Palladium-Catalyzed Allylation of Cyclopropyl Acetylenes with Oxindoles to Construct 1,3-Dienes

Article abstract of DOI:10.1002/ejoc.201901536

A novel palladium-catalyzed allylic alkylation of oxindoles with cyclopropyl acetylenes has been developed. Various 1,3-diene oxindole framework bearing a quaternary stereocenter at the C3 position were synthesized straightforwardly in good to excellent yields with high regio-, and stereoselectivities. The reaction exhibited high atom economy and good functional group tolerance.

Full text of DOI:10.1002/ejoc.201901536

A Journal of
Accepted Article
Title: Palladium-Catalyzed Allylation of Cyclopropyl Acetylenes with
Oxindoles to Construct 1,3-Dienes
Authors: Chuan-Jun Lu, Xin Yu, Y-Ting Chen, Qing-Bao Song, Zhen-
Ping Yang, and Hong Wang
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201901536
Link to VoR: http://dx.doi.org/10.1002/ejoc.201901536
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10.1002/ejoc.201901536
European Journal of Organic Chemistry
FULL PAPER
Allylic Alkylation
Palladium-Catalyzed Allylation of Cyclopropyl Acetylenes with Oxindoles to
Construct 1,3-Dienes
Chuan-Jun Lu,*[a] Xin Yu,[a] Yu-Ting Chen,[a] Qing-Bao Song,*[a] Zhen-Ping Yang,[a] Hong Wang[a]
Abstract: A novel palladium-catalyzed allylic alkylation of oxindoles
with cyclopropyl acetylenes has been developed. Various 1,3-diene
oxindole framework bearing a quaternary stereocenter at the C3
position were synthesized straightforwardly in good to excellent yields
with high regio-, and stereoselectivities. The reaction exhibited high
atom economy and good functional group tolerance.
to the possibility that cyclopropyl phenyl acetylene could provide
a general system for building 1,3-dienes by the cleavage of C-C
bond.12,13 As part of our ongoing studies of allylation reaction of
alkynes,14 we report herein a palladium catalyzed allylic alkylation
of oxindole with cyclopropyl acetylene for the synthesis of 1,3-
diene oxindole framework bearing a quaternary stereocenter at
the C3 position15 with high regio-, and stereoselectivities in
excellent atom economy (Scheme 1, c)).
Introduction
Transition-metal-catalyzed allylic alkylation provides a powerful
approach to construct C-C and C-heteroatom bonds in organic
synthesis, which has allowed chemists to construct complex
molecular frameworks of natural products and medicinal
chemistry.1 The treatment of allyl alcohol derivatives, such as
acetates, carbonates, and halides, with nucleophiles in the
presence of transition metals is a reliable approach for the
synthesis of this class of compounds.2 However, some
unavoidable limitations of the method still exist with respect to the
formation of stoichiometric valueless byproducts and
prefunctionalization of substrates. Recently, the transition-metal-
catalyzed redox-neutral allylic alkylation of internal or terminal
alkynes in the presence of metal with acid catalyst as the co-
catalyst has been described with excellent atom efficiency without
any waste formation.3 Several C-C and C-heteroatom bonds
formation with these alkynes have been subsequently reported to
establish linear or branched allylated compounds (Scheme 1, a)).4
Conjugated 1,3-dienes are attractive building blocks for
medicinal and natural product synthesis and also participate in an
increasing variety of useful transformations, including
hydrofunctionalizations, ring-forming reactions, and polymeriza-
tions.5 Although a number of synthetic methods, including cross-
coupling,6 eneyne metathesis,7 C-H vinylation,8 and allylic
substitution9 and others,10 to build 1,3-dienes are currently
available, those atom economy method to access 1,3-dienes
remain only a few and still highly attractive. Recently, Yao and Lin
have developed an elegant palladium-catalyzed redox-neutral
allylic alkylation with unactivated skipped enynes to access a wide
array of 1,3-dienes with high atom economy and good functional
group tolerance (Scheme 1, b)).11 Mechanistically, we were drawn
Scheme 1. Redox-neutral allylic alkylation reaction of alkynes.
Results and Discussion
To identify the optimized reaction conditions, we chose N-
methyl-3-phenyloxindole 1a and cyclopropyl phenyl acetylene 2a
as our pilot substrate. Fortunately, the reaction of 1a with 2a in
the presence of 5 mol% of Pd(PPh3)4 and 1.0 equiv of 3-
chlorobenzoic acid in 1.0 mL of anhydrous 1,4-dioxane at 100 ℃
under argon for 12 h, afforded the desired product 3aa and 3aa’
in 87% total yield with good regio-, and stereoselectivity (E/Z =
9.1:1) (Table 1, entry 1). Sreening of palladium catalysts
exhibited that the desired product could be obtained in good
yields (82-95%), when Pd(OAc)2, Pd(dba)2 or Pd2(dba)3 was
used as catalyst (Table 1, entries 2-4). While no product was
obtained with Pd(PPh3)2Cl2 as catalyst (Table 1, entry 5). Ligand
examination showed that PPh3 is the best ligand for this
transformation, dppb, Xantphos and BINAP exhibited sharply
reduced yield of 3aa (Table 1, entries 6-8). Further screening of
[a]
Dr. C.-J. Lu, X. Yu, Y.-T. Chen, Prof. Dr. Q.-B. Song, Z.-P. Yang, Dr.
H. Wang
College of Chemical Engineering, Zhejiang University of Technology,
Chaowang Road 18#, Hangzhou, ZheJiang 310014, China;
E-mail: luchuanjun@zjut.edu.cn
qbsong@zjut.edu.cn
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201901536R1.
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10.1002/ejoc.201901536
European Journal of Organic Chemistry
FULL PAPER
acids suggested that 3-chlorobenzoic acids remained the best
result. Other acids such as 3-F-C6H4CO2H, C6H4CO2H, CH3CO2H
and TsOH showed inferior performance with respect to both
product yields and ratios of 3aa/3aa’ (Table 1, entries 9-12).
Moreover, both the yield and ratio can be slightly enhanced by
lowering the concentration of reaction (Table 1, entry 13). In
addition, there was subtle influence on outcome when catalytic
amount of 3-Cl-C6H4CO2H was used as the co-catalyst (Table 1,
entry 15). Above all, the model reaction conditions was chosen to
be 1a (0.2 mmol), 2a (0.24 mmol), 3-Cl-C6H4CO2H (10 mol %), 5
mol% Pd(dba)2, 12 mol% PPh3 in 2.0 mL dioxane at 100 oC for 12
h (Table 1, entry 15).
Table 2. Scope of cyclopropyl acetylene substrates 2[a],[b]
Ph
Ph
Ph
Ph
OMe
O
O
O
Me
N
N
N
Me
Me
Me
3aa
3ac
3ab
69% (E/Z = 12.0:1)
98% (E/Z = 12.5:1)
80% (E/Z = 10.3:1)
Ph
Ph
Ph
Me
Table 1. Optimization of reaction conditions[a]
O
O
N
F
O
Cl
N
N
Me
Me
Me
3af
3ae
89% (E/Z = 12.5:1)
3ad
77% (E/Z = 9.7:1)
95% (E/Z = 12.2:1)
Ph
Ph
F
Ph
Cl
CF3
O
N
O
O
N
N
3aa:
Me
Me
Entry
Catalyst
Ligand
Additive
Yield[b]
Me
3aa’[c]
9.1:1
10:1
10:1
11.2:1
/
3ah
3ai
3ag
1
2
Pd(PPh3)4
Pd(OAc)2
Pd2(dba)3
Pd(dba)2
/
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-F-C6H4CO2H
CH3CO2H
87
86
95
93
0
88% (E/Z = 12.5:1)
97% (E/Z = 12.7:1)
85% (E/Z = 10.0:1)
PPh3
PPh3
PPh3
PPh3
3
Ph
Ph
Ph
4
Me
O
F
O
O
N
N
Pd(PPh3)2Cl2
5
N
Me
Me
3ak
85% (E/Z = 11.5:1)
Me
6
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
dppb
45
35
37
85
78
76
3
7.7:1
9.1:1
6.7:1
8.4:1
8.4:1
9.1:1
/
3aj
3al
83% (E/Z = 10.0:1)
77% (E/Z = 16:1)
Xantphos
7
8
BINAP
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
Me
9
Ph
Ph
Me
10
11
12
13[d]
14[e]
15[d,f]
O
N
Me
F
O
C6H4CO2H
N
Me
Me
TsOH
3am
3an
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
3-Cl-C6H4CO2H
98
88
97
12.5:1
11.2:1
12.5:1
71% (E/Z = 7.6:1)
87% (E/Z = 11.6:1)
[a]
Reaction conditions: 1a (0.2 mmol), 2 (0.24 mmol), 3-Cl-C6H4CO2H (10
mol %), 5 mol% Pd(dba)2 catalyst, 12 mol% PPh3 in 2.0 mL dioxane at 100 o
C
[a]
Reaction conditions: 1a (0.2 mmol), 2a (0.24 mmol), 3-Cl-C6H4CO2H (1.0
for 12 h. [b] Isolated yields and the yields are reported as a mixture of E and Z
equiv.), 5 mol% Pd catalyst, 12 mol% ligand in 1.0 mL dioxane at 100 oC for 12
h. [b] Isolated yields and the yields are reported as a mixture of 3aa (E) and 3aa’
(Z) isomers. [c] The ratios were determined by 1H NMR. [d] In 2.0 mL dioxane. [e]
In 0.5 mL dioxane. [f] 10 mol % 3-Cl-C6H4CO2H was used.
isomers at 2-position.
