in organic synthesis.
palladium-catalyzed
C2-quaternary
Herein, we report a novel
[c]
n.r.
one-pot
synthesis
of
via
60
90
90
90
90
90
90
90
47%
72%
44%
54%
17%
indolin-3-ones
K
K
2
CO
PO
3
1
2
H-indole-3-sulfonates generated in situ from
3
4
-alkynyl arylazides and sulfonic acids.
Before optimizing the one-pot reaction conditions,
we briefly investigated the conversion of
t-BuOK
DBU
[
d]
[c]
-
Trace
2
2
-phenyl-1H-indol-3-yl methanesulfonate Ⅰ to
-(2-oxo-2-phenylethyl)-2-phenylindolin-3-one 4aa.
[
e]
Cs
Cs
Cs
2
2
2
CO
CO
CO
3
3
3
43%
52%
79%
[
f]
0
1
After performing control experiments to convert Ⅰto
aa, we found that the Pd catalyst, phosphine ligand
reflux
4
[
a]
and inert atmosphere were not needed for this
conversion (Scheme 3). Interestingly, a trace amount
of the desired product 4aa was still observed without
2
Reaction conditions: 1a (0.1 mmol), Pd(OAc) (5
mol%), 2a (3 equiv), 1,4-dioxane (1 mL), base (3.5 equiv),
and 3a (1.5 equiv)
[
b]
employing Cs
preliminary
2
CO
3
[(Scheme 3, (c)]. Based on these
we chose 1-azido-2-
Isolated yield.
Checked using TLC and H NMR measurements from
[
c]
1
results,
(
phenylethynyl)benzene 1a, MsOH 2a, and
the crude mixture.
[
d]
acetophenone 3a as model substrates to establish the
one-pot reaction conditions (Table 1). This
containing 1a and 2a in 1,4-dioxane with 5 mol%
Without base.
PhCl was used as solvent.
CH CN was used as solvent.
3
[e]
[f]
Pd(OAc) at room temperature for 5 min followed by
2
the addition of Cs
desired
2
CO
3
and 3a at 90 ℃ gave the
Only a trace amount of 4aa was obtained without
base. The intermediate Ⅰ was confirmed as the
major compound in this reaction after checking the
product
2
-(2-oxo-2-phenylethyl)-2-phenylindolin-3-one 4aa
in 74% yield (entry 1).
1
TLC and crude H NMR (entry 8). The use of either
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201700838
PhCl or CH
low product yields of 43 and 52%, respectively
entries 9-10). However, the desired product yield
was not significant increased at reflux temperature
entry 11). Due to its long reaction time and safety
consideration, a relatively low temperature was better.
Hence, 90 ℃ was chosen as the most suitable
reaction temperature.
3
CN resulted in the formation of 4aa in
aryl or hetero aryl groups on the alkyne carbon were
also examined, and they provided the corresponding
products in moderate to excellent yields (4aj-4ap).
We also examined the effect of an aliphatic
(
2
(
substituent. For substrates where R = t-Bu, a 67%
2
yield of 4aq was obtained. However, switching R to
carbonyl groups were found to lead to complex on the
1
basis of TLC and H NMR analysis (4ar-4as).
To define the scope of this one-pot protocol, we
next turned our attention to the transformation of a
variety of 2-alkynyl arylazides 1(Table 2). Reactions
of 2-alkynyl arylazides with electron-withdrawing or
electron-donating groups on the aromatic ring gave
Repeating the reactions without addition of Cs
2
CO
3
and acetophenone 3a, the first-step products Ⅱand Ⅲ
were obtained in yields of 61 and 35%, respectively.
To our surprise, the reactions proceeded well when
TsOH was employed instead of MsOH, which
afforded the corresponding products in relatively high
yields after a short time (yields in parentheses).
the desired indolin-3-ones 4 in moderate to excellent
1
yields (4ab-4ai) (R = halide, Me, OMe, CF
3
). In
addition, substrates 1 containing different substituted
The substituent effect on the enolates generated
from ketones and malonates 3 was also investigated
Table 2. Substrates scope of the 2-alkynyl arylazides 1.
(Table 3). The reactions of substituted acetophenones
halide, Me, CF , NO ), 1-(naphthalen-2-yl)ethanone
[
a,b,c]
(
3
2
and dialkyl malonates were found to proceed well
under the standard reaction conditions and gave the
desired indolin-3-ones in moderate to excellent yields
(
4ba-4bn). However, substrates of acetophenones
with F, m-NO and OMe led to relatively low yields
4bf-4bg, 4bk).
2
(
Table 3. Substrates scope of the ketones 3b-3l and
[
a,b,c]
malonates 3m-3n.
[
a]
Reaction conditions: 1 (0.1 mmol), Pd(OAc)
2
(5 mol%),
2
a (3 equiv), 1,4-dioxane (1 mL), Cs CO (3.5 equiv), 3a
2
3
(
1.5 equiv), and 90 ℃.
Isolated yields.
