Design and Application of Indole-Based Allylic Donors for Pd-Catalyzed Decarboxylative Allylation Reactions?

Article abstract of DOI:10.1002/cjoc.202000104

A new class of indole-based allylic donors have been designed and developed for palladium-catalyzed decarboxylative allylations. In addition, the first application of these indole-based allylic donors in palladium-catalyzed decarboxylative [3+2] cycloaddition and allylic amination has been achieved by reacting with isocyanates and sulfonyl amines, respectively. This approach represents the first design of indole-based allylic donors, which is helpful for settling the challenge of designing and developing new class of heterocycle-based allylic donors for Pd-catalyzed decarboxylative allylation reactions. Moreover, the application of this new class of allylic donors in cycloadditions and substitutions will add new contents to the research field of decarboxylative allylation.

Full text of DOI:10.1002/cjoc.202000104

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: Design and Application of Indole-Based Allylic Donors for Pd‐Catalyzed
Decarboxylative Allylation Reactions
Authors: Qing-Qing Hang, Si-Jia Liu, Lei Yu, Ting-Ting Sun, Yu-Chen Zhang,* Guang-
Jian Mei* and Feng Shi*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.202000104.
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Chinese Journal
of Chemistry
Allylic compounds, Allylation, Indole, Cycloaddition, Substitution
Report
CJC
中
国 化 学 - An International Journal
Design and Application of Indole-Based Allylic Donors for Pd-Catalyzed
Decarboxylative Allylation Reactions
Qing-Qing Hang,a Si-Jia Liu,a Lei Yu,a Ting-Ting Sun,a Yu-Chen Zhang,*,a Guang-Jian Mei*,a and Feng Shi*,a
a School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, 221116, P. R. China.
Cite this paper: Chin. J. Chem. 2020, 38, XXX—XXX. DOI: 10.1002/cjoc.202000XXX
Summary of main observation and conclusion A new class of indole-based allylic donors have been designed and developed for palladium-catalyzed
decarboxylative allylations. In addition, the first application of these indole-based allylic donors in palladium-catalyzed decarboxylative [3+2]
cycloaddition and allylic amination has been achieved by reacting with isocyanates and sulfonyl amines, respectively. This approach represents the first
design of indole-based allylic donors, which is helpful for settling the challenge of designing and developing new class of heterocycle-based allylic donors
for Pd-catalyzed decarboxylative allylation reactions. Moreover, the application of this new class of allylic donors in cycloadditions and substitutions will
add new contents to the research field of decarboxylative allylation.
synthesized for Pd-catalyzed DcA reactions, which nevertheless
will provide an easy access to biologically relevant heterocyclic
frameworks. Therefore, it is highly desired to design and develop
new class of heterocycle-based allylic donors for Pd-catalyzed DcA
Background and Originality Content
Transition-metal-catalyzed allylation reactions belong to a class
of important transformations for forming new covalent bonds.[1-2]
Among them, palladium-catalyzed decarboxylative allylation (DcA)
reaction has developed rapidly due to its unique characteristics
reactions.