Next, we turned our attention to explore the generality of the
oxindoles under the standard conditions and the results are
summarized in Table 3. Initially, N-substitution of the oxindole
nitrogen was investigated (Table 3, 3ao-3ap). Other than the
methyl group, benzyl substituent was also well accommodated.
Interestingly, non-protected free NH on the oxindole ring was also
tolerated (3ap), which allows for facile potential N-substitutions on
demand. The substituted group on the phenyl ring of oxindole (R)
was then examined (Table 3). Differently substituted reacted well
With the optimized conditions in hand, we then explored the
substrate scope of the alkynes and the results are summarized in
Table 2. Different aromatic-substituted cyclopropylethynyl were
subjected to the reaction to afford the 1,3-dienes products. The
reactions worked well over different aryl substituents bearing both
electron-donating groups (−OMe, −Me) and electron-withdrawing
groups (−CF3, −F, −Cl) on the phenyl group, delivering the
corresponding linear allylic products in high regio- and
stereoselectivities (3aa-3ak). Generally, the alkynes having the
electron-withdrawing groups, gave better yields than the ones
with electron-donating groups (3ab vs 3ai, 3ad vs 3ac). Ortho-
substituted alkynes also showed good reactivity, giving 3aj, 3ak
and 3an in 83-87% yield. Moreover, when the phenyl group was
changed to 1-naphthalenylgroups, the reaction proceeded
smoothly to deliver 3al in 77% yield with improved E/Z selectivity.
to produce
3 in high yields with excellent regio-, and
stereoselectivities. It was found that oxindoles possessing
electron-rich groups gave better E/Z stereoselectivities than that
possessing electron-deficient groups on the phenyl ring (Table 3,
3aq-3at). Substitution at the C3-position of the oxindole frame
was then evaluated. It was found that the 3-phenyl ring bearing
both electron-withdrawing halogen atoms and electron-donating
methyl and methoxy substituents were well accommodated,
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10.1002/ejoc.201901536
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[a] Reaction conditions: 1 (0.2 mmol), 2a (0.24 mmol), 3-Cl-C6H4CO2H (10 mol %),
5 mol% Pd(dba)2 catalyst, 12 mol% ligand in 2.0 mL dioxane at 100 oC for 12 h.
[b] Isolated yields and the yields are reported as a mixture of E and Z isomers at
2-position. [c] Only one isomer was detected.
affording the desired 1,3-dienes products at good yields and
stereoselectivities. Moreover, for oxindole with an alkyl
substituent at the C3-position, the allylic alkylation proceeded
regioselectively at the terminal position to produce 3az and 3ba
in moderate yields. The final investigation of the reaction was
focused on varying the substituents on the phenyl ring of 2-
oxindoles. The outcome of the reaction depends much on the
nature of the substituents. For example, oxindole substrates with
methoxy at the C-6 position and fluoro at the C-7 position led to
corresponding products 3a1 and 3a2 in 95% and 92% yields,
respectively. However, when 4-Cl substituted oxindole was used,
no desired product 3a3 could be detected probably due to the
steric hindrance at the C-4 position.
Besides the oxindole, we also tried two other ketone and ester
carbon nucleophiles (Scheme 2). Under the optimized conditions,
These two kind of nucleophiles 4 and 5 exhibited marvellous
reactivities to react with cyclopropyl phenyl acetylene 2a. The
desired products 3bb and 3bc could be obtained in 96% and 95%
yields with good stereoselectivities.
Pd(dba)2 (5 mol%)
Ph
Ph
PPh3 (12 mol%)
3-Cl-C6H4COOH
Ph
Table 3. Scope of oxindole substrates 1 [a],[b]
Ph
+
NC
CO2Et
(1)
NC CO2Et
Ar, dioxane, 100oC
3bb
, 96% E/Z = 10.0:1
4
2a
5
3
Pd(dba)2 (5 mol%)
Ph
R1
1
R1
PPh3 (12 mol%)
3-Cl-C6H4COOH
4
2
O
Pd(dba)2 (5 mol%)
PPh3 (12 mol%)
3-Cl-C6H4COOH
O
Ar
Ar
Ph
(2)
, 95% E/Z = 5.3:1
Ph
Ph
+
Ar, dioxane, 100 o
C
Me
Me
N
N
R2
O
O
R2
Ph
+
O
O
Ar, dioxane, 100oC
1
2a
3
3bc
5
2a
Ph
Scheme 2. Scope of other carbon nucleophiles.
Ph
Ph
Ph
Ph
Me
O
O
O
N
N
N
H
Bn
To test the practicability of the present method, a scaled-up
reaction was conducted (Scheme 3, (1)). In the presence of 5
mol % of Pd(dba)2 and 10 mol% of 3-chlorobenzoic acid as
additive in anhydrous 1,4-dioxane at 100 oC under argon for 12 h,
3aa could also be isolated in 96% yield on a 5.0 mmol scale.
Subsequently, synthetic transformations of the product were
conducted. As shown in Scheme 2, Pd/C-catalyzed
hydrogenation of 3aa in ethanol readily afforded oxindole 5 in 89%
yield (Scheme 3, (2)). A Diels-Alder reaction of 3aa with N-
benzylmaleimide produced polycyclic compounds 6a and 6b in
68% combined yield (Scheme 3, (3)).
Me
3ao
3aq
3ap
92% (E/Z = 14.3:1)
86% (E/Z = 11.1:1)
94% (E/Z = 16.7:1)
Ph
Ph
Ph
Ph
Ph
Ph
F
Cl
MeO
O
N
Me
O
N
Me
O
N
Me
3ar
3as
3at
87% (E/Z = 9.4:1)
96% (E/Z = 8.3:1)
90% (E/Z=12.1:1)
Me
MeO
F
Ph
Ph
Ph
O
N
O
O
N
N
Me
Me
Me
3au
3av
83% (E/Z = 10.3:1)
3aw
87% (E/Z = 10.1:1)
85% (E/Z = 14.3:1)
Cl
F3C
R
Ph
Ph
Ph
O
O
N
O
N
N
Me
Me
Me
[c]
[c]
3ax
3ay
3az
3ba
R = H,
R = Me,
42%
35%
74% (E/Z = 9.8:1)
60% (E/Z = 9.1:1)
Ph
Ph
Ph
Cl
Ph
Ph
Ph
O
N
Me
F
O
O
N
Me
N
Me
MeO
3a1
95% (E/Z = 16.7:1)
3a2
(E/Z = 8:1)
3a3
%
0
%
92
Scheme 3. Scaled-up reaction and synthetic transformations of 3aa
Moreover, preliminary result shown in Scheme 4 indicated
that this reaction was amendable to enantioselective catalysis
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10.1002/ejoc.201901536
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Conclusions
albeit the ee value was unsatisfied at this stage. Under the
catalysis of a chiral Palladium/(S)-BINAP complex, the
reaction of methyl-3-phenyloxindole 1a and cyclopropyl
phenyl acetylene 2a proceeded smoothly to afford the
oxindole framework 3aa in 40% yield (12.5:1 E/Z selectivity)
and with 28% ee for the major product. (Scheme 4)
In conclusion, we have developed a palladium-catalyzed allylic
alkylation of oxindoles with cyclopropyl acetylene for the
synthesis of 1,3-diene oxindole framework bearing a quaternary
stereocenter at the C3 position with high regio-, and
stereoselectivities under mild conditions. This methodology was
found to be advantageous in terms of substrate scope and
functional group tolerance and shows excellent atom economy.
Pd(dba)2 (5 mol%)
Ph
Ph
Ph
s-BINAP (6 mol%)
3-Cl-C6H4COOH
Ar, dioxane, 100 o
O
O
Ph
+
C
N
N
Me
Experimental Section
Me
40%, 7:1 E/Z
1a
(0.2mmol)
2a
28% ee for the major
3aa
Materials and methods
Scheme 4. Preliminary result for the enantioselective reaction
Reactions and manipulations involving organometallic or moisture
sensitive compounds were performed under dry nitrogen and using
glassware heated in an oven for 2 h prior to use. 1H and 13C spectra were
recorded on a Bruker AVANCE III 500 MHz instrument using CDCl3 as the
solvent with TMS as the internal standard. Anhydrous dioxane, THF, and
toluene were freshly distilled over Na and stored under nitrogen.
Commercial reagents were used as received without further purification
unless otherwise noted. Melting points (m.p.) were recorded using an
SGW Melting Point X-4 instrument. IR was recorded using a Thermo
Nicolet 6700 instrument. HRMS were recorded using an Agilent 6210 TOF
LC/MS mass spectrometer. Column chromatography was carried out
using a silica gel (200-300 mesh).
