Pd-Catalyzed 2,3-Allenylation of Oxindoles with 2,3-Allenylic Carbonates

Article abstract of DOI:10.1002/cjoc.202100402

Allenes and oxindoles are two classes of very important compounds for medicinal chemistry and organic chemistry. Thus, it is of high interest to combine an allene and an oxindole into one molecule. Herein, the first example of palladium-catalyzed exclusive 2,3-allenylation reaction of oxindoles with 2,3-allenylic carbonates has been successfully developed. A rationale for the selectivity of 2,3-allenylation over the expected 1,3-alkadienylation has been proposed.

Full text of DOI:10.1002/cjoc.202100402

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: Pd-catalyzed 2,3-allenylation of Oxindoles with 2,3-Allenylic Carbonates
Authors: Jie Lin, Minqiang Jia, and Shengming Ma*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2021, 39, 10.1002/cjoc.202100402.
The final Version of Record (VoR) of it with formal page numbers will soon be
published online in Early View: http://dx.doi.org/10.1002/cjoc.202100402.
ISSN 1001-604X • CN 31-1547/O6
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Ma Shengming (Orcid ID: 0000-0002-2866-2431)
Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Pd-catalyzed 2,3-allenylation of Oxindoles with 2,3-Allenylic Car-
bonates
Jie Lin,a Minqiang Jia,a and Shengming Ma*a,b
a Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai 200433,
P. R. China.
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling
Lu, Shanghai 200032, P. R.
Keywords
palladium | allenes | chemoselectivity | allenylation | oxindoles
Main observation and conclusion
Allenes and oxindoles are two classes of very important compounds for medicinal chemistry and organic chemistry. Thus, it is of high
interest to combine an allene and an oxindoles into one molecule. Here the first example of palladium-catalyzed exclusive
2,3-allenylation reaction of oxindoles with 2,3-allenylic carbonates has been successfully developed. A rationale for the selectivity of
2,3-allenylation over the expected 1,3-alkadienylation has been proposed.
Comprehensive Graphic Content
R
R
R
mol%)
Pd(PPh3)4 (5.0
MeCN, 25 o
+
LG
C
VS.
O
O
O
examples
to 98%
27
up
N
PG
N
N
yield
PG
Not formed
PG
Products
R
3,3-rearrangement-
reductive
elimination
type
O-
R
N
Pd(PPh3)4
PG
Path 1
attack
Pd+
Pd
P
O
P
P
P
N
R
O-
-
=
P
PPh3
PG
O
N
PG
Products
Path 2 C-attack
MeO2C
aryl
alkyl
O
O
O
O
R
N
N
N
N
PG
aryl = mono- or
PG
PG
PG
Me, Boc,
Bn, PMP.
H,
1o 2o-alkyl
,
=
di-
substituted
PG
phenyl
Br,
.
=
R
Me,
OMe, Cl,
CF3
F,
♠
♠
♠
♠
♠
scope
Room
Versatile allene
reaction
amide functionalities
chemoselectivity
Wide substrate
High yields
temperature
and
High
*E-mail: masm@sioc.ac.cn.
Chin. J. Chem. 2021, 39, XXX－XXX
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Supporting Information
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through the copyediting, typesetting, pagination and proofreading process which may lead to
differences between this version and the Version of Record. Please cite this article as doi:
10.1002/cjoc.202100402
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First author et al.