such as generating organometallic intermediates via
decarboxylation of allylic donors under mild conditions, which are
Scheme 1 Profile of Pd-catalyzed decarboxylative allylation (DcA) reactions
used
donors for Pd-catalyzed DcA
allylic
reactions
Commonly
a)
easily intercepted by another reaction partner to construct useful
frameworks.[3]
O
O
R
N
O
O
R1
O
O
O
The rapid development of this class of reactions relies on the
design and synthesis of decarboxylative allylic donors with high
reactivity. As illustrated in Scheme 1a, commonly used allylic
donors for Pd-catalyzed DcA reactions mainly include vinyl
N
R1
R
R
Vinyl oxazinanones
Vinyl oxazolidinones
carbonates
Vinylethylene
oxazinanones,[4-6]
vinyl
oxazolidinones,[7-8]
vinylethylene
O
O
O
O
R
O
O
carbonates,[9-10]
γ-methylidene-δ-valerolactones,[11-12]
O
O
2-alkylidenetrimethylene
carbonates,[13]
R
CO2Me
R
R1
5-methylene-1,3-dioxolan-2-ones[14] and so on.[3] Up to date,
Pd-catalyzed DcA reactions of these allylic donors have been
well-established. The general reaction mode of Pd-catalyzed DcA
reactions is summarized in Scheme 1b. Namely, in the presence of
Pd (0) catalyst, allylic donors underwent decarboxylation to
generate zwitterionic π-allylpalladium intermediate, which could
further undergo cycloadditions or substitutions with another
reaction partner.[3]
-
γ
δ
-Methylidene-
valerolactones
2-Alkylidenetrimethylene
carbonates
5-Methylene-1,3-
dioxolan-2-ones
reaction mode
Pd-catalyzed DcA reactions
General
for
b)
R2
Nu
R1
E
R2
R2
Nu
cycloaddition
R1
R1
X
E
Pd
(0)
Pd
(II)
-
R2
O
X
R2
CO2
R1
R1
However, in spite of these progresses, there are still some
challenges required to be solved in this research field. For
example, the type of allylic donors for Pd-catalyzed DcA reactions
is very limited, and these commonly used allylic donors were
designed and first synthesized almost ten years ago. So, it has
become an urgent task to design and develop new class of allylic
donors for Pd-catalyzed DcA reactions. Furthermore,
heterocycle-based allylic donors have scarcely been designed and
O
X
Nu
Nu
H
=
X
NR, CR
or
O,
2
π
-allyl-Pd
zwitterions
substitution
Nu
XH
donors
allylic
XH
Challenges:
and
and
new
class of
Design
Design
develop
develop
donors
allylic
heterocycle-based allylic
donors
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differences between this version and the Version of Record. Please cite this article as doi:
10.1002/cjoc.202000104
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Hang et al.
Report
To fufill this task, we decided to incorporate the indole core to
the structure of allylic donors based on the consideration that
indole represents one of the most important heterocycles[15] and
the efficient synthesis of indole derivatives has become a lasting
goal in the synthetic community.[16] So, on the basis of our
understanding of indole-based platform molecules,[16f,17] we
designed this new class of indole-based allylic donors for DcA
reactions (Scheme 2). In the presence of Pd (0) catalyst, this class
of indole-based allylic donors would transform into π-allyl-Pd
zwitterion intermediate, which could principally undergo
cycloaddition and substitution reactions with different reaction
partners, thus providing an easy access to indole derivatives.
Enlightened by this design, we synthesized this new class of
indole-based allylic donors and realized two different types of DcA
reactions. Herein, we reported the details of our investigation.
Scheme 2 Design of new class of indole-based allylic donors for DcA
reactions
O
R
R
NaH
Cl
BnO
CHO
CHO
DMF, 0 o
C
N
N
H
Cbz
S2
S2a 68%
yield
S1
,
,
:
=
S1a R
H
S2b 58%
:
=
yield
S1b R Me
MgBr
CeCl3
THF, -78 o
R
C
R
NaHCO3
r.t
N
MeOH,
N
OH
O
Cbz
1
S3
O
33%
26%
1a
,
S3a 59%
S3b 49%
,
,
yield
yield
yield
yield
1b
,
At first, the application of this new class of indole-based allylic
donors was commenced with Pd-catalyzed decarboxylative [3+2]
cycloaddition of vinyl oxazoloindol-3-one 1a with sulfonyl
isocyanate 2a to testify our hypothesis (Table 1). Gratifyingly, in
the presence of Pd(PPh3)4, this reaction in toluene at 25 oC
smoothly occurred to give decarboxylative [3+2] cycloaddition
product 3aa albeit with a low yield (entry 1). Nevertheless, this
preliminary result demonstrated the feasibility of our design on
this new class of indole-based allylic donors for DcA reactions. To
improve the yield, a series of representative solvents were
evaluated for this reaction (entries 1-6), and other solvents did
not display better capability than toluene in promoting the
reaction (entries 2-6 vs entry 1). Then, the reaction temperature
was altered (entries 7-11). It was found that lowering the
temperature would decrease the yield (entries 7-8 vs entry 1),
while elevating the temperature could remarkably enhance the
yield (entries 9-11 vs entry 1). Among different temperatures, 70
oC was revealed to be the most suitable reaction temperature
with regard to the yield (entry 10). To further enhance the yield,
the reagents ratio was modulated (entries 12-15), and it was
discovered that suitably increasing the amount of sulfonyl
isocyanate 2a could increase the yield to a high level of 80% (entry
13). So, these conditions as listed in entry 13 were selected as the
optimal conditions for this Pd-catalyzed decarboxylative
cycloaddition.