In order to explore the mechanism of this reaction, we
synthesized penta-1,2,4-trien-1-ylbenzene 7 and used it to react
with oxindole 1a (Scheme 5, (1)). Under the optimized reaction
conditions, the reaction proceeded smoothly to afford allylation
product 3aa in 70% yield and 12.5:1 E/Z selectivity, suggesting
that the alkyne 2 is capable of undergoing C-C activation to allene
through a β-C-elimination.
The reasonable mechanism for the direct allylic alkylation of the
oxindoles can be envisioned (Scheme 5, (2)). The palladium (0)
complex is able to undergo oxidative addition to acid to generate
a hydridopalladium complex, which then reacts with alkynes
forming vinyl palladium intermediate B. The resulting
vinylpalladium species would produce active alkylpalladium(II)
intermediate C via β-C elimination. β-Hydrogen elimination of
alkylpalladium(II) species C produces the vinyl allene D. Next,
hydropalladation of vinyl allene intermediate D delivers the π-
allylpalladium species E (Cycle II), which delivers intermediate F
through π−σ−π isomerization. Finally, the palladium-allyl species
F is captured by the oxindole nucleophile 1 to afford the desired
product 3 and regenerated intermediate A to achieve the catalytic
cycle.
General procedure for the synthesis of alkynes16
CuI (77 mg, 0.4 mmol, 4.0 mol%), (PPh3)2PdCl2 (141 mg, 0.2 mmol, 2.0
mol%), PPh3 (105 mg, 0.4 mmol, 4.0 mol%), and NEt3 (30 mL) were placed
in a round-bottomed flask equipped with a magnetic stirring bar. After
addition of the aryl halide (10.0 mmol), the mixture was stirred at 25 °C for
30 min, and cyclopropylacetylene (661 mg, 10.0 mmol) was then added.
The reaction mixture was stirred at the same temperature for 16 h,
saturated NH4Cl solution was added. The mixture was extracted with ethyl
acetate and the combined organic layers were dried with MgSO4 and
concentrated under vacuum. The residue was purified by flash
chromatography (SiO2) to get the alkyne products.
Pd(dba)2 (5 mol%)
Ph
Ph
PPh3 (12 mol%)
3-Cl-C6H4COOH
Ph

General procedure for the synthesis of substituted oxindoles17
Substituted isatins (10.0 mmol) were dissolved in anhydrous DMF (15 mL),
and the resultant solution was cooled to 0 oC. Sodium hydride (60%
dispersion in oil, 0.95 g, 12.0 mmol) was added in one portion and stirred
for 5 min. Alkyl halide (15.0 mmol) was added and the reaction was stirred
at 0 oC for 30 min. The reaction mixture was then poured into saturated
aqueous NH4Cl and extracted with ethyl acetate. The combined organic
layers were washed with water and brine, dried over Na2SO4, filtered, and
concentrated to give the crude N-substituted isatins.
O
O
+
Ar, dioxane, 100 o
C
(1)
N
Me
1a
N
Me
70%, 12.5:1 E/Z
7
3aa
(0.2 mmol)
1,3-dienes
Oxindole
1
Ar
3
2
H
Pd-OOCAr'
Pd(0)+Ar'CO2H
Pd-OOCAr'
Ar
The crude N-substituted isatins (10.0 mmol) were dissolved in anhydrous
THF (15 mL) and cooled to 0 oC, followed by dropwise addition of a 2.0 M
of Grignard reagent in THF (12.0 mL, 24.0 mmol). Then the reaction was
stirred under argon atmosphere at room temperature for 30 min with the
consumption of the starting material. The reaction mixture was poured into
saturated aqueous NH4Cl, and extracted with ethyl acetate. The combined
organic layers were washed with brine, dried over anhydrous Na2SO4,
filtered, and concentrated to give the crude alcohol.
B
Cycle II
Cycle I
Ar
F
(2)
H-Pd-OOCAr'
A

Pd-OOCAr'

Ar
Pd-OOCAr'
C
Ar
E
Ar
D
Scheme 5. Control reaction and proposed mechanism for the tandem allylic
The crude alcohol (1.2 g, 5.0 mmol) was dissolved in 30 ml of glacial acetic
acid and SnCl2•2 H2O (10.0 mmol) was added. The reaction mixture was
alkylation reaction
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10.1002/ejoc.201901536
European Journal of Organic Chemistry
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stirred at 80 oC for 4 h at which point TLC analysis indicated consumption
of the starting material. Then the reaction solution was cooled to room
temperature, concentrated in vacuo, and diluted with ethyl acetate. The
solution was then washed with water and brine. The organic layer was
dried with anhydrous Na2SO4, filtered, and concentrated in vacuo. The
residue was purified by flash column chromatography with EA/PE to afford
the oxindole products.
126.94, 126.62, 125.25, 122.48, 114.05, 108.28, 56.73, 55.28, 41.20,
26.40. HRMS (ESI) m/z calculated for [C27H25NO2+H]+ 396.1958, found
396.1961.
1-Methyl-3-phenyl-3-((2E,4E)-5-(m-tolyl)penta-2,4-dien-1-yl)indolin-2-
one (3ac). Total isolated yield: 80%, 2E/2Z = 10.3:1. Purified 3ac, yellow
oil. 1H NMR (500 MHz, CDCl3) δ 7.45-7.42 (m, 2H), 7.38-7.33 (m, 3H),
7.32-7.28 (m, 2H), 7.19-7.11 (m, 4H), 7.03 (d, J = 7.0 Hz, 1H), 6.92 (d, J =
7.5 Hz, 1H), 6.56 (dd, J = 15.5, 10.5 Hz, 1H), 6.38 (d, J = 16.0 Hz, 1H),
6.21 (dd, J = 15.0, 10.5 Hz, 1H), 5.44-5.38 (m, 1H), 3.22 (s, 3H), 3.21-3.16
(m, 1H), 3.08 (dd, J = 13.5, 8.5 Hz, 1H), 2.33 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 177.92, 143.81, 139.35, 138.04, 137.18, 134.70, 131.62, 131.59,
128.55, 128.42, 128.38, 128.26, 128.18, 127.98, 127.36, 127.10, 126.85,
125.23, 123.42, 122.47, 108.27, 56.67, 41.15, 26.40, 21.35. HRMS (ESI)
m/z calculated for [C27H25NO+H]+ 380.2009, found 380.2012.
General procedure for the synthesis of 3-benzyl-1-methylindolin-2-
one17
Benzaldehyde (1.7 mL, 17 mmol) and piperidine (0.3 mL, 30 mmol) were
added to a suspension of oxindole (2.0 g, 15 mmol) in ethanol (2 mL). The
resulting mixture was heated to 150 oC. The solution was then allowed to
cool to 0 oC. The precipitate was filtered, washed with small amount of
ether, and dried to give 3-benzylidene-oxindole as a yellow solid, which
was used without further purification.
3-((2E,4E)-5-(3-Fluorophenyl)penta-2,4-dien-1-yl)-1-methyl-3-
phenylindolin-2-one (3ad). Total isolated yield: 95%, 2E/2Z = 12.2:1.
Purified 3ad, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.46-7.42 (m, 2H),
7.39-7.33 (m, 3H), 7.32-7.28 (m, 2H), 7.24 (td, J = 8.0, 6.0 Hz, 1H), 7.16
(td, J = 7.5, 1.0 Hz, 1H), 7.092-7.071 (m, 1H), 7.03 (dt, J = 10.5, 2.0 Hz,
1H), 6.94-6.87 (m, 2H), 6.55 (dd, J = 16.0, 10.5 Hz, 1H), 6.37 (d, J = 15.5
Hz, 1H), 6.21 (dd, J = 15.0, 10.5 Hz, 1H), 5.49-5.43 (m, 1H), 3.23 (s, 3H),
3.22-3.17 (m, 1H), 3.13-3.07 (m, 1H). 13C NMR (125 MHz, CDCl3) δ 177.85,
163.08 (d, 1J = 245.1 Hz), 143.80, 139.67 (d, 3J = 7.6 Hz), 139.31, 134.19,
131.56, 130.22(d, 4J = 2.8 Hz), 129.91(d, 3J = 8.5 Hz), 129.82, 129.39,
The crude benzylidene oxindole was dissolved in DMF (30 mL) and cooled
to 0 oC. NaH (720 mg, 18 mmol, 60% in mineral oil) was added and the
resulting solution was stirred for 15 min before methyl iodide (2.9 g,
20mmol) was added dropwise. The reaction was allowed to warm to room
temperature and stirred for another 2 h. Water was then added to quench
the reaction. The mixture was extracted with EtOAc and the combined
organic layer was washed with water and brine, and dried over MgSO4,
and concentrated to about 10 mL in volumn. The solution was filtered
through a pad of silica to afford the oxindole.
4
The crude oxindole was dissolved in EtOAc and Pd/C (10%) was added.
