Pd-Catalyzed One-Pot Insertion Reaction of Cyclic C-Acylimines into Carbon-Carbon σ-Bonds for the Synthesis of Polyfunctional Indolin-3-ones from 2-Alkynyl Arylazides and Aryl Ketones

Article abstract of DOI:10.1002/adsc.201801162

A method to prepare polyfunctional indolin-3-ones by Pd-catalyzed one-pot insertion reaction of cyclic C-acylimines into carbon-carbon σ-bonds is described. The reaction was accomplished in good to excellent yields under mild reaction conditions. (Figure presented.).

Full text of DOI:10.1002/adsc.201801162

Title: Pd-catalyzed One-pot Insertion Reaction of Cyclic C-acylimines
into Carbon–carbon σ-Bonds for the Synthesis of Polyfunctional
Indolin-3-ones from 2-Alkynyl Arylazides and Aryl ketones
Authors: Xiaoxiang Zhang, Ping Li, Wanxiong Yong, Rong Sheng,
Weidong Rao, and Xinbao Zhu
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.201801162
Link to VoR: http://dx.doi.org/10.1002/adsc.201801162

Advanced Synthesis & Catalysis
10.1002/adsc.201801162
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Pd-catalyzed One-pot Insertion Reaction of Cyclic C-acylimines
into Carbon–carbon σ-Bonds for the Synthesis of Polyfunctional
Indolin-3-ones from 2-Alkynyl Arylazides and Aryl Ketones
Ping Li, Wanxiong Yong, Rong Sheng,Weidong Rao, Xinbao Zhu
and Xiaoxiang Zhang*
[
Jiangsu key lab of Biomass-based Green Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry
University, Nanjing 210037, China. Tel ： (+86) 25-854270 ； Fax: (+86) 25-85427024; E-mail:
zhangxiaoxiang@njfu.edu.cn]
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))
[
8]
Abstract.
A
method to prepare polyfunctional
multi-steps and often harsh conditions. Recently, Li
[9]
indolin-3-ones by Pd-catalyzed one-pot insertion reaction
of cyclic C-acylimines into carbon-carbon σ-bonds is
described. The reaction was accomplished in good to
excellent yields under mild reaction conditions.
group reported the ring expansion reactions of
indene-1,3-dione for the synthesis of functionalized
benzoannulated seven-membered ring compounds. In
this work, the alkyne functional groups were inserted
into the indene-1,3-dione [Scheme 1, (2)].
Keywords: Pd-catalyzed; insertion reaction; cyclic
C-acylimines; polyfunctional indolin-3-ones
In this context, we envisioned that the
development of novel alternatives generated from
easily accessible substrates for the insertion reaction
of C-C σ-bonds would be particularly attractive.
Indolin-3-ones are versatile synthetic building
blocks and utilized as core structures in the
The development of carbon-carbon σ-bonds
insertion reactions is of considerable very important
in organic chemistry.[ The mild and selective
insertion methods provide an efficient synthetic
strategy for the construction of polyfunctional
molecules, which are found particularly high
1]
[10]
preparation of various natural products,
such as
[10a]
[10b]
[10c]
austamide,
halichrome A,
cephalinone,
and fluorocurine.[
10d]
Especially, polyfunctional
indolidin-3-ones are of considerable useful
intermediates for the construction of natural products.
[
2]
significance in bioactive product synthesis,
[3]
[4]
molecular recognition, drug design and novel
[11]
[5]
materials preparation. Among the reported reactions
in this area, the insertion of arynes into C-C σ-bonds
is a powerful method for the synthesis of
polysubstituted arenes by introducing two functional
groups into triple bonds [Scheme 1, (1)]. In this
type of reaction, a formal acyl-alkylated bifunctional
product was obtained via a four-membered ring
formation and followed by an acyl group migration
[6]
[7]
process. In these insertion reactions, malononitriles,
[
7a]
[7b]
[7c]
α-cyanocarbonyls,
acylated [7efl] uorenes,
β-ketosulfones,[
7d]
β-ketoesters
or
β-ketophosphonates[ were normally employed as
the precursors of C-C σ-bonds. And the key
intermediates arynes, due to their high activity, were
generated in situ from ortho-silyl aryltriflates in the
7f]
Scheme 1
Insertion reactions of functional groups into
C-C σ-bonds.