N
O
R
R
N
H
O
indole-based
indole
donors
allylic
-
CO2 Pd
(0)
Nu
Nu
NH
or
R
R
Nu
H
Nu
E
N
R
Pd
(II)
N
substitution
R
E
cycloaddition
Nu
π
zwitterion
-allyl-Pd
NH
Results and Discussion
Based on our design of this new class of indole-based allylic
donors, we developed synthetic route for vinyl
a
oxazoloindol-3-ones 1 (Scheme 3). Indole-2-carbaldehydes S1
were utilized as starting materials, which underwent an acylation
reaction with benzoyl chloride to give N-Cbz-protected
Indole-2-carbaldehydes S2 in moderate to good yields. Then, the
addition of vinylmagnesium bromide to the aldehyde group of S2
resulted in allylic alcohols S3 in moderate yields. Finally, an
intramolecular ester-exchange led to the cyclization and the
generation of vinyl oxazoloindol-3-ones 1.
Table 1 Conditions optimization for Pd-catalyzed decarboxylative [3+2]
cycloadditiona
Scheme 3 Synthetic route for vinyl oxazoloindol-3-ones 1
Ts
5 mol%
Pd(PPh3)4
N
C
+
N
N
Ts
N
O
solvent, T o
C
O
O
O
2a
1a
3aa
entry
solvent
T (oC)
1a:2a
yield (%)b
1
2
3
4
5
toluene
DCE
25
25
25
25
25
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
28
23
EtOAc
acetone
CH3CN
23
24
trace
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Chin. J. Chem.
6
7
1,4-dioxane
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
25
0
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:2
trace
22
5
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
p-ClC6H4 (2e)
m-CH3C6H4 (2f)
m-OCH3C6H4 (2g)
m-FC6H4 (2h)
3ae
3af
98
63
67
70
79
80
59
81
70
39
92
72
80
90
90
6
8
-10
50
70
90
70
70
70
70
11
7
3ag
3ah
3ai
9
49
8
10
11
12
13
14
15
70
9
o-CH3C6H4 (2i)
o-OCH3C6H4 (2j)
o-FC6H4 (2k)
65
10
11
12
13
14
15
16
17
18
19
3aj
75
3ak
3al
1:3
80
o-ClC6H4 (2l)
1:4
63
ClCH2CH2CH2 (2m)
cyclopentyl (2n)
3am
3an
3ba
3bb
3be
3bh
3bj
2:1
51
aUnless indicated otherwise, the reaction was carried out at 0.1 mmol
scale in
solvent (0.5 mL) for 12 h. bIsolated yield. DCE
1,2-dichloroethane.