The suspension was stirred in the presence of a H2 balloon for 10 h. The
reaction was then filtered through a pad of wet celite and the filtrate was
concentrated to give a slightly yellow oil. After purification by flash column
chromatography of the crude oil, 3-benzyl-1-methylindolin-2-one was
achieved as a white solid.
128.57, 128.32, 127.39, 127.07, 125.18, 122.50, 122.15(d, J = 2.8 Hz),
114.07(d, 2J = 21.4 Hz), 112.43(d, 2J = 21.8 Hz), 108.30, 56.60, 41.14,
26.39. HRMS (ESI) m/z calculated for [C26H22FNO+Na]+ 406.1567, found
406.1571.
3-((2E,4E)-5-(3-Chlorophenyl)penta-2,4-dien-1-yl)-1-methyl-3-
phenylindolin-2-one (3ae). Total isolated yield: 89%, 2E/2Z = 12.5:1.
Purified 3ae, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.44-7.41 (m, 2H),
7.38-7.28 (m, 6H), 7.21-7.13 (m, 4H), 6.92 (d, J = 8.0 Hz, 1H), 6.54 (dd, J
= 15.5, 10.5 Hz, 1H), 6.33 (d, J = 16.0 Hz, 1H), 6.19 (dd, J = 15.0, 10.5 Hz,
1H), 5.48-5.42 (m, 1H), 3.22 (s, 3H), 3.20-3.16 (m, 1H), 3.11-3.07 (m, 1H).
13C NMR (125 MHz, CDCl3) δ 177.87, 143.81, 139.30, 139.20, 134.51,
134.19, 131.57, 129.94, 129.72, 129.51, 128.58, 128.34, 127.41, 127.20,
127.08, 125.94, 125.19, 124.48, 122.53, 108.32, 56.62, 41.14, 26.42.
HRMS (ESI) m/z calculated for [C26H22ClNO+Na]+ 422.1284, found
422.1286.
General procedure for the palladium-catalyzed allylation of oxindole
with cyclopropyl acetylene derivatives
To a mixture of oxindole 1 (0.20 mmol, 1.0 equiv), cyclopropyl acetylene
derivatives 2 (0.24 mmol, 1.2 equiv), Pd(dba)2 (0.01 mmol, 5 mol%), PPh3
(0.024 mmol, 12 mol%) and m-chlorobenzoic acid (0.02 mmol, 10 mol%)
in a sealed tube (10 mL) was added 2.0 mL dry dioxane. The resulting
mixture was then stirred at 100 oC under argon atmosphere for 12 h. The
solvent was then removed under vacuum and the residue was purified with
chromatography on silica (PE/EA
stereoisomers of compound 3 and the E/Z ratio was determined by 1H
NMR. The mixture of stereoisomers was separated by second
= 20:1) to afford a mixture of
1-Methyl-3-phenyl-3-((2E,4E)-5-(p-tolyl)penta-2,4-dien-1-yl)indolin-2-
one (3af). Total isolated yield: 77%, 2E/2Z = 9.7:1. Purified 3af, Purified
3af, yellow solid, m. p. 84–86 oC; 1H NMR (500 MHz, CDCl3) δ 7.46-7.42
(m, 2H), 7.38-7.33 (m, 3H), 7.31-7.28 (m, 2H), 7.23 (d, J = 8.0 Hz, 2H),
7.15 (td, J = 7.5, 1.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 2H), 6.92 (d, J = 7.5 Hz,
1H), 6.52 (dd, J = 15.5, 10.5 Hz, 1H), 6.39 (d, J = 15.5 Hz, 1H), 6.20 (dd,
J = 15.0, 10.5 Hz, 1H), 5.42-5.37 (m, 1H), 3.24-3.17( m, 1H), 3.22 (s, 3H),
3.11-3.07 (m, 1H). 13C NMR (125 MHz, CDCl3) δ 177.93, 143.83, 139.40,
137.21, 134.77, 134.50, 131.67, 131.45, 129.25, 128.54, 128.25, 127.64,
127.55, 127.35, 127.12, 126.12, 125.24, 122.46, 108.26, 56.69, 41.18,
26.39, 21.18. HRMS (ESI) m/z calculated for [C27H25NO+H]+ 380.2009,
found 380.2014.
a
chromatography on silica (PE/EA = 30:1) to afford the major stereoisomer.
1-Methyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-yl)indolin-2-
one (3aa). Total isolated yield: 98%, 2E/2Z = 12.5:1. Purified 3aa, pale
o
yellow solid, m. p. 108–110 C . 1H NMR (500 MHz, CDCl3) δ 7.45-7.41
(m, 2H), 7.38-7.32 (m, 5H), 7.31-7.27 (m, 4H), 7.23-7.18 (m, 1H), 7.15 (td,
J = 7.6, 1.0 Hz, 1H), 6.92 (d, J = 7.8 Hz, 1H), 6.56 (dd, J = 15.5, 10.5 Hz,
1H), 6.41 (d, J = 15.5 Hz, 1H), 6.21 (dd, J = 15.0, 10.5 Hz, 1H), 5.45-5.38
(m, 1H), 3.22 (s, 3H), 3.21-3.19 (m, 1H), 3.08 (dd, J = 14.0, 8.5 Hz, 1H).
HRMS (ESI) m/z calculated for [C26H23NO+H]+ 366.1852, found 366.1858.
3-((2E,4E)-5-(3-Methoxyphenyl)penta-2,4-dien-1-yl)-1-methyl-3-
phenylindolin-2-one (3ab). Total isolated yield: 69%, 2E/2Z = 12.0:1.
Purified 3ab, yellow solid, m. p. 100–102 oC. 1H NMR (500 MHz,CDCl3) δ
7.47-7.42 (m, 2H), 7.38-7.33 (m,3H), 7.32-7.26 (m,4H), 7.15 (td, J = 7.5,
1.0 Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 6.86- 6.82 (m, 2H), 6.45 (dd, J = 15.0,
10.0 Hz, 1H), 6.37 (d, J = 15.5 Hz, 1H), 6.20 (dd, J = 15.0, 10.0 Hz, 1H),
5.41-5.35 (m, 1H), 3.80 (s, 3H), 3.23-3.17 (m, 1H), 3.22(s, 3H), 3.10-3.06
(m, 1H). 13C NMR (125 MHz, CDCl3) δ 177.98, 159.13, 143.84, 139.44,
134.84, 131.72, 131.06, 130.12, 128.56, 128.26, 127.42, 127.36, 127.14,
3-((2E,4E)-5-(4-Fluorophenyl)penta-2,4-dien-1-yl)-1-methyl-3-
phenylindolin-2-one (3ag). Total isolated yield: 85%, 2E/2Z = 10.0:1.
Purified 3ag, yellow solid, m. p. 94–96 oC. 1H NMR (500 MHz, CDCl3) δ
7.45-7.41 (m, 2H), 7.41-7.38 (m, 1H), 7.38-7.32 (m, 3H), 7.31-7.28 (m, 2H),
7.19-7.12 (m, 2H), 7.08-6.98 (m, 2H), 6.92 (d, J = 8.0 Hz, 1H), 6.63 (dd, J
= 16.0, 10.0 Hz, 1H), 6.55 (d, J = 15.5 Hz, 1H), 6.22 (dd, J = 15.0, 10.0 Hz,
1H), 5.50-5.43 (m, 1H), 3.22 (s, 3H), 3.22-3.17 (m, 1H), 3.11-3.06 (m, 1H).
13C NMR (125 MHz, CDCl3) δ 177.89, 160.19 (d, 1J = 247.5 Hz), 143.80,
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201901536
European Journal of Organic Chemistry
FULL PAPER
3
139.31, 134.82, 131.59, 130.89 (d, J = 5.0 Hz), 129.15, 128.57, 128.45
3H), 3.23-3.21 (m, 1H), 3.18-3.12 (m, 1H). 13C NMR (125 MHz, CDCl3) δ
177.93, 143.83, 139.37, 134.88, 134.54, 133.71, 131.64, 131.31, 131.06,
128.58, 128.56, 128.53, 128.30, 128.11, 127.77, 127.39, 127.11, 125.97,
125.71, 125.50, 125.21, 123.53, 123.01, 122.52, 108.29, 56.68, 41.18,
26.41. HRMS (ESI) m/z calculated for [C30H25NO+Na]+ 438.1824, found
438.1821.
(d, 2J = 8.8 Hz), 128.31, 127.39, 127.10, 126.94 (d, 4J = 3.8 Hz), 125.23,
2
5
125.11 (d, J = 11.8 Hz), 124.02 (d, J = 3.8 Hz), 123.76 (d,6J =2.5 Hz),
122.52, 115.69 (d, 2J = 22.5 Hz), 108.30, 56.60, 41.14, 26.42. HRMS (ESI)
m/z calculated for [C26H22FNO+H]+ 384.1758, found 384.1763.
3-((2E,4E)-5-(4-Chlorophenyl)penta-2,4-dien-1-yl)-1-methyl-3-
phenylindolin-2-one (3ah). Total isolated yield: 88%, 2E/2Z = 12.5:1.