Report
Table
1
Optimization of reaction conditions for Pd-catalyzed
Background and Originality Content
2,3-allenylation reaction of oxindole 1a with 2a.a
Oxindoles are a very important class of compounds1 exist in
many natural products such as Horsfiline2a and Coerulescine2b and
various bioactive compounds.2c-2g In addition, they are also im-
portant building blocks in organic synthesis.1b,3 Thus, much atten-
tion has been paid to the synthesis of this type of compounds4-18
(Scheme 1a). On the other hand, allenes19-20 have become more
and more important in medicinal chemistry and organic chemistry
due to their unique pharmacological, biological,21 and chemical
properties,22-23 we reasoned that the 2,3-allenylation of oxindoles
would not only be an excellent combination for medicinal chemis-
try but also dramatically increase the diversity of the oxindole
derivatives. The challenge is the possible formation of the
1,3-dienylation products due to the nature of oxindole anion (pKa
= 23.5; ~ 16 for malonate)24 since nucleophiles with a pKa value of
approximately 20 to 25 is in the border between “hard” and
“soft”.25,26 Herein we wish to report the Pd-catalyzed
2,3-allenylation reaction of oxindoles with 2,3-allenylic carbonates
providing oxindoles bearing an allene unit (Scheme 1b).27
Ph
Ph
Ph
mol%)
C
Pd(PPh3)4 (5
OCbz
+
O
O
O
MeCN, 25 o
N
N
N
Me
Me
3aa
Me
3aa'
1a
2a
NOT observed
NMR yields
(3aa/1a, %)b
91/0
Entry
Deviation from standard conditions
1
2c, d
3d
4c
5c
6c
7 c
8
Standard conditions
Pd(OAc)2 (5 mol%) as catalyst
Pd(PPh3)2Cl2 as catalyst
Pd(dba)2 (5 mol%) as catalyst
Pd2(dba)3 (2.5 mol%) as catalyst
0/72
0/98
84/0
8 3/0
79/0
8 3/0
Pd2(dba)3•CHCl3 (2.5 mol%) as catalyst
Pd(dmdba)2 (5 mol%) as catalyst
Toluene as solvent
88/0
76/0
9
THF as solvent
10
11
12
13
14
15
Dioxane as solvent
DCM as solvent
DCE as solvent
Acetone as solvent
Ethyl acetate as solvent
Ethanol as solvent
88/0
90/0
88/0
6 8/0
70/0
7 7/0
Scheme 1 Types of reactions for the synthesis 3,3-disubstituted oxindoles,
pKa value of some compounds, and 2,3-allenylation of oxindoles.
of reactions for the
oxindoles
3,3-disubstituted
synthesis
a) Types
R1
R1 R2
R3
Carbometalation ref. 5
O
Pd, Ni
Pd, Rh
N
(
)
6)
7)
Arylation (ref.
N
O
Radical
cyclization (ref.
X
=
PG
X
PG
X
Br. R1 alkyl
=
=
X
Cl, Br.
I,
F,
R1, R2
=
amino
aryl,
group
EWG
alkyl,
R2
R1
[a] Standard reaction conditions: The reaction of 1a (0.24 mmol), 2a (0.20
mmol) and Pd(PPh3)4 (5 mol%) in MeCN (1.0 mL) was conducted at 25 C.
[b] NMR yield with CH2Br2 as the internal standard. [c] PPh3 (10 mol%) was
added. [d] DCE as solvent.
R1
O
o
catalysts
Organic
catalysts
Organic
O
Conjugate
1,2-Addition
O
addition reaction
reaction
8)
N
reaction
N
PG
(ref.
Cycloaddition
Other addition reactions
(ref.10)
N
9)
11)
(ref.
PG
(ref
PG
R1
R1
Pd, Mo,
catalysts
Sc,Organic
2-LG
Sc, Pd,
catalysts
Organic
R
With the optimized reaction conditions (Table 1, entry 1), the
scope of the N-substituent was investigated. Methyl or
tert-butoxycarbonyl groups provided the products 3aa and 3ba in
90% yield and 88% yield, respectively (Table 2, entries 1 & 2). The
reaction also worked with easily removable benzyl
group-substituted oxindole 1c, p-methoxyphenyl group-substi-
tuted oxindole 1c’ (with the reported pKa of 23.5),24 and even the
N-non-substituted oxindole 1d, leaving further opportunities for
elaboration of the N-substituent (Table 2, entries 3-5). Again, the
corresponding 3aa’-type 1,3-diene products were NOT formed
(see Scheme 1c).