Yields in parentheses employing TsOH instead of
[
a]
Reaction conditions: 1 (0.1 mmol), Pd(OAc)
2
(5 mol%),
[
b]
2
a (3 equiv), 1,4-dioxane (1 mL), Cs CO (3.5 equiv), 3
2
3
[
c]
(
1.5 equiv), and 90 ℃.
MsOH.
[
b]
[
d]
Isolated yields.
Yields in parentheses employing TsOH instead of
The first-step products Ⅱand Ⅲwere isolated:
[
c]
MsOH.
Based on the above experimental results, we
tentatively proposed that the present Pd-catalyzed
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201700838
C2-quaternary indolin-3-ones forming reaction by the
mechanism outlined in Scheme 4, although this is
highly speculative. This process could involve the
activation of 2-alkynyl arylazides substrate through
coordination of the Pd catalyst with the triple bond.
This activation delivered the Pd-coordinated
intermediate Ⅳ, which underwent cyclization to give
Scheme 6. Control experiments for converting 1a to 4aa.
To examine the efficiency of this method, a large-
scale experiment was carried out. A reaction
containing 1 mmol of 1a was performed under the
standard reaction conditions; the desired product 4aa
was obtained in 80% yield after 50 min (Scheme 7).
species Ⅴ. After releasing N , α-imino palladium
2
[6]
carbenes Ⅵ were formed, followed by subsequent
trapping of TsOH to provide complex Ⅶ. The
protodemetalation step of Ⅶ would then deliver the
intermediate 1H-indole-3-sulfonate Ⅷ. Under heating
and basic conditions, Ⅷcould undergo a 1,3-sulfonyl
shift (O to C)[ to form α-amino sulfone Ⅸ ,
followed by reductive desulfonation to deliver the
intermediate 2-phenyl-3H-indol-3-one Ⅹ.[ Finally, a
Mannich-like trapping of acetophenone 3a led to the
formation of the desired product 4aa.
7]
[8]
9]
Scheme 7. A large-scale experiment.
Conclusions
In summary, we developed a novel method to
obtain C2-quaternary indolin-3-ones via the
palladium-catalyzed one-pot reactions of 2-alkynyl
arylazides with sulfonic acids. The results showed
that the reaction tolerates a structurally diverse set of
2
-alkynyl arylazides and enolates generated from
ketones and malonates that can be obtained
commercially. Efforts to explore the synthetic
applications of these reactions are currently underway
and will be reported in future studies.
Scheme 4. Tentative mechanism for the Pd-catalyzed
one-pot reactions of 2-alkynyl arylazides 1.
In order to prove the formation of intermediate Ⅸ,
a reaction of 1a to Ⅸ was conducted at room
temperature. We found that a yellow compound was
formed checked by TLC, which was unstable after
purification by column. Therefore, the crude reaction
solution was characterized by LC-MS and the
corresponding peaks of Ⅸand Ⅹwere found from the
mass spectrum (Scheme 5).[
Experimental Section
General Procedure for the Preparation of
C2-quaternary Indolin-3-ones 4 in One-pot Process
10]
To a solution of 2-alkynyl arylazides 1 (0.1 mmol, 1
equiv), Pd(OAc)
2
(5 mol%) and 1,4-dioxane (0.5 mL) was
added 2a MsOH or 2b TsOH (3 equiv.) diluted in
1
2
,4-dioxane (0.5 mL) at room temperature. After the
-alkynyl arylazides 1 were disappear monitored by TLC
(
2 3
about 5 min for most of 1), Cs CO (0.35 mmol, 3.5
equiv) and ketones and malonates 3 (0.15 mmol, 1.5
equiv.) were added to the reaction solution, which was then
stirred at 90 ℃ and monitored by TLC analysis. On
completion, the reaction mixture was directly subjected to
purification by flash column chromatography on silica gel
to give the desired C2-quaternary indolin-3-ones 4. (eluent:
petrol ether: ethyl acetate = 40:1 to 8:1).
Scheme 5. Control experiments for converting 1a to Ⅸ.
Later, we repeated the reaction in two steps under
the standard reaction conditions for the conformation
of another intermediate 2-phenyl-3H-indol-3-one Ⅹ.
After 20 min, Ⅹ was isolated in 54% yield, which
was then converted to the desired product 4aa in 66%
yield (Scheme 6).
General Procedure for the Preparation of
2
-Phenyl-3H-indol-3-one Ⅹ and Its Conversion to
2
-(2-Oxo-2-phenylethyl)-2-phenylindolin-3-one 4aa
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201700838
To a solution of 1-azido-2-(phenylethynyl)benzene 1a
0.1 mmol) in dioxane (0.4 mL) was added Pd(OAc) (5
2
mol%) and TsOH 2b (3 equiv.) in sequence at room
temperature. The resulting solution was stirred and
monitored by TLC analysis (3min). On completion,
Huang, G.-Q. Li, L. Wang, R.-W. Jiang, T.-T. Yang,
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Chem. 2010, 75, 6830; d) A. Karadeolian, M. A. Kerr,
Angew. Chem., Int. Ed. 2010, 49, 1133.