-
presence of F source. While the synthesis of
While this has led to many efficient synthetic
ortho-silyl aryltriflates has been reported to need
[12]
methods, those that describe the preparation of
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201801162
polyfunctional indolin-3-ones via insertion of
cyclic C-acylimines into C-C σ-bonds process
have not been reported [Scheme 1, (3)].
at 90 ℃ for 40 min gave the best result (entry 1).
Under
these
conditions,
1-benzoyl-2-(2-oxo-2-phenylethyl)-2-phenylindolin-3
Recent reports have shown the use of 2-alkynyl
arylazides as efficient substrates in many
nitrogen-containing heterocycles formation reactions
-
one 4aa was obtained in 95 % yield, which was
1
confirmed by H NMR analysis and X-ray crystal
structure determination (Fig. 1).
[13]
via α-imino metal carbenes intermediates.
For
Pd-catalyzed
one-pot synthesis of C2-quaternary indolin-3-ones
[14]
instance, we recently reported
[14a]
from 2-alkynyl arylazides and aryl ketones.
To
our surprise, we later found that substitution with
strongly electron-withdrawing groups at α-position of
aryl ketones resulted in the formation of
polyfunctional compounds via unexpected insertion
reaction of cyclic C-acylimines into C-C σ-bonds. To
our
knowledge,
however,
approaches
to
polyfunctional indolin-3-ones from 2-alkynyl
arylazides via pd-catalyzed one-pot insertion process
have not been reported. As part of an ongoing
examining the utility of 2-alkynyl arylazides in
heterocycles synthesis, we report herein the facile
insertion reaction of cyclic C-acylimines generated in
situ into carbon–carbon σ-bonds for the synthesis of
polyfunctional indolin-3-ones.
Figure 1 ORTEP drawing of 4aa with thermal ellipsoids
at 50% probability.
Repeating this reaction at room temperature was
found to result in dramatically low yield of 20% and
need longer reaction time (entry 2). when the
temperature was decreased to 60 ℃, a similar yield
was obtained after 7 hours (entry 3). In contrast,
repeating the reaction in the presence of other bases
at the same temperature was found to give different
Table 1 Optimization of the reaction conditions [a]
results. When K
2
CO was employed as a base, the
3
desired product was obtained in high yield of 95%,
but need a longer time (entry 4). However, either
Entry
Base
T (℃)
Time (h)
Yield/%[b]
1
2
3
4
5
6
7
8
9
Cs
Cs
Cs
2
2
2
CO
CO
CO
3
3
3
90
r.t.
60
90
90
90
90
90
90
0.8
24
7
12
24
0.5
0.5
24
0.8
95
20
94
95
56
65
46
K
3
PO , t-BuOK or DBU was used as the base, low
4
products yields of 46-65% were obtained (entries 5-7).
It was noted that the reaction was completed in
relatively short time when stronger or organic base
was employed. On the other hand, some unknown
compounds were observed by checking the crude
mixture of the reaction using t-BuOK or DBU as the
K
K
2
CO
PO
3
3
4
t-BuOK
DBU
----
[
[
c] [d]
e]
trace
74
1
base, which could not be analyzed by H NMR
2 3
Cs CO
[
a]
analysis. Trace amount of the desired product 4aa
was also afforded without employing a base and the
rest of the mixture solution were mainly
2-phenyl-1H-indol-3-yl 4-methylbenzenesulfonate E
and 2-phenyl-3H-indol-3-one G checked by TLC and
Reaction conditions: 1a (0.1 mmol), Pd(OAc)
a (3 equiv), 1,4-dioxane (1 mL), base (3.5 equiv), and 3a
2
(5 mol%),
2
(
1.5 equiv).
[
[
[
b]
c]
d]
Isolated yield.
Without base.