O
O
R2
Rearrangement reaction
12)
(ref.
Alkylation, allylation, acylation,
arylation, vinylation,
13-18)
N
PG
N
cyanation
PG
(ref.
α
work:
vs.
1,3-allenylation
This
of oxindoles:
-allenylation
2,3-allenylation
b)
R
R
R
N
LG
mol%)
3
4
) (5
Pd(PPh
O
+
O
N
O
N
MeCN, 25 °C
PG
PG
PG
not
formed
Results and Discussion
Oxindole 1a and 2,3-allenylic benzyl carbonate 2a were se-
lected as the model substrates for optimizing reaction conditions.
After some screening, the standard reaction conditions have been
Table 2 Survey on N-substituents.a
Ph
Ph
o
defined as using Pd(PPh3)4 (5 mol%) in MeCN at 25 C, affording
mol%)
C
Pd(PPh3)4 (5
OCbz
+
O
O
the 2,3-allenylation product 3aa in 91% NMR yield, exclusively.
Pd(PPh3)2Cl2 or Pd(OAc)2-PPh3 failed to catalyze the reaction (Table
1, entries 2 & 3). Other palladium (0) sources, such as Pd(dba)2,
Pd2(dba)3, Pd2(dba)3•CHCl3, and Pd(dmdba)2, were also screened
and Pd(PPh3)4 was still the optimal (Table 1, entries 4-7). With
Pd(PPh3)4 as the catalyst, the reaction in toluene at 25 oC afforded
the product 3aa in 88% yield (Table 1, entry 8). When using etheric
solvents such as THF and dioxane, the yield was lower (Table 1,
entries 9 & 10). DCM, DCE, acetone, ethyl acetate, and ethanol
were also inspected with no better results (Table 1, entries 11-15).
It is worth noting that 3aa was selectively generated in this reac-
tion, and 1,3-dienylation product 3aaʹ was NOT observed in all the
cases during our optimization of the reaction conditions.
MeCN, 25 o
N
N
R
R
2a
1
3
Entry
R
Yield (3, %)b
90% (3aa)
88% (3ba)
80% (3ca)
84% (3c’a)
81% (3da)
1
2
3
4
5
Me (1a)
Boc (1b)
Bn (1c)
PMP (1c’)
H (1d)
[a] Standard reaction conditions: The reaction of
1 (1.2 mmol), 2a
(1.0 mmol) and Pd(PPh3)4 (5 mol%) in MeCN (5.0 mL) was conducted
at 25 oC. [b] Isolated yield.
A series of 3-mono-substituted oxindoles smoothly underwent
this transformation, producing a variety of 3-(2,3-butadien- yl)
oxindoles in moderate to good yields. 3-Aryl-substituted oxindoles
bearing different substituents on the 3-phenyl were tested. As
shown in Table 3, the variation of electronic and steric effects was
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Running title
Chin. J. Chem.
tolerated: the substrates with methoxy, fluoro, chloro, methyl,
ethyl, isopropyl at the para- or ortho-position of the phenyl ring
could react with 2,3-allenylic carbonate 2 afforde the correspond-
ing products in 74%-99% yields (Table 3, entries 3-9). 2,4-Dimethyl,
2,5-dimethyl, 4-methoxy-2-methyl, and 4-chloro-2-methyl substi-
tuted aryl groups were also tolerated (66%-96%, Table 3, entries
10-13). Further exploration of the substrate scope was focused on
the left hand phenyl ring on the oxindoles. Various
3-(o-tolyl)-oxindoles substituted with electron-donating groups
(methyl and methoxy) and electron-withdrawing groups (fluoro,
chloro, bromo and trifluoromethyl) also reacted to afford the
2,3-allenylation products (44%-96%, Table 3, entries 14-23). In
addition, this reaction also worked with 3-alkyl-substituted oxin-
doles affording the corresponding products in 60%-70% (Table 3,
entries 24-27).
if the amount of 1D was 2.3 equiv, the reaction at 25°C in the ab-
sence of a base still afforded double 2,3-allenylation product 3Db
albeit in a low yield (Table 4, entry 3).