(
Cs
2
CO
3
(0.35 mmol, 3.5 equiv) was added to the reaction
[3] For recent selected synthesis of C2-quaternary
indolin-3-ones, see: a) S. K. Guchhait, V. Chaudhary,
V. A. Rana, G. Priyadarshani, S. Kandekar, M.
Kashyap, Org. Lett. 2016, 18, 1534; b) G. Zhao, X.
Xie, H. Sun, Z. Yuan, Z. Zhong, S. Tang, X. She, Org.
Lett. 2016, 18, 2447; c) S. K. Guchhait, V. Chaudhary,
V. A. Rana, G. Priyadarshani, S. Kandekar, M.
Kashyap, Org. Lett. 2016, 18, 1534; d) Y. Shao,
Y.-M. Zeng, J.-Y. X.-Q. Ji, Sun, H.-T. Yang, C.-B.
Miao, J. Org. Chem. 2016, 81, 12443; e) N. Li, T.-Y.
Wang, L.-Z. Gong, L. Zhang, Chem.- Eur. J. 2015,
21, 3585; f) J.-R. Huang, L. Qin, Y.-Q. Zhu, Q. Song,
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Kumar, C. V. Ramana, Org. Lett. 2015, 17, 2870; h)
R. Kuppusamy, P. Gandeepan, C.-H. Cheng, Org.
Lett. 2015, 17, 3846; i) S. Lerch, L.-N. Unkel, M.
Brasholz, Angew. Chem., Int. Ed. 2014, 53, 6558; j) S.
C. V. Kumar, C. V. Ramana, Org. Lett. 2014, 16,
4766; k) S. Han, K. C. Morrison, P. J. Hergenrother,
M. J. Movassaghi, Org. Chem. 2014, 79, 473; l) W.
Ding, Q.-Q. Zhou, J. Xuan, T.-R. Li, L.-Q. Lu, W.-J.
Xiao, Tetrahedron Lett. 2014, 55, 4648; m) P.-X.
Zhou, Z.-Z. Zhou, Z.-S. Chen, Y.-Y. Ye, L.-B. Zhao,
Y.-F. Yang, X.-F. Xia, J.-Y. Luo, Y.-M. Liang, Chem.
Commun. 2013, 49, 561; n) Y. Goriya, C. V. Ramana,
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solution. Then the reaction was stirred at 90 ℃ and
monitored by TLC analysis. After 20 min, the reaction
solution was then directly passed through a pad of celite
and rinsed with eluent (petrol ether: ethyl acetate = 1: 40).
The 2-phenyl-3H-indol-3-one Ⅹ was obtained as a red
solid.
To a solution of 2-phenyl-3H-indol-3-one Ⅹ (0.05
2 3
mmol) in 1,4-dioxane (0.5 mL) was added Cs CO (1.5
equiv) and acetophenone 3a (1.5 equiv.) in sequence at
room temperature. The resulting solution was stirred at
9
0 ℃ and monitored by TLC analysis. After 10 min, the
reaction solution was then directly subjected to purification
by flash column chromatography on silica gel to give the
desired product 4aa. (eluent: petrol ether: ethyl acetate =
8
:1 to 4:1).
Supporting Information
Detailed descriptions of experimental procedures and their
spectroscopic data are presented in the Supporting
Information.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China Grants (21302096 and 21502093), Natural
Science Foundation of Jiangsu Province Grants (BK20171449,
BK20130962 and BK20150871), and the Project Fund from the
Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD).
[
4] For our recent studies on transformtion of 2-alkynyl
arylazides, see: a) X. Zhang, X. Sun, H. Fan, C. Lyu,
P. Li, H. Zhang, W. Rao, RSC Adv. 2016, 6, 56319;
b) X. Zhang, X. Sun, H. Fan, P. Li, C. Lyu, W. Rao,
Eur. J. Org. Chem. 2016, 25, 4265.
[
5] For recent selected a review on the generation of
α-imino gold carbenes, see: a) P. W. Davies, M.
Garzûn, Asian J. Org. Chem. 2015, 4, 694; for recent
selected examples, see: b) G. H. Lonca, C. Tejo, H. L.
Chan, S. Chiba, F. Gagosz, Chem. Commun. 2017, 53,
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[
10] Please see Supporting Information for more details.
6
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Advanced Synthesis & Catalysis
10.1002/adsc.201700838
COMMUNICATIONS
Palladium-Catalyzed One-Pot Synthesis of
C2-Quaternary
Indolin-3-ones
via
1
2
H-indole-3-sulfonates Generated in Situ from
-Alkynyl Arylazides and Sulfonic Acids
Adv. Synth. Catal. Year, Volume, Page – Page
Xiaoxiang Zhang,* Ping Li,† Chang Lyu,
,
†
†
†
†
‡
Wanxiong Yong, Jing Li, Xinyu Pan, Xinbao
Zhu, and Weidong Rao*
†
,†
7
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