Me (1b) p-CH3C6H4SO2 (2a)
a
=
Me (1b)
Me (1b)
Me (1b)
Me (1b)
p-CH3C6H4 (2b)
p-ClC6H4 (2e)
m-FC6H4 (2h)
o-OCH3C6H4 (2j)
Then, we performed the application of indole-based allylic
donors 1 in Pd-catalyzed decarboxylative [3+2] cycloaddition with
a wide range of isocyanates 2 under the optimal reaction
conditions (Table 2). Apart from sulfonyl isocyanate 2a (entry 1), a
variety of phenyl isocyanates 2b-2l could be utilized as suitable
reaction partners to undergo decarboxylative [3+2] cycloadditions
with vinyl oxazoloindol-3-one 1a in generally high yields of 59% to
98% (entries 2-12). In detail, either para-substituted (entries 2-5),
meta-substituted (entries 6-8) or ortho-substituted (entries 9-12)
phenyl groups could serve as competent R1 groups for isocyanates
2. Among them, para-chlorophenyl isocyanate 2e reacted with
vinyl oxazoloindol-3-one 1a in the highest yield of 98% (entry 5).
In addition, isocyanate 2m bearing an aliphatic substituent could
smoothly participate in the decarboxylative [3+2] cycloaddition
with 1a in a good yield of 70%. Moreover, cyclopentyl isocyanate
2n could undergo the desired [3+2] cycloaddition with 1a
although the yield was unsatisfying (entry 14). In addition to
substrate 1a, methyl-substituted vinyl oxazoloindol-3-one 1b
could also serve as a suitable indole-based allylic donor, which
successfully underwent decarboxylative [3+2] cycloadditions with
a series of phenyl isocyanates 2 in overall high yields of 72%-92%
(entries 15-19).
aUnless indicated otherwise, the reaction was carried out at 0.1 mmol
o
scale in toluene (0.5 mL) at 70 C for 12 h, and the molar ratio of 1:2 was
1:3. bIsolated yield.
After establishing the decarboxylative [3+2] cycloaddition, we
then performed the application of this new class of indole-based
allylic donors in Pd-catalyzed decarboxylative substitution. As
shown in Table 3, the decarboxylative allylic amination reaction of
vinyl oxazoloindol-3-one 1a with sulfonyl amine 4a was employed
as a model reaction to examine the possibility of our design.
Indeed, in the presence of Pd(PPh3)4, the reaction in toluene at
room temperature occurred to generate allylic amination product
5aa with a linear selectivity in a moderate yield of 56% (entry 1),
which demonstrated the feasibility of our design on this new class
of indole-based allylic donors in Pd-catalyzed decarboxylative
substitution. Then, the evaluation of representative solvents
revealed that toluene is much better than other solvents in terms
of the yield (entry 1 vs entries 2-6). To further enhance the yield,
the reaction temperature was changed by either lowering or
elevating the reaction temperature (entries 7-10). It was found
that the yield could be greatly enhanced to 90% when the
reaction temperature was lowered to 0 oC (entry 7 vs entry 1).
Finally, the modulation of reagents ratio (entries 11-12)
discovered that properly increasing the amount of sulfonyl amine
4a could further improve the yield to 95% (entry 11). It should be
noted that only (E)-isomer of 5aa was observed in all cases. So,
these conditions as listed in entry 11 were chosen as the optimal
reaction conditions for this allylic amination reaction.
Table 2 Application of indole-based allylic donors 1 in Pd-catalyzed
decarboxylative [3+2] cycloadditiona
R1
R
5 mol%
Pd(PPh3)4
N
C
O
R
N
N
R1
+
N
O
toluene, 70 o
C
O
O
1
3
2
entry
R1 (2)
3
yield (%)b
R (1)
1
2
3
4
H (1a)
H (1a)
H (1a)
H (1a)
p-CH3C6H4SO2 (2a)
p-CH3C6H4 (2b)
p-OMeC6H4 (2c)
p-FC6H4 (2d)
3aa
3ab
3ac
3ad
80
90
66
66
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Hang et al.