Purified 3ah, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.43-7.40 (m, 2H),
7.38-7.31 (m, 3H), 7.30-7.28 (m, 2H), 7.24 (s, 4H), 7.15 (td, J = 7.5, 1.0
Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 6.52 (dd, J = 15.5, 10.5 Hz, 1H), 6.34 (d,
J = 15.5 Hz, 1H), 6.19 (dd, J = 15.0, 10.5 Hz, 1H), 5.46-5.39 (m, 1H), 3.22
(s, 3H), 3.20-3.15 (m, 1H), 3.11-3.05 (m, 1H). 13C NMR (125 MHz, CDCl3)
δ 177.88, 143.80, 139.30, 135.79, 134.33, 132.86, 131.59, 130.12, 129.15,
128.94, 128.68, 128.58, 128.32, 127.40, 127.35, 127.09, 125.20, 122.51,
108.31, 56.61, 41.14, 26.42. HRMS (ESI) m/z calculated for
[C26H22ClNO+Na]+ 422.1286, found 422.1288.
3-((2E,4E)-5-(3,5-Dimethylphenyl)penta-2,4-dien-1-yl)-1-methyl-3-
phenylindolin-2-one (3am). Total isolated yield: 71%, 2E/2Z = 7.6:1.
Purified 3am, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.46-7.42 (m, 2H),
7.38-7.32 (m, 3H), 7.3-7.28 (m, 2H), 7.15 (td, J = 7.5, 1.0 Hz, 1H), 6.97 (s,
2H), 6.92 (d, J = 8.0 Hz, 1H), 6.86 (s, 1H), 6.57-6.52 (dd, J=15.5,10.5
Hz ,1H), 6.35 (d, J = 16 Hz, 1H), 6.20 (dd, J = 15.0, 10.5 Hz, 1H), 5.43-
5.37 (m , 1H), 3.25-3.17 (m, 1H), 3.40 (s, 3H), 3.11-3.06 (m, 1H), 2.30 (s,
6H). 13C NMR (125 MHz, CDCl3) δ 177.94, 143.86, 139.41, 137.95, 137.19,
134.79, 131.71, 131.68, 129.17, 128.55, 128.26, 128.26, 127.78, 127.35,
127.12, 125.25, 124.13, 122.46, 108.25, 56.71, 41.19, 29.71, 26.39, 21.21.
HRMS (ESI) m/z calculated for [C28H27NO+Na]+ 416.1985, found
416.1985.
1-Methyl-3-phenyl-3-((2E,4E)-5-(4-(trifluoromethyl)phenyl)penta-2,4-
dien-1-yl)indolin-2-one (3ai). Total isolated yield: 97%, 2E/2Z = 12.7:1.
Purified 3ai, solid, m. p. 98–100 oC; 1H NMR (500 MHz, CDCl3) δ 7.54 (d,
J = 8.2 Hz, 2H), 7.47-7.43 (m, 2H), 7.42-7.39 (m, 2H), 7.39-7.33 (m, 3H),
7.33-7.29 (m, 2H), 7.17 (td, J = 7.5, 1.0 Hz, 1H), 6.94 (d, J = 7.5 Hz, 1H),
6.64 (dd, J = 15.5, 10.5 Hz, 1H), 6.42 (d, J = 15.5 Hz, 1H), 6.24 (dd, J =
15.0, 10.5 Hz, 1H), 5.55-5.49 (m, 1H), 3.23 (s, 3H), 3.22-3.18 (m, 1H),
3.15-3.09 (m, 1H). 13C NMR (125 MHz, CDCl3) δ 177.82, 143.80, 140.77,
3-((2E,4E)-5-(2-Fluoro-4-methylphenyl)penta-2,4-dien-1-yl)-1-methyl-
3-phenylindolin-2-one (3an). Total isolated yield: 87%, 2E/2Z = 11.6:1.
Purified 3an, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.45-7.41 (m, 2H),
7.38-7.32 (m, 3H), 7.31-7.28 (m, 2H), 7.27-7.24 (m, 1H), 7.15 (td, J = 7.5,
1.0 Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 6.85 (dd, J = 15.5, 8.0 Hz, 2H), 6.59
(dd, J = 16.0, 10.0 Hz, 1H), 6.51 (d, J = 15.5 Hz, 1H), 6.21 (dd, J = 15.0,
10.5 Hz, 1H), 5.47-5.40 (m, 1H), 3.22 (s, 3H),3.22-3.16 (m, 1H), 3.10-3.05
(m, 1H), 2.32 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 177.91, 160.07 (d, 1J
= 249.6 Hz), 143.81, 139.36, 139.14 (d, 3J = 8.1 Hz), 134.97, 131.63,
139.27, 134.12, 131.54, 130.95, 130.25, 129.87, 128.96(q,2J
=
32.3),128.59, 128.36, 127.43, 127.06, 126.25, 125.44 (q, 3J = 3.9 Hz),
125.16,124.20(q, 1J = 268.8), 122.52, 108.33, 56.57, 41.13, 26.38. HRMS
(ESI) m/z calculated for [C27H22F3NO+Na]+ 456.1543, found 456.1541.
1-Methyl-3-phenyl-3-((2E,4E)-5-(o-tolyl)penta-2,4-dien-1-yl)indolin -2-
one (3aj). Total isolated yield: 83%, 2E/2Z = 10.0:1. Purified 3aj, yellow oil.
1H NMR (500 MHz, CDCl3) δ 7.46-7.42 (m, 2H), 7.39-7.33 (m, 3H), 7.32-
7.28 (m, 2H), 7.21-7.12 (m, 4H), 7.03 (d, J = 7.0 Hz, 1H), 6.92 (d, J = 7.5
Hz, 1H), 6.56 (dd, J = 15.5, 10.5 Hz, 1H), 6.39 (d, J = 15.5 Hz, 1H), 6.21
(dd, J = 15.0, 10.5 Hz, 1H), 5.45-5.39 (m, 1H), 3.22 (s, 3H), 3.22-3.17 (m,
1H), 3.11-3.07 (m, 1H), 2.34 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 177.96,
143.87, 139.41, 138.07, 137.24, 134.75, 131.68, 131.64, 128.59, 128.47,
128.43, 128.31, 128.23, 128.02, 127.40, 127.15, 126.90, 125.27, 123.48,
122.51, 108.31, 56.72, 41.21, 26.43, 21.39. HRMS (ESI) m/z calculated
for [C27H25NO+H]+ 380.2009, found 380.2016.
3
129.91 (d, J = 5.2 Hz), 128.57, 128.48, 128.29, 127.37, 127.12, 126.69
(d, 3J = 4.3 Hz), 125.25, 124.83 (d, 4J = 2.9 Hz), 123.88 (d, 4J = 3.0 Hz),
122.50, 122.17 (d, 2J = 12.4 Hz), 116.21 (d, 2J = 22.0 Hz), 108.29, 56.62,
41.17, 26.41, 21.07. HRMS (ESI) m/z calculated for [C27H24FNO+Na]+
420.1730, found 420.1728.
1-Benzyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-yl)indolin-2-
one (3ao). Total isolated yield: 92%, 2E/2Z = 14.3:1. Purified 3ao, yellow
oil. 1H NMR (500 MHz, CDCl3) δ 7.48 (d, J = 7.5 Hz, 2H), 7.40-7.35 (m,
4H), 7.35-7.29 (m, 5H), 7.27-7.21 (m, 4H), 7.20-7.16 (m, 1H), 7.13 (t, J =
7.5 Hz, 1H), 6.79 (d, J = 7.5 Hz, 1H), 6.56 (dd, J = 15.5, 10.5 Hz, 1H), 6.46
(d, J = 15.5 Hz, 1H), 6.33 (dd, J = 15.0, 10.0 Hz, 1H), 5.43-5.37 (m, 1H),
5.15 (d, J = 16.0 Hz, 1H), 4.73 (d, J = 16.0 Hz, 1H), 3.33-3.26 (m, 1H),
3.24-3.20 (m, 1H). 13C NMR (125 MHz, CDCl3) δ 177.97, 142.98, 139.74,
137.25, 135.74, 134.89, 131.72, 131.70, 128.71, 128.62, 128.57, 128.55,
128.27, 128.20, 127.45, 127.43, 127.39, 127.36, 127.01, 126.23, 125.03,
122.57, 109.41, 56.79, 43.97, 41.16. HRMS (ESI) m/z calculated for
[C32H27NO+Na]+ 464.1980, found 464.1976.
3-((2E,4E)-5-(2-Fluorophenyl)penta-2,4-dien-1-yl)-1-methyl-3-
phenylindolin-2-one (3ak). Total isolated yield: 85%, 2E/2Z = 11.5:1.
