Palladium-Catalyzed Cyclization Reaction of o-Iodoanilines, CO2, and CO: Access to Isatoic Anhydrides

Article abstract of DOI:10.1021/acscatal.7b03000

Isatoic anhydrides, a class of valuable synthetic intermediates and RNA structure probing reagents, are usually prepared with highly toxic phosgene or stoichiometric oxidants. Herein we report a highly selective palladium-catalyzed cyclization reaction for the efficient synthesis of isatoic anhydrides from readily available o-iodoanilines, CO₂, and CO. The reaction proceeds under mild conditions and is redox-neutral. Both CO₂ and CO are indispensable C1 building blocks for this catalytic reaction.

Full text of DOI:10.1021/acscatal.7b03000

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Letter
Palladium-Catalyzed Cyclization Reaction of o-
Iodoanilines, CO2 and CO: Access to Isatoic Anhydrides
Wen-Zhen Zhang, Ning Zhang, Yu-Qian Sun, Yu-Wei Ding, and Xiao-Bing Lu
ACS Catal., Just Accepted Manuscript • Publication Date (Web): 23 Oct 2017
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Palladium-Catalyzed Cyclization Reaction of o-Iodoanilines, CO2 and
CO: Access to Isatoic Anhydrides
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Wen-Zhen Zhang,* Ning Zhang, Yu-Qian Sun, Yu-Wei Ding, and Xiao-Bing Lu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, P. R. China
ABSTRACT: Isatoic anhydrides, a class of valuable synthetic intermediates and RNA structure probing reagents, are usu-
ally prepared with highly toxic phosgene or stoichiometric oxidants. Herein we report a highly selective palladium-
catalyzed cyclization reaction for the efficient synthesis of isatoic anhydrides from readily available o-iodoanilines, CO2
and CO. The reaction proceeds under mild conditions and is redox-neutral. Both CO2 and CO are indispensable C1 build-
ing blocks for this catalytic reaction.
KEYWORDS: carbon dioxide, carbonylation, palladium, homogeneous catalysis, anhydrides
Isatoic anhydrides are valuable synthetic intermediates
in the preparation of biologically important compounds
in medicinal chemistry.1,2 They have also been well-
validated as SHAPE (selective 2'-hydroxyl acylation ana-
lyzed by primer extension) reagent in RNA structure
probing chemistry.3 In general, isatoic anhydrides are syn-
thesized by cyclization reactions of anthranilic acids using
phosgene or its substitutes (Scheme 1, a),1a,1h,1j,4 or oxida-
tive reactions of indoles or isatins (Scheme 1, b).5 Despite
their practicality, these approaches involve the use of
highly toxic phosgene reagents/stoichiometric oxidants
and require the multi-step synthesis of starting materials.
Therefore, a transition-metal-catalyzed method for the
synthesis of isatoic anhydrides from readily available
starting materials in a redox-neutral and step-economical
way is highly desirable.
mented. Maleic anhydrides can be accessed by nickel-
catalyzed double carboxylation of internal alkynes with
CO2 using excess metal powder as reductive agents,9 or
palladium-catalyzed double carbonylation of terminal
alkynes using CO with external oxidants.10In addition,
double carbonylation of epoxides with CO using an Al-Co
bimetallic catalyst afforded succinic anhydrides.11 Recently,
Guan group reported carbonylation of N-alkyl anilines or
anthranilic acids using CO to yield isatoic anhydrides
with stoichiometric amounts of copper(II) oxidants.12 CO2
is an abundant, renewable C1 feedstock and can serve as
an alternative for the combined use of CO and oxidants.13
Inspired by the precedented formation of anhydride moi-
ety via reductive elimination of an acyl metal carboxylate
complex,14,15 we proposed that anhydride compounds
could be constructed more economically by the combined
use of CO2 and CO as building blocks. Given that o-
haloanilines were used as substrates for CO insertion and
CO2 capture to form aryl acyl and carbamate16 intermedi-
ates respectively, isatoic anhydrides could be accessed via
a
redox-neutral transition-metal catalyzed reaction
(Scheme 1, c). Herein, we describe a highly selective and
efficient synthesis of isatoic anhydrides by palladium-
catalyzed cyclization of easily available o-iodoanilines,
CO2 and CO under mild conditions.