Report
Table
3 Conditions optimization for Pd-catalyzed decarboxylative
3
4
H (1a)
H (1a)
p-BrC6H4 (4c)
p-CF3C6H4 (4d)
m-FC6H4 (4e)
m-BrC6H4 (4f)
o-CH3C6H4 (4g)
o-FC6H4 (4h)
o-ClC6H4 (4i)
Ph (4j)
5ac
5ad
5ae
5af
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
>95:5
70
61
85
88
95
98
91
76
67
87
84
89
64
90
substitutiona
10 mol%
HN Ts
Boc
Pd(PPh3)4
Ts
+
5
H (1a)
N
O
N
solvent, T o
C
N
H
Boc
O
6
H (1a)
1a
4a
5aa
7
H (1a)
5ag
5ah
5ai
entry
solvent
T (oC)
1a:4a
yield (%)b
8
H (1a)
1
2
toluene
DCE
25
25
25
25
25
25
0
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:2
56
30
40
30
40
46
90
54
45
26
95
9
H (1a)
10
11
12
13
14
15
16
H (1a)
5aj
3
EtOAc
Me (1b)
Me (1b)
Me (1b)
Me (1b)
Me (1b)
Me (1b)
p-CH3C6H4 (4a)
p-FC6H4 (4b)
m-BrC6H4 (4f)
o-CH3C6H4 (4g)
o-FC6H4 (4h)
o-ClC6H4 (4i)
5ba
5bb
5bf
5bg
5bh
5bi
4
acetone
CH3CN
5
6
1,4-dioxane
toluene
toluene
toluene
toluene
toluene
7
8
-10
-30
50
0
9
aUnless indicated otherwise, the reaction was carried out at 0.1 mmol
scale in toluene (0.5 mL) at 0 oC for 12 h, and the molar ratio of 1:4 was
1:2. bDetermined by 1H NMR. cIsolated yield.
10
11
aUnless indicated otherwise, the reaction was carried out at 0.1 mmol
scale in a solvent (0.5 mL) for 12 h. bIsolated yield and only (E)-isomer of
5aa was observed in all cases.
The structures of products 3 and 5 were unambiguously
determined by NMR, IR and HR MS. In addition, the structures of
products 3aa and 5bi were confirmed by their single-crystal X-ray
diffraction analysis (Figure 1).[18]
With the optimal reaction conditions in hand, we carried out
the investigation on the application of indole-based allylic donors
1 in Pd-catalyzed decarboxylative substitution (Table 4). As shown
in entries 1-10, vinyl oxazoloindol-3-one 1a could undergo
decarboxylative allylic amination with sulfonyl amines 4a-4j
bearing various para-, meta-, and ortho-substituted phenyl groups,
and these reactions successfully generated allylic amination
products 5aa-5aj with uniformly linear selectivity in overall high
yields (61%-98%). In addition, methyl-substituted vinyl
oxazoloindol-3-one 1b could also be utilized as an allylic donor to
undergo decarboxylative allylic amination with different sulfonyl
N
N
Ts
O
3aa
O
S
N
O
Cl
N
Boc
H
5bi
amines
4 with exclusively linear selectivity in good yields
(64%-90%, entries 11-16). Notably, this reaction has an excellent
(E/Z)-selectivity, and only (E)-isomers of 5 were observed in all
cases.
Figure 1 Single-crystal structures of products 3aa and 5bi
In addition, to examine the practicability of the Pd-catalyzed
decarboxylative [3+2] cycloaddition and allylic amination, we
performed two one-mmol-scale reactions (Scheme 4). Compared
with small-scale reactions (Table 2, entry1 and Table 4, entry 1),
these one-mmol-scale reactions smoothly occurred to give
products 3aa and 5aa in nearly retained high yields, which
demonstrated that these reactions could be scaled up.
Table 4 Application of indole-based allylic donors 1 in Pd-catalyzed
decarboxylative substitutiona
R
H
N
R
10 mol%
Pd(PPh3)4
toluene, 0 o
N
SO2R1
+
N
O
N
H
Boc
SO2R1
Boc
C
O
1
4
5
Scheme 4 One-mmol-scale reactions
entry
R (1)
R1 (4)
5
E/Z b
yield (%)c
1
2
H (1a)
H (1a)
p-CH3C6H4 (4a)
p-FC6H4 (4b)
5aa
5ab
>95:5
>95:5
95
75
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Chin. J. Chem.