Table 4. Pd(PPh3)4-catalyzed 2,3-allenylation of 3-non-substituted oxin-
dole 1D.
mo
Pd PPh
(
5
l
%
)
)
(
(
4
s
3 z e u v
C
2CO3
q
i
)
O
oc
OB
+
N
O
O
CN T o
,
C
,
e
M
t h
N
N
oc
B
oc
B
oc
B
'
3Db
x mmo
mmo
l
)
1D
2b
3Db
l
y
(
(
)
s
e
recover
,
1D
2b
C
(
2CO3
NMR yi ld
NMR
(
y
T o
50
C
n r
E
t y
t h
'
,
z e u v
x mmo
mmo
1D
l
y
(
l
q
.
i
3Db 3Db
/
%
%
)
)
(
)
(
)
)
.
.
1
2
3
4
5
0 5
1 2
1 2
18
12
12
18
18
78 76 /0
0
(
)
.
.
.
0 23
0 1
1 2
25
25
50
50
,
3
/
7 0
43
73
33
42
.
.
0 23
0 1
0
.
21/0
16/0
30/0
Table 3 Substrate scope of Pd(PPh3)4-catalyzed 2,3-allenylation of oxin-
.
.
0 24
0 1
1 2
doles.a
.
.
0 24
0 1
0
,
,
an
d
a
eac on con ons: e reac on o
s
mo
l
%
)
n
e
M
C
i
R1
[
]
(
.
ti
d
diti
Th
e
ti
d NMR yi ld ith CH2B
f
1D 2b
d Pd PPh
5
) (
4
t
i
N
th
R
C
2CO3
l
R1
3
.
was con uc e
aren eses
th
w
r
as e n erna s an ar so a e
e
s
ven n
e
4
5
t
th
i
t
t
d I
l
d yi ld i gi
2
mol%)
C
.
Pd(PPh3)4 (5
LG
R2
R2
p
+
O
O
MeCN, 25 o
N
6
N
7
PG
PG
=
2a
2b
1
LG OCbz
3
=
LG OBoc
However, the reaction of 1,1-disubstituted allenylic carbonate
as the substrates failed (2c & 2d) (Scheme 2, eqs (1) & (2)). No
reaction occurred to pyrrolidin-2-one (1E) and
1-methylpyrrolidin-2-one (1F) (Scheme 2, eqs (3) & (4)).
Entry
1c
R1
R2
H
H
H
H
H
H
H
H
H
H
H
H
H
5-Me
5-MeO
5-F
5-Cl
5-Br
6-Cl
6-Cl
6-Br
7-Cl
7-CF3
H
PG
Me
Boc
Me
Me
Me
Boc
Boc
Boc
Boc
Boc
Boc
Boc
Boc
Boc
Boc
Boc
Boc
Boc
Me
Boc
Boc
Boc
Boc
Boc
Me
Boc
Boc
Yield (3, %)b
90% (3aa)
88% (3ba)
89% (3eb)
87% (3fa)
99% (3ga)
98% (3hb)
84% (3ib)
78% (3jb)
74% (3kb)
66% (3lb)
77% (3mb)
80% (3nb)
96% (3ob)
80% (3pb)
58% (3qb)
95% (3rb)
94% (3sb)
95% (3tb)
96% (3ua)
89% (3vb)
44% (3wb)
92% (3xb)
85% (3yb)
65% (3zb)
60% (3Ab)
70% (3Bb)
69% (3Cb)
C6H5 (1a)
C6H5 (1b)
4-MeOC6H4 (1e)
4-FC6H4 (1f)
4-ClC6H4 (1g)
2-MeC6H4 (1h)
2-EtC6H4 (1i)
2-MeOC6H4 (1j)
2-i-PrC6H4 (1k)
2c
Scheme 2 Some failed substrates of Pd(PPh3)4-catalyzed 2,3-allenylation
reaction.