The initial reaction of o-iodoaniline (1a) under 1 MPa of
CO2 and 0.5 MPa of CO with 5 mol% Pd(PPh3)4 as catalyst
and 2 equivalent Cs2CO3 as base in THF at 60 oC furnished
86% yield of the desired isatoic anhydride 2a, along with
6% yield of urea 3a and 1% yield of anthranilic acid 4a
(Table 1, entry 1, and see Supporting Information). Varia-
tion of the palladium source and ligand led to decreased
yields of 2a and/or increased yields of byproducts (entries
2-5, see SI). The reaction at an elevated temperature (80
oC) gave lower selectivity for the anhydride product while
a significantly lower conversion of 1a was observed when
the temperature was decreased to 40 oC (see SI).
Scheme 1. Approaches to synthesize isatoic anhy-
drides.
Regarding the syntheses of anhydride compounds using
carbon dioxide (CO2)6,7 or carbon monoxide (CO)8 as a
sole C1 building block, several reactions have been docu-
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Table 1. Optimization of the reaction conditionsa
which conformed the catalytic role of the palladium com-
1
2
3
4
5
6
7
8
plex (entry 15). It is noteworthy that no anhydride prod-
uct was detected when the reactions were conducted in
the absence of either CO2 or CO (entry 16), indicating that
both C1 building blocks were indispensable. The excellent
selectivity of the reaction could be maintained with CO2
and CO balloons, though a decreased yield (86%) of 2a
was obtained (entry 17).
O
I
[Pd]/base
solvent, 60 oC, 16 h
O
+
+
CO2
CO
NH2
O
N
H
1a
2a
COOH
O
COOH
byproduct:
Table 2. Substrate scope for iodoanilinesa
NHPh
N
NH2
9
H
4a
3a
10
11
12
13
14
15
16
17
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60
Base
Yieldb
(%)
Entry
Catalyst (mol%)
Pd(PPh3)4 (5)
(equiv.)
1
Cs2CO3 (2.0)
Cs2CO3 (2.0)
86
69
2
Pd(CH3CN)2Cl2/PPh3
(5/20)
O
O
O
O
tBu
Me
Me
MeO
3
4
5
Pd(CH3CN)2Cl2/dppf
(5/10)
O
O
O
O
Cs2CO3 (2.0)
Cs2CO3 (2.0)
Cs2CO3 (2.0)
82
86
77
O
O
N
H
O
N
H
O
N
H
N
H
Me
2c
Pd(CH3CN)2Cl2/DPEPhos
(5/10)
2b
2e
, 92%
, 93%
2d
, 92%
, 91%
O
O
O
O
Pd(CH3CN)2Cl2/S-Phos
(5/10)
Br
F
Cl
Cl
O
O
O
O
O
O
O
N
H
6
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (1)
Pd(PPh3)4 (0.1)
Pd(PPh3)4 (1)
Pd(PPh3)4 (1)
Pd(PPh3)4 (1)
-
CsOAc (2.0)
KOAc (2.0)
NaOAc (2.0)
NEt3 (2.0)
96
N
O
N
H
N
H
H
X
7
94
b
2f
2g
, 85%
2j
, 90%
, 81%
2h
, X = F, 65%
b
2i
, X = Cl, 60%
8
46
O
O
O
O
O
OMe
9
92
NC
F3C
O2N
O
O
O
O
10
11
CsOAc (2.0)
CsOAc (2.0)
CsOAc (1.0)
CsOAc (0.5)
-
99
O
O
O
N
H
N
H
O
N
H
N
H
99(90)
c
d
c
b
2l
2n
, 55%
2k
, 88%
, 83%
2m
, 73%
12
13
14
15
16c
99(90)
a
Reaction conditions: 1 (0.2-0.4 mmol), Pd(PPh3)4 (1
mol%), CsOAc (1.0 equivalent), CO2 (1.0 MPa), CO (0.5
55
-
o
b
MPa), THF (0.1 M), 60 C, 16 h. Isolated yiled. With 2.5
mol% Pd(PPh3)4. c 36 h. d With 5.0 mol% Pd(PPh3)4.