Ts
a)
N
C
Ts
5 mol%
Pd(PPh3)4
+
N
N
Ts
N
O
N
C
Pd
(0)
toluene, 70 o 12 h
+
N
N
Ts
C,
N
O
O
2a
mmol
3
O
O
[3+2] cycloaddition
1a
3aa
O
2a
O
O
1a
mmol
3aa
1
74%
mg)
(260.3
-
Pd
CO2
(0)
Pd
(0)
Ts
10 mol%
HN Ts
Boc
Pd(PPh3)4
N
O
+
N
branched selectivity
N
H
toluene, 0 o 12 h
C,
Boc
O
1a
mmol
5aa
4a
mmol
Pd
Pd
(II)
Ts
(II)
N
N
94%
mg)
1
2
N
(400.2
N
B
Ts
A
C
O
O
2a
reaction
intramolecular
Based on the experimental results, we suggested possible
reaction pathways to explain the chemistry and regioselectivity of
the two decarboxylative allylation reactions (Scheme 5). As
exemplified by the formation of products 3aa and 5aa, the two
reactions commenced with the generation of zwitterionic
aza-Mannich
amination
allylic
b)
Pd
Ts
HN Ts
Boc
(0)
N
O
+
N
N
H
5aa
amination
Boc
allylic
O
1a
π-allylpalladium intermediate
A via decarboxylation in the
4a
CO2
presence of Pd (0). In the [3+2] cycloaddition (Scheme 5a), this
intermediate A first attacked sulfonyl isocyanate 2a to undergo an
aza-Mannich reaction, producing another intermediate B. Then,
an intramolecular allylic amination of intermediate B occurred
with a branched selectivity to form a five-membered ring. If the
intramolecular allylic amination occurred with a linear selectivity,
a seven-membered ring would be constructed. Perhaps because
five-membered ring is easier to form than seven-membered ring,
the second step of intramolecular allylic amination occurred with
a branched selectivity, thus accomplishing the observed [3+2]
cycloaddition. Instead, the linear selectivity of intermolecular
allylic amination of 1a with 4a could be explained by the absence
of hydrogen-bond direction (Scheme 5b), which was reported to
be a crucial factor to control the regioselectivity in Pd-catalyzed
allylic reactions.[3b] Namely, π-allylpalladium intermediate A could
transform into intermediate C via deprotonation of sulfonyl amine
4a. There was no hydrogen-bond direction between the NH group
of intermediate C and the deprotonated amine anion, thus
leading to the linear selectivity of the allylic amination.
-
Pd
(0)
Pd
(0)
linear selectivity
Pd
Pd
(II)
(II)
N
N
N
Ts
H
A
H
C
Boc
N
Ts
4a
no
direction
hydrogen-bond
Boc
Furthermore, to examine the utility of vinyl
oxazoloindol-3-ones in [3+2] cycloadditions, we utilized
benzylidene malononitrile 6, an electron-deficient alkene, as a
dipolarophile[4b,5b,19] to react with oxazoloindol-3-one 1a under
the catalysis of palladium (Scheme 6). This [3+2] cycloaddition
smoothly occurred to generate product 7 in a high yield of 94%
albeit with a low diastereoselectivity of 56:44 dr. Nevertheless,
this result indicated that oxazoloindol-3-ones could be utilized in
palladium-catalyzed 1,3-dipolar [3+2] cycloadditions.