3c
4c
R1
N
R1
5c
mol%)
Pd(PPh3)4 (5
OBoc
R2
O
6c
+
O
MeCN, 25 o
C
N
PG
R2
7
8
9
PG
1
2
3
o
-Tolyl
Ph
O
1h
2b
10
11
12
13
14c
15
16d
17c
18c
19c
20c
21
22
23
24
25
26
27
2-Me-4-MeC6H3 (1l)
2-Me-5-MeC6H3 (1m)
Ph
O
(1)
(3)
O
N
OBoc
H
N
H
N
Boc
4-MeO-2-MeC6H3 (1n)
4-Cl-2-MeC6H3 (1o)
2-MeC6H4 (1p)
2-MeC6H4 (1q)
2-MeC6H4 (1r)
2-MeC6H4 (1s)
2-MeC6H4 (1t)
C6H5 (1u)
2c
3hc,
1E
3Eb,
Not observed
Not observed
mmol)
recovery
mmol)
O
recovery
1h
2b
58% NMR
81% NMR
(0.1
(0.24
o
-Tolyl
n
-Bu
2b
1h
n
-Bu
O
(2)
(4)
N
O
N
OBoc
N
Me
Me
Boc
2d
3hd
1F
3Fb, Not observed
mmol)
mmol)
recovery
2b
80% NMR
mol%) in MeCN
Pd(PPh3)4 (5
(0.1
complicated
(0.24
,
and
2
was
1
Reaction conditions: The reaction of
conducted. NMR
[a]
(1.2 equiv),
or recovery
as
with CH2Br2
the internal standard.
yield
2-MeC6H4 (1v)
2-MeC6H4 (1w)
2-MeC6H4 (1x)
2-MeC6H4 (1y)
n-C7H15 (1z)
As mentioned in the introduction, the regioselectivity of the
Pd-catalyzed allenol derivatives with nucleophiles depended on
the nature of the nucleophiles: Gore28a pioneered the Pd-catalyzed
2,3-allenylation reaction of 2,3-allenol derivatives with soft nucle-
ophile forming allene products, exclusively28-29 (Scheme 3a, path a).
On the other hand, Vermeer30a reported the Pd-catalyzed coupling
reaction of 2,3-allenol derivatives with hard nucleophile, affording
1,3-diene product (Scheme 3a, path b). Due to the nucleophile
nature of oxindole anion, 1,3-dienes should be the expected
products,30 however, 2,3-allenylation products were formed exclu-
sively here. We further performed a deuterium-labeling experi-
ment to gain some insight into the reaction mechanism. The reac-
tion of oxindole 1h with terminal deuterium 2,3-allenylic tert-butyl
carbonate 2b-d2 gave product 3hb-d2 (Scheme 3b). Thus, we pro-
posed a possible mechanism as shown in Scheme 4b. Firstly, oxi-
dative addition of 2b with Pd(0) would form η1-dienyl-Pd, which
would immediately isomerize to the delocalized methylene-π-allyl
palladium η3-int I21 via the σ-π rearrangement involving the coor-
dination of the terminal C=C bond with Pd (Scheme 3c). The oxin-
CH2CO2Me (1A)
i-Pr (1B)
H
H
H
Cy (1C)
[a] Standard reaction conditions: The reaction of
(0.5 mmol) and Pd(PPh3)4 (5 mol%) in MeCN (2.5 mL) was conducted
at 25 C. [b] Isolated yield. [c] The reaction of
mmol) and Pd(PPh3)4 (5 mol%) in MeCN (5.0 mL) was conducted at 25
oC. [d] The reaction of 1r (0.5 mmol), 2b (0.6 mmol) and Pd(PPh3)4 (5
mol%) in MeCN (2.5 mL) was conducted at 25 oC.