CsOAc (1.0)
CsOAc (1.0)
CsOAc (1.0)
-
With the optimized reaction conditions in hand, the
cyclization reactions of various o-iodoanilines (1) with
CO2 and CO were investigated with 1 mol% Pd(PPh3)4 and
1 equivalent CsOAc in THF at 60 oC (Table 2). Alkyl-,
methoxy-, fluoro-, chloro-, and bromo-substituted o-
iodoanilines participated in the reaction to afford the cor-
responding isatoic anhydrides (2b-g, 2j) in good to excel-
lent yields. Substrates bearing electron-withdrawing
group such as 1k and 1l furnished the desired products
with a prolonged reaction time in 83% and 88% yield re-
spectively. Trifluoromethyl- and nitro-contained o-
iodoanilines also reacted to provide the corresponding
products in moderate to good yields using 2.5-5.0 mol%
catalyst. Unfortunately, o-bromoaniline was inert under
these reaction conditions.
Pd(PPh3)4
-
17 d
Pd(PPh3)4
86
a
Reaction conditions: 1a (0.4 mmol), CO2 (1.0 MPa),
CO (0.5 MPa), THF (4 mL), 60 oC, 16 h. b Yields of 2a were
determined by NMR using 1,1,2,2-tetrachloroethane as
internal standard. Yields of 2a in parentheses are isolated
yields. c In the absence of CO2 or CO. d Using CO2 and CO
balloons.
Gratifyingly, it is found that the switching base to
CsOAc, CsF, KOAc or NEt3 gave rise to enhanced yields
and selectivity for 2a (entries 6-9). CH3CN, 1,4-dioxane,
DME, and DMF also proved to be suitable solvent for this
reaction, while toluene and DMSO gave the inferior re-
sults (see SI). Notably, a lower catalyst loading (1 mol%)
improved the yield of the anhydride product (entry 10).
The reaction with 0.1 mol% Pd(PPh3)4 still proceeded
smoothly (entry 11). The use of 1 equivalent CsOAc gave
excellent isolated yield of 2a (entry 12). Only 55% yield of
2a was obtained when the reaction was conducted with
0.5 equivalent CsOAc (entry 13). No product was observed
in the absence of a base (entry 14), implicating its necessi-
ty. The Reaction without the catalyst gave no product,
The substrate scope with regard to N-substituted o-
iodoanilines (5) was evaluated (Table 3). The use of N-
methyl, N-butyl and N-benzyl iodoanilines (5a-c) re-
quired an enhanced catalyst loading to achieve full con-
version. A wide range of functional groups including elec-
tron-donating alkoxy and dimethyl amino and electron-
withdrawing trifluoromethyl group, on N-benzyl o-
iodoanilines are tolerated. Electronic modulations of the
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N-benzyl substituents had no substantial effect on the
yields of the cyclization reaction. Substrates containing
1
2
3
4
5
6
7
8
furan and thiophene gave the desired product 6m and 6n.
Single-crystal X-ray analyses of 6c, 6g, and 6l confirmed
the structural assignment of these products (See SI).17
This catalytic approach is scalable, as highlighted by the
synthesis of 6c (91% yield) with 2 mol % palladium cata-
lyst on 1.5 mmol scale. Since N-substituted o-iodoanilines
5 could be readily prepared from o-iodoanilines 1, this
reaction provided a more convenient way to access N-
substituted isatoic anhydrides 6 than post-modification of
isatoic anhydrides 2. Taking advantage of the highly
reactive anhydride group, the isatoic anhydride obtained
could be easily converted into urea-substituted benzoic
acid1a and many biologically important heterocyclic com-
pounds1,18 (Scheme 2).
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Table 3. Substrate scope for N-substituted iodoan-
ilinesa
Scheme 2. Synthesis of urea-substituted benzoic acid
and other heterocycles using obtained anhydrides
b
products. a 2b, CyNH2, H2O, rt, 15 min. 2b, isatin, NEt3,
c
d
toluene, reflux, 4 h. 2b, proline, DMSO, reflux, 3 h. 2b,
ethyl acetoacetate, NaH, DMAc, 120 oC, 0.5 h. e 2b, iPr2NH, rt,
f
o
48 h. 2b, 2-carboxybenzaldehyde, NH4OAc, AcOH, 110 C, 1
h. g 2j, o-phenyldiamine, AcOH, 100 oC, 3 h. h 6c, diethyl ma-
lonate, NaH, DMF, reflux, 5 h.