1
1
H NMR analysis (entry 8). A relatively low product
Checked using TLC and H NMR measurements from
the crude mixture.
yield of 74% was also obtained when the amount of
[
e]
2
.5 equiv of Cs
2
CO
3
was used.
Cs
2
CO
3
was decreased to 2.5 equiv (entry 9).
To define the scope of the pd-catalyzed one-pot
At the outset of this study, we chose 1-azido-2-
insertion reactions, we applied this method to a series
of 2-alkynyl arylazides 1 and aryl ketones with
electron-withdrawing group at α-position 3 to define
the scope of this one-pot protocol. The results are
shown in Tables 2-3.
As shown in Table 2, we first examine the one-pot
insertion reaction of 2-alkynyl arylazides bearing
electron-withdrawing and electron-donating groups
(
1
phenylethynyl)benzene
,3-diphenylpropane-1,3-dione
1a
3a
and
model
as
substrates to explore the optimal conditions (Table 1).
This revealed that treating a solution of reaction
containing 1a (1 equiv) and TsOH (3 equiv) with 5
mol % of Pd(OAc)
2
at room temperature for 10 min
(3.5 equiv) and 3a (1.5 equiv)
and then added Cs CO
2
3
1a-r with 1,3-diphenylpropane-1,3-dione 3a. Under
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201801162
the optimized reaction conditions, we found the
reactions of 2-alkynyl arylazides 1 bearing an
electron-withdrawing or electron-donating group on
pendant groups were also examined. Substrate with
R = cyclopropyl group provided the corresponding
2
product 4aq in 95% yield. However, only 63% yield
of product 4ar was obtained when the terminal
1
the aromatic ring (R = Me, halide and ester) with 3a
2
to proceed in excellent yields of 92-95% (4aa-4af).
substituted group R = t-Bu, which might be the steric
1
When the substituted group R = CF
3
, slightly lower
effects of substrates 1.
yields of 76-88% were obtained (4ag-4ah). On the
other hand, the yield of the product 4ai with dichloro
substituted on the aromatic ring was decreased to
To further examine the substrate scope of the
present pd-catalyzed one-pot process, the insertion
reactions of 1a with different substituted ketones 3
were also investigated (Table 3). Under the standard
reaction conditions, the desired products 4ba-4bf
were obtained in good to excellent yields of 80-95%
when β-ketoester 3b and β-ketosulfones 3c-3g were
employed.
69%.
Table 2 Substrates scope of the 2-alkynyl arylazides 1 [a][b]
Table 3 Substrates scope of the aryl ketones 3 [a][b]
[
a]
Reaction conditions: 1a (0.1 mmol), Pd(OAc)
(3 equiv), 1,4-dioxane (1 mL), Cs CO (3.5 equiv), and 3
1.5 equiv).
2
(5 mol%),
2
2
3
(
[
b]
Isolated yield.
Likewise, α-nitrocarbonyl 3h and β-ketophosphonate
3i were also employed to repeat the reactions, which
led to lower product yields of 28-68% (4bg-4bh).
Moreover, α-bromocarbonyl 3j was also tested under
the optimized reaction conditions but was found to
give a mixture of decomposition compounds that
[
a]
Reaction conditions: 1a (0.1 mmol), Pd(OAc)
2
(5 mol%),
2
3
(3 equiv), 1,4-dioxane (1 mL), Cs
a (1.5 equiv).
2 3
CO (3.5 equiv), and
[
b]
Isolated yield.
The present method was also shown to work well for
the insertion reactions of 2-alkynyl arylazides 1
containing different substituted aryl or hetero aryl
groups on the terminal alkyne carbon, which gave the
desired products 4aj-4ap in excellent yields of
1
could not be identified by the analysis of TLC and H
NMR (4bi). Similarly, reaction of 1a with
α-cyanocarbonyl substrate 3k was found to result in
formation of Mannich-like addition adduct 5a in 95%
yield with diastereomers ratio of more than 99:1. No
insertion reaction occurred could be due to the quite
9
2-96%. In addition, substrates 1 containing aliphatic
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201801162
active carbon anion without sufficient stabilized
groups, which was generated after 1,3-acyl shift step.