1 (0.6 mmol), 2b
o
1 (1.2 mmol), 2 (1.0
Besides, 3-non-substituted oxindole 1D and 2,3-allenylic
tert-butyl carbonate 2b also worked well in this reaction, and only
double-substituted product 3Db was formed and no sin-
gle-substituted product 3Db’ was observed (Table 4, entry 1). Even
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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First author et al.
Report
dole enol anion may approach the methylene-π-allyl palladium
intermediate by the direct oxygen attack of the enolate at the Pd
atom to form int II, which may most probably proceed via the
inner-sphere 3,3-rearrangement- type reductive elimination32 to
afford 3. It is also difficult to exclude the possibility of having η3-int
I reacted directly with the oxindole anion to form the final product
3.
1369, 1344, 1252, 1182, 1158, 1128, 1086, 1019; MS (70 eV, EI)
m/z (%): 275 [M+, 46.27], 222 (100); HRMS Calcd for C19H17NO [M+]:
275.1310; Found: 275.1308.
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
Scheme 3 Pd-catalyzed reaction of 2,3-allenol derivatives with soft and
hard nucleophiles, control experiment, and a proposed mechanism.
Acknowledgement
and
Pd-catalyzed reaction of
derivatives with soft
hard
2,3-allenol
a)
nucleophiles:
soft Nu-
Nu
R1
Financial support from the National Natural Science Founda-
tion of China (Grant No. 21690063) is greatly appreciated. We
thank Mr. Yifan Cui in this group for reproducing the results of 3ba
presented in Table 3.
b
a
R2
path
R2
LG
PdL*
a
PdL*
R1
R1
R2
hard Nu-
3
1
2
Nu
R1
R2
b
path
According to the
Soft nucleophiles
Hard nucleophiles
law that Pd catalyzes the reaction of
derivatives with
2,3-allenol
empirical
nucleophiles:
π
are
are
that attack the
C1
C3
of
of
-allyl
-allyl
to obtain allene
reagents
position methylene-
palladium
products.
π
References
that
attack the
to
obtain
reagents
1,3-diene
products.
position methylene-
palladium
Control
experiment
b)
D
[1] For selected reviews on natural products and bioactive compounds
containing oxindole scaffolds, see: (a) Marti, C.; Carreira, E. M. Con-
struction of Spiro[pyrrolidine-3,3’-oxindoles]-Recent Applications to
the Synthesis of Oxindole Alkaloids. Eur. J. Org. Chem. 2003,
2209-2219; (b) Galliford, C. V.; Scheidt, K. A. Pyrroldinyl-Spirooxindole
Natural Products as Inspirations for the Development of Potential
Therapeutic Agents. Angew. Chem. Int. Ed. 2007, 46, 8748-8758; (c)
Peddibhotla, S. 3-Substituted-3-hydroxy- 2-oxindole, an Emerging
New Scaffold for Drug Discovery with Potential Anti-Cancer and other
Biological Activities. Current Bioactive Compounds 2009, 5, 20-38; (d)
Millemaggi, A.; Taylor, R. J. K. 3-Alkenyl-oxindoles: Natural Products,
Pharmaceuticals, and Recent Synthetic Advances in Tan-
dem/Telescoped Approaches. Eur. J. Org. Chem. 2010, 4527-4547.
[2] (a) Jossang, A.; Jossang, P.; Hadi, H. A.; Sévenet, T.; Bodo, B. Horsfiline,
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2170-2173.