Notably, the allylic amination reaction (Scheme 5b) proceeded
o
Scheme 6 Using electron-deficient alkene 6 as a dipolarophile
well at 0 C, while the [3+2] cycloaddition reaction (Scheme 5a)
o
5 mol% Pd2dba3 CHCl3
CN
occurred at a higher temperature of 70 C. The rate difference
CN
CN
10 mol% DPPE
Ph
N
N
O
between the two reactions might stem from the first step after
the formation of π-allylpalladium intermediate A. Specially, in
the [3+2] cycloaddition reaction (Scheme 5a), the first step was
the nucleophilic addition of intermediate A to the C=N bond of
sulfonyl isocyanate 2a, which displayed the nucleophilicity of
intermediate A. While in the allylic amination reaction (Scheme
5b), the first step was the deprotonation of sulfonyl amine 4a by
intermediate A, which exhibited the basicity of intermediate A.
Because the basicity of intermediate A (nitrogen anion) was very
strong, the deprotonation of sulfonyl amine 4a by intermediate
A could occur easily. However, the nucleophilic addition of
+
toluene, 50 o 8 h
CN
C,
Ph
O
7
1a
6
94%
56:44 dr
yield,
Finally, we performed an investigation on the catalytic
asymmetric version of the [3+2] cycloaddition between 1a and 2a
(Table 5). As listed in entries 1-13, a variety of BINOL, H8-BINOL,
and SPINOL-derived chiral phosphoramidites L1-L13 were utilized
as chiral ligands for this palladium-catalyzed allylation reaction.
However, in most cases, very weak enantio-control of product 3aa
was observed. Among these ligands, L5, L10 and L12 could deliver
the [3+2] cycloaddition with some extent of enantioselectivity
(around 20% ee). In addition, several chiral bidentate phosphine
ligands L14-L18 were tested for this reaction (entries 14-18).
Nevertheless, these chiral ligands could hardly control the
enantioselectivity of the [3+2] cycloaddition (< 8% ee). So, it
seemed that L10 was a promising chiral ligand for this reaction
considering the relatively higher yield and better
intermediate
A to the C=N bond was relatively difficult
compared with the deprotonation of sulfonyl amine 4a by
intermediate A. These reasons might result in the observed rate
difference between the two reactions.
Scheme 5 Suggested reaction pathways
Chin. J. Chem. 2020, 38, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Hang et al.
Report
enantioselectivity of the [3+2] cycloaddition in the presence of
L10 (entry 10). However, it is still a challenging task to realize a
highly enantioselective [3+2] cycloaddition between 1a and 2a,
which might require exquisite elaboration of reaction conditions
and structural modifications of chiral ligands.
15
16
17
18
L15
L16
L17
L18
23
33
33
12
<5
<5
<5
8
Table 5 Preliminary investigation on the catalytic asymmetric versiona
aUnless indicated otherwise, the reaction was carried out at 0.05 mmol
scale in toluene (1 mL) for 12 h, and the molar ratio of 1a:2a was 1:1.2.
bIsolated yield. c The ee value was determined by HPLC.
Ph Ph
O
P
O
O
O
O
O
O
O
O
O
O
O
P
N
N
P
N
P
N
P
N
Ph Ph
L4
L5
L2
L1
L3
Conclusions
Me
In summary, we have designed and developed a new class of
O
O
O
O
O
O
O
P
N
P
N
P
N
P
N
O
O
indole-based
allylic
donors
for
palladium-catalyzed
decarboxylative allylations. In addition, we have realized their first
application in palladium-catalyzed decarboxylative [3+2]
cycloaddition and allylic amination, respectively, by reacting with
isocyanates and sulfonyl amines. This approach represents the
first design of indole-based allylic donors, which is helpful for
settling the challenge of designing and developing new class of
heterocycle-based allylic donors for Pd-catalyzed decarboxylative
allylation reactions. Moreover, the application of this new class of
allylic donors in cycloadditions and substitutions will add new
contents to the research field of decarboxylative allylation.