In contrast, other substituted groups at the α-position
of aryl ketones 3, such as phenyl and methyl, were
also examined. Under the standard reaction
conditions, the direct addition products 5b and 5c
were furnished in 90-93% yields as a mixture of
inseparable diastereomers in ratios of 1:1 and 2:1,
respectively.
yield after simple filtration through a pad of celite.
Under basic conditions, the reaction was performed
in 1,4-dioxane at 90 ℃ by employing the key
intermediate G and 3a, which provided the desired
insertion product 4aa in 81% yield.
Based on the above results, we tentatively propose
a possible pathway in scheme 2 for converting 1a to
Scheme 3 Control experiments.
4aa, although it is highly speculative. This could
involve activation of 1a through coordination of the
Pd catalyst with triple bonds. This delivers a
pd-coordinated intermediate A which could undergo
intramolecular cyclization to give species B. The
We later conducted a crossover experiment in
order to understand the cleavage of C-C σ-bond. The
reaction was repeated by employing two different
ketones 3a and 3g, which provided non-crossover
products 4aa and 4bf in yields of 98% and 68%,
respectively. The result of crossover experiment
suggested that the C-C σ-bond cleavage was an
intramolecular process.
newly formed α-imino palladium carbene
generated by releasing the N would be attacked by
TsOH to form complex D. Subsequent
C
2
protodemetalation gave the aryl sulfonate E, which
would further be transformed to active intermediate F
after 1,3-Ts shift step.[
15]
Under basic reaction
conditions, subsequent reductive desulfonation of
α-amino sulfone F [ led to the formation of another
16]
[17]
key intermediate 2-phenyl-3H-indol-3-one G
,
which would undergo Mannich-like addition to
deliver the alkylated compound H. Intramolecular
attacking of N to C gave a four-membered ring
complex I followed by a carbon-carbon σ-bond
cleavage process to 1,3-acyl shift complex J, which
would further provide the insertion product 4aa after
protonation process.
Scheme 4 Crossover experiment.
Conclusions
In conclusion, an efficient palladium-catalyzed
one-pot insertion reaction of 3H-indol-3-ones into
carbon–carbon σ-bonds has been reported. The
desired products polyfunctional indolin-3-ones were
obtained in good to excellent yields under mild
reaction conditions.These results show that the
reaction tolerates various 2-alkynyl arylazides and
aryl ketones. Our studies show that the insertion
reaction of cyclic C-acylimines generated in situ into
carbon–carbon σ-bonds represents an attractive
alternative synthetic method to polyfunctional
indolin-3-ones. Further applications of this strategy
are currently underway and will be reported in the
future.
Scheme 2 Proposed mechanism.
Experimental Section
To further verify the mechanism, we conducted
some control experiments and isolated successfully
the key intermediate 2-phenyl-3H-indol-3-one G.
When a solution of 1,4-dioxane containing 1a was
General Procedure for the Preparation of
Polyfunctional Indolin-3-ones 4 in One-pot Process
treated with 5 mol % of Pd(OAc)
temperature under the conditions shown in Scheme 3,
-phenyl-3H-indol-3-one G was obtained in 59%
2
at room
To a 10 ml of flask was added 2-alkynyl arylazides 1
(
0.1 mmol, 1 equiv), TsOH (3 equiv.), Pd(OAc)
2
(5 mol%),
2
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201801162
and 1,4-dioxane (1 mL). The reaction mixture was stirred
at room temperature. After the 2-alkynyl arylazides 1
disappeared monitored by TLC (about 10 min for most of
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aa in 81% yield (eluent: petrol ether: ethyl acetate = 40:1
to 8:1)
Supporting Information
Detailed descriptions of experimental procedures and
their spectroscopic data are presented in the Supporting
Information.
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CCDC for compound 4aa: 1864448 contains the
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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,
and BK20150871), and the Project Fund from the Priority
Academic Program Development of Jiangsu Higher Education
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