Me
D
Me
D
D
Me
mol%)
Pd(PPh3)4 (5
D
D
+
O
MeCN, 25 o 12 h
C,
OBoc
O
N
O
N
N
Boc
Boc
Boc
3hb'-d2
Not observed
,
1h
0.6
2b-d2
0.5
D
3hb-d
D
2, >99%
>99%
mmol
mmol
94%
A
mechanism
proposed
c)
R
O
R
N
oxidative
addition
OBoc
η1 η3
to
Boc
OBoc
Pd+
O
N
Pd+
Pd
P
P
P
η3
P
P
P
Boc
-
η1
int I
-dienyl-Pd
2b
R
3
=
P
PPh3
O
N
Boc
R
inner
sphere
3,3-rearrangement-
3
O-Pd
P
reductive
type
N
P
elimination
Boc
int II
Conclusions
In conclusion, we have developed the first example of
Pd-catalyzed 2,3-allenylation reaction of oxindoles with
2,3-allenylic carbonates for the efficient construction of allene
derivatives bearing an oxindole unit. The reaction enjoys a wide
substrate range and good yields with a different mechanism. Fur-
ther studies are being pursued in our laboratory.
Experimental
Typical procedure for the synthesis of 3-(2,3-butadienyl)-1-
methyl-3-phenylindolin-2-one (3aa): To a flame-dried Schlenk
tube were added Pd(PPh3)4 (57.5 mg, 0.05 mmol), 1a (266.5 mg,
1.2 mmol), and 2a (203.8 mg, 1.0 mmol)/MeCN (5.0 mL) sequen-
tially under Ar atmosphere at room temperature. The resulting
o
mixture was stirred at 25 C for 5.5 h as monitored by TLC and
filtrated through a short column of silica gel (height: 3 cm, Φ: 3.5
cm) eluted with diethyl ether (60 mL). After evaporation, the resi-
due was purified by column chromatography on silica gel to afford
3aa (246.7 mg, 90%) as an oil [eluent: petroleum ether/ ethyl ace-
tate = 15/1]: 1H NMR (400 MHz, CDCl3) δ = 7.37 (d, J = 7.6 Hz, 2 H,
ArH), 7.36-7.18 (m, 5 H, ArH), 7.10 (t, J = 7.4 Hz, 1 H, ArH), 6.87 (d,
J = 7.6 Hz, 1 H, ArH), 4.80-4.70 (quintet, J = 7.0 Hz, 1 H, =CH),
4.56-4.48 (m, 1 H, one proton of =CH2), 4.44-4.36 (m, 1 H, one
proton of =CH2), 3.18 (s, 3 H, CH3), 3.03-2.90 (m, 2 H, CH2); 13C
NMR (100 MHz, CDCl3) δ = 210.0, 177.7, 143.9, 139.2, 131.4, 128.4,
128.3, 127.3, 127.0, 125.2, 122.4, 108.2, 84.3, 74.4, 56.3, 37.0,
26.3; IR (neat, cm-1): 3056, 2930, 1954, 1707, 1608, 1491, 1468,
[4] For selected reviews on synthesis of 3,3-disubstituted oxindoles, see:
www.cjc.wiley-vch.de
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem. 2021, 39, XXX－XXX

Running title
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Synthesis
of
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© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de

First author et al.
Report
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2021
Manuscript revised: XXXX, 2021
Manuscript accepted: XXXX, 2021
Accepted manuscript online: XXXX, 2021
Version of record online: XXXX, 2021
Chin. J. Chem. 2021, 39, XXX－XXX
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Entry for the Table of Contents
Pd-catalyzed 2,3-allenylation of Oxindoles with 2,3-Allenylic Carbonates
Jie Lin, Minqiang Jia, and Shengming Ma*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
R
R
mol%)
Pd(PPh3)4 (5.0
MeCN, 25 o
LG
C
+
O
O
examples
to 98%
27
up
N
N
yield
PG
PG
reaction
Room
√
temperature
chemoselectivity
√
√
√
High
Wide substrate
Versatile allene
scope
and
amide functionalities
A palladium-catalyzed reaction of oxindoles with 2,3-allenylic carbonates afforded 3-allenyloxindoles efficiently under mild reaction conditions with an
excellent chemoselectivity.
a Department, Institution, Address 1
E-mail:
c Department, Institution, Address 3
E-mail:
b Department, Institution, Address 2
E-mail:
Chin. J. Chem. 2018, template
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