Purified 3ak, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.46-7.42 (m, 2H),
7.41-7.33 (m, 4H), 7.32-7.28 (m, 2H), 7.19-7.14 (m, 2H), 7.08-6.99 (m, 2H),
6.92 (d, J = 8.0 Hz, 1H), 6.64 (dd, J = 16.0, 10.0 Hz, 1H), 6.55 (d, J = 16.0
Hz, 1H), 6.23 (dd, J = 15.0, 10.0 Hz, 1H), 5.50-5.44 (m, 1H), 3.23 (s, 3H),
3.22-3.18 (m, 1H), 3.12-3.07 (m, 1H). 13C NMR (125 MHz, CDCl3) δ 177.87,
160.18 (d, 1J = 249.7 Hz), 143.79, 139.31, 134.82, 131.58, 130.89 (d, 3J =
5.2 Hz), 129.15, 128.56, 128.45 (d, 3J = 8.3 Hz), 128.30, 127.38, 127.10,
126.94 (d, 3J = 3.6 Hz), 125.22, 125.10 (d, 2J = 12.1 Hz), 124.00 (d, 4J =
3.5 Hz), 123.75 (d, 4J = 3.2 Hz), 122.51, 115.68 (d, 2J = 22.2 Hz), 108.29,
56.59, 41.14, 26.40. HRMS (ESI) m/z calculated for [C26H22FNO+Na]+
406.1573, found 406.1570.
3-Phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-yl)indolin-2-one (3ap).
Total isolated yield: 94%, 2E/2Z = 16.7:1. Purified 3ap, yellow oil. 1H NMR
(500 MHz, CDCl3) δ 8.91 (s, 1H), 7.44-7.41 (m, 2H), 7.36-7.32 (m, 2H),
7.30-7.27 (m, 6H), 7.25-7.23 (m, 1H), 7.22-7.18 (m, 1H), 7.11 (td, J = 7.5,
1.5 Hz, 1H), 6.98 (d, J = 8.0 Hz, 1H), 6.55 (dd, J = 15.5, 10.5 Hz, 1H), 6.35
(d, J = 15.5 Hz, 1H), 6.22 (dd, J = 15.0, 10.5 Hz, 1H), 5.50-5.44 (m, 1H),
3.21-3.17 (m, 1H), 3.13-3.09(m, 1H). 13C NMR (125 MHz, CDCl3) δ 180.50,
140.98, 139.22, 137.23, 134.79, 132.40, 131.55, 128.62, 128.54, 128.48,
128.23, 127.97, 127.42, 127.32, 127.06, 126.23, 125.38, 122.49, 110.19,
57.21, 40.81. HRMS (ESI) m/z calculated for [C25H21NO+Na]+ 374.1512,
found 374.1510.
1-Methyl-3-((2E,4E)-5-(naphthalen-2-yl)penta-2,4-dien-1-yl)-3-
phenylindolin-2-one (3al). Total isolated yield: 77%, 2E/2Z = 16.0:1.
Purified 3al, yellow oil. 1H NMR (500 MHz, CDCl3) δ 8.14-8.10 (m, 1H),
7.85 (dd, J = 8.0, 1.5 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 7.0 Hz,
1H), 7.55-7.49 (m, 2H), 7.49-7.44 (m, 2H), 7.44-7.40 (m, 1H), 7.39-7.29
(m, 5H), 7.22-7.15 (m, 2H), 6.93 (d, J = 8.0 Hz, 1H), 6.64 (dd, J = 15.5,
10.5 Hz, 1H), 6.38 (dd, J = 15.5, 10.5 Hz, 1H), 5.51-5.45 (m, 1H), 3.24 (s,
1,5-Dimethyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3aq). Total isolated yield: 86%, 2E/2Z = 11.1:1. Purified
3aq, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.45-7.42 (m, 2H), 7.37-7.34
(m, 4H), 7.32-7.28 (m, 3H), 7.23-7.15 (m, 2H), 7.12 (d, J = 1.5 Hz, 1H),
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10.1002/ejoc.201901536
European Journal of Organic Chemistry
FULL PAPER
1
6.81 (d, J = 8.0 Hz, 1H), 6.58 (dd, J = 15.5, 10.5 Hz, 1H), 6.43 (d, J = 15.5
Hz, 1H), 6.25 (dd, J = 15.0, 10.5 Hz, 1H),5.46-5.39 (m, 1H), 3.21 (s, 3H),
3.20-3.16 (m, 1H),3.14-3.09 (m, 1H), 2.40 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 177.86, 141.44, 139.62, 137.29, 134.53, 131.96, 131.79, 131.37,
128.62, 128.52, 128.50, 128.32, 127.30, 127.28, 127.08, 126.18, 125.84,
107.95, 56.77, 40.96, 26.39, 21.25. HRMS (ESI) m/z calculated for
[C27H25NO+Na]+ 402.1824, found 402.1820.
14.0, 8.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 177.74, 162.06 (d, J =
246.7 Hz), 143.71, 137.15, 134.98 (d, 4J = 3.4 Hz), 134.77, 131.64, 131.25,
3
128.85 (d, J = 8.1 Hz), 128.51, 128.43, 128.40, 127.80, 127.38, 126.19,
125.16, 122.56, 115.31 (d, 2J = 21.3 Hz), 108.41, 56.01, 41.43, 26.39.
HRMS (ESI) m/z calculated for [C26H22FNO+Na]+ 406.1573, found
406.1570.
3-(4-Methoxyphenyl)-1-methyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
5-Fluoro-1-methyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3ar). Total isolated yield: 87%, 2E/2Z = 9.4:1. Purified
3ar, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.42-7.39 (m, 2H), 7.37-7.33
(m, 4H), 7.32-7.28 (m, 3H), 7.23-7.19 (m, 1H), 7.09-7.03 (m, 2H), 6.83 (dd,
J = 8.0, 4.0 Hz, 1H), 6.56 (dd, J = 15.5, 10.5 Hz, 1H), 6.43 (d, J = 15.5 Hz,
1H), 6.22 (dd, J = 15.0, 10.0 Hz, 1H), 5.43-5.36 (m, 1H), 3.21 (s, 3H), 3.18-
3.08 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 177.63, 159.15 (d, 1J = 240.9
yl)indolin-2-one (3aw). Total isolated yield: 85%, 2E/2Z = 14.3:1. Purified
o
3aw, yellow solid, m. p. 126–129 C. 1H NMR (500 MHz, CDCl3) δ 7.39-
7.32 (m, 5H), 7.29 (t, J = 7.3 Hz, 3H), 7.23-7.19 (m, 1H), 7.15 (t, J = 7.5
Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 6.90-6.86 (m, 2H), 6.57 (dd, J = 15.5,
10.5 Hz, 1H), 6.41 (d, J = 16.0 Hz, 1H), 6.21 (dd, J = 15.0, 10.5 Hz, 1H),
5.46-5.40 (m, 1H), 3.80 (s, 3H), 3.21 (s, 3H), 3.16 (dd, J = 14.0, 6.0 Hz,
1H), 3.04 (dd, J = 13.5, 9.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 178.14,
158.79, 143.74, 137.21, 134.50, 131.71, 131.38, 131.29, 128.55, 128.49,
128.34, 128.20, 127.30, 126.15, 125.15, 122.41, 113.88, 108.23, 55.93,
55.21, 41.22, 26.34. HRMS (ESI) m/z calculated for [C27H25NO2+Na]+
418.1772, found 418.1769.
4
3
Hz), 139.75 (d, J = 1.6 Hz), 138.77, 137.14, 134.96, 133.34 (d, J = 8.1
Hz), 131.80, 128.69, 128.54, 128.33, 127.60, 127.49, 127.43, 126.92,
126.23, 114.57 (d, 2J = 23.6 Hz), 113.17 (d, 2J = 24.8 Hz), 108.71 (d, 3J =
8.1 Hz), 57.11, 40.95, 26.54. HRMS (ESI) m/z calculated for
[C26H22FNO+H]+ 384.1758, found 384.1765.
3-(4-Chlorophenyl)-1-methyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3ax). Total isolated yield: 74%, 2E/2Z = 9.8:1. Purified
3ax, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.40-7.36 (m, 3H), 7.35-7.28
(m, 7H), 7.23-7.19 (m, 1H), 7.16 (td, J = 7.5, 1.0 Hz, 1H), 6.93 (d, J = 8.0,
1H), 6.56 (dd, J = 15.5, 10.5 Hz, 1H), 6.41 (d, J = 15.5 Hz, 1H), 6.20 (dd,
J = 15.0, 10.0 Hz, 1H), 5.42-5.36 (m, 1H), 3.22 (s, 3H), 3.14 (dd, J = 14.5,
6.5 Hz, 1H), 3.02 (dd, J = 14.0, 8.5 Hz, 1H). 13C NMR (125 MHz, CDCl3)
5-Chloro-1-methyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3as). Total isolated yield: 96%, 2E/2Z = 8.3:1. Purified
3as, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.42-7.39 (m, 2H), 7.38-7.33
(m, 5H), 7.33-7.28 (m, 4H), 7.24-7.19 (m, 1H), 6.83 (d, J = 8.0 Hz, 1H),
6.57 (dd, J = 16.0, 10.0 Hz, 1H), 6.44 (d, J = 16.0 Hz, 1H), 6.24 (dd, J =
15.0, 10.5 Hz, 1H), 5.39 (dt, J = 15.0, 7.5 Hz, 1H), 3.21 (s, 3H), 3.18-3.09
(m, 2H). 13C NMR (125 MHz, CDCl3) δ 177.46, 142.40, 138.73, 137.17,
135.04, 133.51, 131.86, 128.71, 128.53, 128.32, 128.28, 127.92, 127.63,
127.43, 127.34, 126.91, 126.24, 125.42, 109.17, 57.00, 40.92, 26.48.