6d, R = 2-Me, 86%
O
O
6e, R = 4-OMe, 71%
6a, R = Me, 92%b
6f, R = 4-But, 90%
O
6b, R = Bu, 93%b
6c, R = Bn, 95%c
6c, R = Bn, 91%c,d
O
O
6g, R = 4-NMe2, 87%
6h, R = 4-F, 67%
N
O
N
R
O
O
6i
, R = 4-Cl, 90%
R
6j, R = 4-Br, 87%
O
6k, R = 4-CF3, 89%
O
O
O
N
N
O
O
Br
O
N
O
O
O
S
N
O
Bn
6l, 95%
6m, 31%
6n, 60%
6o, 82%
O
O
N
O
N
Br
Me
F3C
O
O
O
O
N
O
O
Scheme 3. Cyclization reaction using labeled CO2 and
CO.
Me
Me
Me
6p, 81%
6q, 99%
6r, 73%
a
Reaction conditions: 5 (0.2-0.4 mmol), Pd(PPh3)4 (1
mol%), CsOAc (1.0 equivalent), CO2 (1.0 MPa), CO (0.5
To verify whether the anhydride group in the product
originated from CO2 and CO, the cyclization reactions
using isotopically-labeled reactants were carried out
(Scheme 3). The 13C NMR and mass spectra of the
obtained product indicated that labeled CO2 or CO were
incorporated into the anhydride molecules (see SI). The
1H-13C COSY spectra of13C2-6c and 13C4-6cshowed that the
carbonyl group in the carbamate moiety came from CO2,
while the carbonyl group linked to the aryl ring derived
from CO (see SI).
o
b
MPa), THF (0.1 M), 60 C, 16 h. Isolated yiled. With 5
c
d
mol% Pd(PPh3)4. With 2 mol% Pd(PPh3)4. 1.5 mmol 5c
was used.
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ACKNOWLEDGMENT
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This work was supported by the Natural Science Foundation
of Liaoning Province (20170540156), and the Fundamental
Research Funds for the Central Universities (DUT17ZD210).
X.-B Lu acknowledges the Program for Changjiang Scholars
and Innovative Research Team in University (IRT13008,
IRT_17R14). We thank John C. K. Chu for the proofreading of
this manuscript.
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Scheme 4. Possible mechanism.
Based on the labeling experiments in Scheme 3, a
possible mechanism was proposed (Scheme 4). The
oxidative addition of Pd0 catalyst A into iodoaniline af-
forded PdII species B. CO insertion gave acyl palladium
intermediate C which underwent reaction with CO2 to
form seven-membered acyl palladium carbamate D. Sub-
sequent reductive elimination provided isatoic anhydride
product and regenerated the Pd0 catalyst. Another
pathway first involved the formation of six-membered
palladium carbamate E from Pd0 catalyst A, o-iodoaniline,
and CO2. Subsequent CO insertion gave intermediate D.
Although intermediate B, but not E, was detected by MS
in the reaction system of o-iodoaniline, stoichiometric
Pd(PPh3)4, CsOAc, and CO2 in the absence of CO, the
possibility of latter route could not be excluded at this
stage.
In summary, we have developed a highly selective pal-
ladium-catalyzed cyclization reaction for the preparation
of a broad range of substituted isatoic anhydrides from o-
iodoaniline, CO2, and CO. The reaction takes place under
mild conditions and can be carried out even at atmos-
pheric pressure. With the combined use of CO2 and CO as
C1 feedstocks, this reaction is redox-neutral. Further in-
vestigations of the mechanism and the combined use of
CO2 and CO as an anhydride source for other transition-
metal-catalyzed reactions are in progress in our laborato-
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ASSOCIATED CONTENT
The Supporting Information is available free of charge via the
Internet at http://pubs.acs.org.
X-ray crystallographic data for compound 6c, 6g, and 6l (CIF)
Experimental details, optimization of reaction conditions,
characterization of products, copies of H and 13C NMR spec-
1
tra of all products.
AUTHOR INFORMATION
Corresponding Author
* E-mail: zhangwz@dlut.edu.cn
Notes
The authors declare no competing financial interest.
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