L8
L9
L6
L7
Ph
N
Me
N
Me
Ph
N
O
P
O
Me
Me
Me
Me
Ph
Ph
Ph
Ph
O
O
O
O
P
P
N
P
O
O
Ph
Me
Me
Ph
L12
L13
L11
L10
PPh2
O
O
O
O
NH PPh2
NH PPh2
NH
PPh2
PPh2
Ph
Ph
NH PPh2
NH PPh2
PPh2
PPh2
NH
O
O
Experimental
L14
L15
Ph2P
L16
L17
L18
General Procedure for the synthesis of products 3:
A flame-dried 10 mL flask tube was charged with indole-based
allylic donors 1 (0.1 mmol) and Pd(PPh3)4 (0.005 mmol), sealed
with a septum, and evacuated and backfilled with argon for three
times. Then, isocyanates 2 (0.3 mmol) and toluene (0.5 mL) was
added via syringe. The reaction mixture was stirred at 70 oC for 12
h. After the completion of the reaction which was indicated by
TLC, the reaction mixture was directly purified through
preparative thin layer chromatography on silica gel to afford pure
products 3.
5 mol% Pd2dba3.CHCl3
Ts
∗
N
C
L*
10 mol%
toluene,
+
N
N
Ts
N
O
r.t.
O
O
2a
O
1a
3aa
entry
L*
yield (%)b
ee (%)c
1
2
L1
L2
L3
L4
L5
L6
L7
L8
L9
15
20
15
11
11
20
16
19
18
66
23
12
40
18
<5
<5
8
General Procedure for the synthesis of products 5:
3
A flame-dried 10 mL flask tube was charged with indole-based
allylic donors 1 (0.1 mmol), sulfonyl amines 4 (0.2 mmol) and
Pd(PPh3)4 (0.01 mmol), sealed with a septum, and evacuated and
backfilled with argon for three times. Then, toluene (0.5 mL) was
4
<5
20
<5
11
<5
-8
5
o
6
added via syringe. The reaction mixture was stirred at 0 C for 12
h. After the completion of the reaction which was indicated by
TLC, the reaction mixture was directly purified through
preparative thin layer chromatography on silica gel to afford pure
products 5.
7
8
9
10
11
12
13
14
L10
L11
L12
L13
L14
-20
<5
22
6
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement
<5
We are grateful for financial support from NSFC (21772069,
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2020, 38, XXX－XXX
This article is protected by copyright. All rights reserved.

Chin. J. Chem.
21831007 and 21702077), Natural Science Foundation of Jiangsu
Province (BK20170227) and Six Kinds of Talents Project of Jiangsu
Province (SWYY-025).
Catalyzed Asymmetric Cascade Allylation/2-aza-Cope Rearrangement:
An Efficient Route to Homoallylic Amines from Aldimine Esters, Chin.
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© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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Hang et al.
Report
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2020
Manuscript revised: XXXX, 2020
Manuscript accepted: XXXX, 2020
Accepted manuscript online: XXXX, 2020
Version of record online: XXXX, 2020
Chin. J. Chem. 2020, 38, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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Hang et al.
Report
Entry for the Table of Contents
R1
Page No.
O
C
N
N
N
R1
R
[3+2]
cycloaddition
O
Design and Application of Indole-Based Allylic
Donors for Pd-Catalyzed Decarboxylative
Allylation Reactions
Pd
-
(0)
N
O
19
to 98%
R
examples, up
yield
H
N
Pd
(II)
N
CO2
R
O
N
R
R2
Boc
indole-based
donors
allylic
R2
π
N
H
zwitterion
Boc
-allyl-Pd
substitution
examples
19
all >95:5 E/Z
to 98%
,
up
yield
A new class of indole-based allylic donors have been designed and applied in palladium-catalyzed
decarboxylative [3+2] cycloaddition and allylic amination.
Qing-Qing Hang, Si-Jia Liu, Lei Yu, Ting-Ting Sun,
Yu-Chen Zhang,* Guang-Jian Mei* and Feng Shi*
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2020, 38, XXX－XXX
This article is protected by copyright. All rights reserved.