HRMS (ESI) m/z calculated for [C26H22ClNO+Na]+ 422.1277, found
422.1274.
δ
177.50, 143.73, 137.77, 137.15, 134.87, 133.40, 131.72, 131.02,
128.64, 128.61, 128.53, 128.37, 127.66, 127.42, 126.21, 125.18, 122.62,
108.46, 56.14, 41.28, 26.45. HRMS (ESI) m/z calculated for
[C26H22ClNO+Na]+ 422.1282, found 422.1300.
1-Methyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-yl)-3-(4-
5-Methoxy-1-methyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3at). Total isolated yield: 90%, 2E/2Z = 12.1:1. Purified
3at, yellow solid, m. p. 101–103 oC. 1H NMR (500 MHz, CDCl3) δ 7.44-
7.41 (m, 2H), 7.37-7.28 (m, 7H), 7.23-7.18 (m, 1H), 6.93-6.88 (m, 2H), 6.82
(d, J = 8.0 Hz, 1H), 6.58 (dd, J = 15.5, 10.5 Hz, 1H), 6.42 (d, J = 15.5 Hz,
1H), 6.23 (dd, J = 15.0, 10.5 Hz, 1H), 5.46-5.40 (m, 1H), 3.81 (s, 3H), 3.20
(s, 3H), 3.19-3.15 (m, 1H), 3.10-3.06 (m, 1H). 13C NMR (125 MHz, CDCl3)
δ 177.58, 155.84, 139.29, 137.36, 137.23, 134.66, 132.97, 131.48, 128.56,
128.51, 128.16, 127.36, 127.33, 127.06, 126.18, 112.54, 108.51, 57.06,
55.79, 40.96, 26.47. HRMS (ESI) m/z calculated for [C27H25NO2+H]+
396.1958, found 396.1963.
(trifluoromethyl)phenyl)indolin-2-one (3ay). Total isolated yield: 60 %,
1
2E/2Z= 9.1:1. Purified 3ay, yellow oil. H NMR (500 MHz, CDCl3) δ 7.58
(q, J = 8.5 Hz, 4H), 7.40 (td, J = 7.5, 1.5 Hz, 1H), 7.35-7.28 (m, 5H), 7.23-
7.16 (m, 2H), 6.94 (d, J = 8.0 Hz, 1H), 6.56 (dd, J = 15.5, 10.5 Hz, 1H),
6.42 (d, J = 15.5 Hz, 1H), 6.21 (dd, J = 15.0, 10.5 Hz, 1H),5.42-5.36 (m,
1H), 3.23 (s, 3H),3.21-3.16 (m, 1H),3.10-3.05 (m, 1H). 13C NMR (125 MHz,
CDCl3) δ 177.18, 143.77, 143.31, 137.13, 135.08, 131.90, 130.76,
129.64(q, 2J = 32.5), 128.71, 128.56, 128.30, 127.65, 127.48, 127.32,
126.25, 125.47 (q, 3J = 3.9 Hz), 125.22, 124.07(q, 1J = 270.0), 122.75,
108.58, 56.61, 41.28, 26.50. HRMS (ESI) m/z calculated for
[C27H22F3NO+Na]+ 456.1542, found 456.1540.
1-Methyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-yl)-3-(p-tolyl)indolin-2-
one (3au). Total isolated yield: 87%, 2E/2Z = 10.1:1. Purified 3au, yellow
oil. 1H NMR (500 MHz, CDCl3) δ 7.40-7.35 (m, 2H), 7.34-7.28 (m, 6H),
7.24-7.20 (m, 1H), 7.18-7.15 (m, 3H), 6.92 (d, J = 7.5 Hz, 1H), 6.58 (dd, J
= 15.5, 10.5 Hz, 1H), 6.42 (d, J = 16.0 Hz, 1H), 6.23 (dd, J = 15.0, 10.5 Hz,
1H), 5.48-5.42 (m, 1H), 3.22 (s, 3H), 3.20-3.17 (m, 1H), 3.10-3.05(m, 1H),
2.35 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 178.02, 143.77, 137.22, 137.03,
136.31, 134.51, 131.75, 131.37, 129.24, 128.56, 128.49, 128.34, 128.17,
127.30, 126.94, 126.15, 125.13, 122.42, 108.20, 56.32, 41.04, 26.35,
20.94. HRMS (ESI) m/z calculated for [C27H25NO+Na]+ 402.1824, found
402.1821.
3-Benzyl-1-methyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-yl)indolin-2-
one (3az). Isolated yield: 42%, yellow oil. 1H NMR (500 MHz, CDCl3) δ
7.35-7.32 (m, 2H), 7.31-7.27 (m, 2H), 7.24-7.18 (m, 3H), 7.10-7.04 (m, 4H),
6.87 (dd, J = 7.5, 2.5 Hz, 2H), 6.60 (d, J = 8.0 Hz, 1H), 6.57 (d, J = 10.5
Hz, 1H), 6.42 (d, J = 15.5 Hz, 1H), 6.23 (dd, J = 15.0, 10.5 Hz, 1H), 5.50-
5.44 (m, 1H), 3.20 (d, J = 13.0 Hz, 1H), 3.09 (d, J = 13.0 Hz, 1H), 2.97 (s,
3H), 2.85-2.75 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 143.67, 137.27,
135.85, 134.29, 131.32, 130.68, 129.85, 128.66, 128.52, 128.31, 127.87,
127.48, 127.31, 126.39, 126.18, 123.75, 121.99, 107.75, 54.72, 43.29,
40.32, 25.85. HRMS (ESI) m/z calculated for [C27H25NO+H]+ 380.2003,
found 380.2000.
3-(4-Fluorophenyl)-1-methyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3av). Total isolated yield: 83%, 2E/2Z = 10.3:1. Purified
3av, yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.43-7.39 (m, 2H), 7.38-7.32
(m, 3H), 7.31-7.28 (m, 3H), 7.23-7.19 (m, 1H), 7.17 (td, J = 7.5, 1.0 Hz,
1H), 7.05-7.01 (m, 2H), 6.93 (d, J = 8.0 Hz, 1H), 6.57 (dd, J = 15.5, 10.5
Hz, 1H), 6.42 (d, J = 15.5 Hz, 1H), 6.21 (dd, J = 15.0, 10.5 Hz, 1H),5.43-
5.37 (m, 1H), 3.22 (s, 3H), 3.15 (dd, J = 14.0, 6.5 Hz, 1H), 3.04 (dd, J =
6-methoxy-1-methyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3a1). Total isolated yield: 95%, 2E/2Z = 16.7:1. Purified
3a1, colorless oil. 1H NMR (600 MHz, CDCl3) δ 7.46-7.42 (m, 2H), 7.36-
7.32 (m, 4H), 7.32-7.28 (m, 3H), 7.23-7.18 (m, 2H), 6.66 (dd, J = 8.4, 2.4
Hz, 1H), 6.58 (dd, J = 15.6, 10.8 Hz, 1H), 6.51 (d, J = 2.4 Hz, 1H), 6.42 (d,
J = 15.6 Hz, 1H), 6.22 (dd, J = 15.0, 10.8 Hz, 1H), 5.47-5.40 (m, 1H), 3.89
(s, 3H), 3.20 (s, 3H), 3.17 (dd, J = 14.4, 6.0 Hz, 1H), 3.04 (dd, J = 14.4, 8.4
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201901536
European Journal of Organic Chemistry
FULL PAPER
Hz, 1H).13C NMR (150 MHz, CDCl3) δ 178.49, 160.25, 145.06, 139.70,
137.29, 134.53, 131.42, 128.64, 128.56, 128.54, 127.36, 127.32, 127.14,
126.21, 125.89, 123.43, 106.37, 96.20, 56.16, 55.53, 41.37, 26.45.
7-fluoro-1-methyl-3-phenyl-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3a2). Total isolated yield: 92%, 2E/2Z = 8:1. Purified 3a2,
pale yellow oil.1H NMR (500 MHz, CDCl3) δ 7.41-7.38 (m, 2H), 7.36-7.33
(m, 4H), 7.32-7.28 (m, 3H), 7.24-7.19 (m, 1H), 7.09-7.05 (m, 3H), 6.58 (dd,
J = 15.5, 10.5, 1H), 6.43 (d, J = 16.0 Hz, 1H), 6.22 (dd, J = 15.0, 10.5Hz,
1H), 5.44-5.37 (m, 1H), 3.44 (d, J = 2.8 Hz, 3H), 3.19-3.08 (m, 2H). 13C
NMR (125 MHz, CDCl3) δ 177.59, 147.88 (d, 1J = 242.4 Hz), 138.98,
1H), 6.07 (dt, J = 9.5, 3.0 Hz, 1H), 6.04 (dt, J = 9.5, 3.0 Hz, 1H), 4.56 (d, J
= 14.0 Hz, 1H), 4.46 (d, J = 14.0 Hz, 1H), 3.29-3.20 (m, 5H), 3.16-3.10 (m,
2H), 2.84 (dd, J = 8.5, 5.5 Hz, 1H), 2.07-2.02 (m, 1H). 13C NMR (125 MHz,
CDCl3) δ 178.25, 176.84, 175.39, 143.88, 140.16, 138.78, 135.87, 134.34,
131.79, 130.03, 128.63, 128.59, 128.58, 128.41, 128.12, 127.71, 127.44,
126.99, 126.94, 124.98, 122.83, 108.36, 56.52, 46.73, 45.30, 42.06, 41.43,
39.32, 33.43, 26.43. HRMS (ESI) calculated for [C37H32N2O3+H]+ 553.2486,
found 553.2482.
2-Benzyl-4-(1-methyl-2-oxo-3-phenylindolin-3-yl)methyl)-7-phenyl-
hexahydro-1H-isoindole-1,3(2H)-dione (6b). Total isolated yield of 6a
and 6b: 68%, 6a:6b = 1.4:1. Purified 6b, white solid, 210-212 oC; 1H NMR
(500 MHz, CDCl3) δ 7.51-7.47 (m, 2H), 7.38-7.26 (m, 13H), 7.14 (td, J =
7.5, 1.0 Hz, 1H), 7.06-7.02 (m, 2H), 6.89 (d, J = 7.5 Hz, 1H), 5.83 (dt, J =
9.5, 3.5 Hz, 1H), 5.35 (dt, J = 9.5, 3.5 Hz, 1H), 4.56 (d, J = 14.0 Hz, 1H),
4.46 (d, J = 14.0 Hz, 1H), 3.41-3.37 (m, 1H), 3.33 (dd, J = 14.5, 2.5 Hz,
1H), 3.27 (s, 3H), 3.24 (t, J = 8.0Hz, 1H), 3.17 (dd, J = 8.5, 5.0 Hz, 1H),
3.09 (dd, J = 14.5, 10.0 Hz, 1H), 2.31-2.25 (m, 1H). 13C NMR (125 MHz,
CDCl3) δ 178.49, 177.11, 175.39, 143.56, 140.28, 138.72, 135.91, 133.81,
132.07, 129.42, 128.67, 128.65, 128.54, 128.48, 128.40, 128.14, 127.71,
127.44, 126.95, 126.78, 125.32, 122.77, 108.53, 56.99, 46.67, 46.11,
42.07, 41.49, 39.34, 34.04, 26.45. HRMS (ESI) calculated for
[C37H32N2O3+Na]+ 575.2305, found 575.2313.
4
3
137.17, 134.95, 134.58 (d, J = 3.0 Hz), 131.78, 130.54 (d, J = 8.1 Hz),
128.67, 128.56, 128.40, 127.63, 127.52 (d, 2J = 16.9 Hz), 126.98, 126.25,
122.97 (d, 3J = 6.3 Hz), 121.06, 121.03, 116.24 (d, 2J = 19.0 Hz), 57.01,
41.22, 28.90 (d, J = 6.3 Hz).
1-Methyl-3-(3-methylbenzyl)-3-((2E,4E)-5-phenylpenta-2,4-dien-1-
yl)indolin-2-one (3ba). Isolated yield: 35 %, yellow oil. 1H NMR (500 MHz,
CDCl3) δ 7.35-7.31 (m, 2H), 7.29-7.26 (m, 2H), 7.23-7.17 (m, 3H), 7.06 (td,
J = 7.5, 1.0 Hz, 1H), 6.95 (t, J = 7.5 Hz, 1H), 6.88 (d, J = 7.5 Hz, 1H), 6.71-
6.65 (m, 2H), 6.63-6.54 (m, 2H), 6.41 (d, J = 15.5 Hz, 1H), 6.25-6.18 (m,
1H), 5.51-5.43 (m, 1H), 3.15 (d, J = 13.0 Hz, 1H), 3.06 (d, J = 13.0 Hz, 1H),
2.98 (s, 3H), 2.85-2.73 (m, 2H), 2.17 (s, 3H). 13C NMR (125 MHz, CDCl3)
δ 178.69, 143.74, 137.33, 136.96, 135.78, 134.26, 131.29, 130.83, 130.72,
128.72, 128.53, 128.43, 127.82, 127.33, 127.30, 127.08, 126.94, 126.19,
123.87, 121.89, 107.71, 54.63, 43.26, 40.24, 25.85, 21.18. HRMS (ESI)
m/z calculated for [C28H27NO+H]+ 394.2165, found 394.2165.
Acknowledgments
Ethyl (4E,6E)-2-cyano-2,7-diphenylhepta-4,6-dienoate(3bb).
Financial support from the National Natural Science Foundation
of China (21402175, 21875219) is acknowledged.
Total isolated yield: 96%, 2E/2Z = 10.0:1. Purified 3bb, pale yellow oil. 1H
NMR (500 MHz, CDCl3) δ 7.61-7.57 (m, 2H), 7.47-7.43 (m, 2H), 7.42-7.37
(m, 3H), 7.32-7.30 (m, 2H), 7.26-7.22 (m, 1H), 6.74 (dd, J = 15.5, 10.5 Hz,
1H), 6.54 (d, J = 16.0 Hz, 1H), 6.40 (dd, J = 15.0, 10.5 Hz, 1H), 5.74 (dt, J
= 15.0, 7.5 Hz, 1H), 4.32-4.22 (m, 2H), 3.23 (ddd, J = 14.0, 7.5, 1.0 Hz,
1H), 2.96 (ddd, J = 14.0, 7.0, 1.5 Hz, 1H), 1.27 (t, J = 7.0 Hz, 3H). 13C NMR
(125 MHz, CDCl3) δ 167.14, 137.01, 136.39, 134.14, 133.01, 129.16,
128.93, 128.59, 128.02, 127.66, 126.40, 126.15, 125.66, 118.10, 63.28,
54.46, 41.63, 13.87. HRMS (ESI) m/z calculated for [C22H21NO2+Na]+
354.1465, found 354.1469.
Keywords: Palladium • Allylation • 1,3-Diene • C-C Bond
cleavage • Quaternary stereocenter
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Hz, 2H), 7.25-7.20 (m, 1H), 6.67 (ddd, J = 15.5, 10.5, 1.0 Hz, 1H), 6.49 (d,
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127.62, 126.73, 126.33, 57.11, 39.10, 35.41, 18.89. HRMS (ESI) m/z
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2386–2389; n) U. Gellrich, A. Meißner, A. Steffani, M. Kähny, H. J.
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1-Methyl-3-phenyl-3-(5-phenylpentyl)indolin-2-one (5). 89%, colorless
oil. 1H NMR (500 MHz, CDCl3) δ 7.37-7.29 (m, 3H), 7.29-7.27 (m, 1H),
7.26-7.19 (m, 5H), 7.16-7.07 (m, 4H), 6.89 (d, J = 8.0 Hz, 1H), 3.20 (s, 3H),
2.49 (t, J = 8.0, 2H), 2.36 (td, J = 13.0, 4.5 Hz, 1H), 2.17 (td, J = 13.0, 4.5
Hz, 1H), 1.55-1.47 (m, 2H), 1.35-1.20 (m, 3H), 1.18-1.08 (m, 1H), 0.97-
0.86 (m, 1H). 13C NMR (125 MHz, CDCl3) δ 178.63, 142.51, 132.35,
128.45, 128.32, 128.17, 128.06, 127.16, 126.85, 125.56, 124.72, 122.53,
108.19, 56.69, 37.85, 35.75, 31.00, 29.28, 26.31, 24.33. HRMS (ESI) m/z
calculated for [C26H27NO+H]+ 370.2165, found 370.2174.
2-Benzyl-4-(1-methyl-2-oxo-3-phenylindolin-3-yl)methyl)-7-phenyl-
hexahydro-1H-isoindole-1,3(2H)-dione (6a). Total isolated yield of 6a
and 6b: 68%, 6a:6b = 1.4:1. Purified 6a, white solid, 194–196 oC; 1H NMR
(500 MHz, CDCl3) δ 7.51-7.46 (m, 2H), 7.40-7.32 (m, 4H), 7.32-7.26 (m,
9H), 7.16 (td, J = 7.5, 1.0 Hz, 1H), 7.08-7.03 (m, 2H), 6.92 (d, J = 7.5 Hz,
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10.1002/ejoc.201901536
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Palladium-Catalyzed Allylation of
Cyclopropyl Acetylenes with
Oxindoles to Construct 1,3-Dienes
Chuan-Jun Lu,* Xin Yu, Yu-Ting Chen,
Qing-Bao Song,* Zhen-Ping Yang, Hong
Wang
A novel palladium-catalyzed allylic alkylation of oxindoles with cyclopropyl
acetylenes has been developed. Various 1,3-diene oxindole framework bearing a
quaternary stereocenter at the C3 position were synthesized straightforwardly in good
to excellent yields with high regio-, and stereoselectivities.
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