Supported Palladium Nanoparticles that Catalyze Aminocarbonylation of Aryl Halides with Amines using Oxalic Acid as a Sustainable CO Source

Article abstract of DOI:10.1002/chem.201900271

Polystyrene-supported palladium (Pd@PS) nanoparticles (NPs) have been used to catalyze the aminocarbonylation of aryl halides with amines using oxalic acid as a CO source for the first-time for the synthesis of amides. Furthermore, o-iodoacetophenones participated in amidation and cyclization reactions to give isoindolinones in a single step following a concerted approach. Oxalic acid has been used as a safe, environmentally benign and operationally simple ex situ sustainable CO source under double-layer-vial (DLV) system for different aminocarbonylation reactions. Catalyst stability under a CO environment is a challenging task, however, Pd@PS was found to be recyclable and applicable for a vast substrate scope avoiding regeneration steps. Easy handling of oxalic acid, additive and base-free CO generation, catalyst stability and effortless catalyst separation from the reaction mixture by filtration and introduce of DLV are the added advantages to make the overall process a sustainable approach.

Full text of DOI:10.1002/chem.201900271

A Journal of
Accepted Article
Title: Supported palladium nanoparticles catalyzed aminocarbonylation
of aryl halides with amines using oxalic acid as sustainable CO
source
Authors: C. Bal Reddy, Shankar Ram, Ajay Kumar, Richa Bharti, and
Pralay Das
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To be cited as: Chem. Eur. J. 10.1002/chem.201900271
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10.1002/chem.201900271
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COMMUNICATION
Supported palladium nanoparticles catalyzed aminocarbonylation
of aryl halides with amines using oxalic acid as sustainable CO
source†
C. Bal Reddy,[a,b] Shankar Ram,[a,b] Ajay Kumar,[a] Richa Bharti [a,b] and Pralay Das*[a,b]
heterocyclic scaffolds has emerged as efficient protocols in
recent decades.[11] Isoindolinone frameworks are frequently
found in many bioactive molecules and drug candidates
exhibiting HIV-1 reverse transcriptase inhibitor,[12a] diuretic,[12b]
anti-hypertensive,[12c] dopamine D4 receptor antagonist,[12d]
benzodiazepine receptor agonist for the treatment of anxiety etc.
(Figure 1).[12e, 12f]
Abstract: Polystyrene supported palladium (Pd@PS) nanoparticles
(NPs) catalyzed aminocarbonylation of aryl halides with amines
using oxalic acid as CO source has been attempted first-time for the
synthesis of amides. Further, o-iodoacetophenones under similar
conditions participated in amidation and cyclization reaction to give
isoindolinones in single-step following
a concerted approach.
Oxalic acid has been used as a safe, environmentally benign and
operationally simple ex situ sustainable CO source under double-
layer-vial (DLV) system for different aminocarbonylation reactions.
The catalyst stability under CO environment is a challenging/ difficult
task however, Pd@PS catalyst was found to be recyclable and
applicable for vast substrate scope avoiding regeneration steps.
Easy handling of oxalic acid, additive and base free CO generation,
catalyst stability and effortless catalyst separation from reaction
mixture by filtration and introduce of DLV are the added advantages
to make the overall process a Sustainable approach.
OMe
O
OMe
O
O
MeO
MeO
NH
N
N
HO
HO
O
Me
N
Cl
SO2NH2
O
O
O
Chilenine
Chlorthalidone
Fumadensine
O
Figure 1. Bioactive molecules containing isoindolin-1-one.
Due to its immense importance, several transition metal or
phase transfer catalyzed transformations have been developed
for their synthesis.[13] In addition, few carbonylative coupling
reactions were also developed using CO gas and homogeneous
palladium catalysts.[14] But there is no single report yet available
for isoindolinones synthesis directly from haloacetophenones
and amines following carbonylative amidation and cyclization
reaction in a concerted approach.
Amides are important class of compounds found in a wide range
of chemical products such as adhesives, pesticides,
pharmaceuticals and polymers.[1] Aminocarbonylation of aryl
halides with amines has established as an attractive method for
the synthesis of amides. Many efficient protocols have been
developed for aminocarbonylation using CO gas under transition
metal catalyzed conditions.[2] Recently, Adolfsson et al.
demonstrated the aminocarbonylation reaction using CO gas
under palladium nanoparticles supported on mesocellular foam.
The methodology exhibited the 'release and catch' effect of the
catalyst.[3a] Although, carbon monoxide is cheap and readily
available CO source, but its toxicity, difficult handling and need
for specialized high pressure equipment limits its practical utility
for general lab practices. Therefore, the development of
alternative safer sources of CO would be preferential for
carbonylation reactions.[3b] The CO sources such as metal
carbonyls,[4] acid chlorides,[5] silacarboxylic acids,[6] chloroform,[7]
carbomylsilanes,[8] formamides[9] and formates[10] have been
extensively used for the aminocarbonylation reactions under
transition metal catalyzed conditions. The CO generation from
most of these sources requires strong bases, catalyst and
activators.[10d] In addition, the development of catalytic
carbonylation reactions for the synthesis of biologically active
This report (oxalic acid as ex situ CO source)
O
Pd@PS
R1
X
(COOH)2
N
HNR1R2
R
R
R2
+
Solvent, 130 o
C
Pd@PS
O
I
(COOH)2
R-NH2
+
N R
Me
Me
Solvent, 130 o
C
HO
O
Scheme 1. Preparation of amides and isoindolinone derivatives via Pd@PS
catalyzed carbonylation reaction
In continuous to our earlier development,15 herein, we report the
aminocarbonylation reaction of aryl halides with amines using
(CO2H)2 as an ex situ CO source under Pd@PS catalyzed
conditions in a double layer single vial system. Further, first
report of isoindolinones targeted from 2-iodoacetophenones
following concerted approaches.
The Pd@PS catalyst was prepared as described in our previous
reports (supporting information).[15d] The Transmission electron
microscopy (TEM) experiments were performed to confirm the
impregnation of palladium nanoparticles (NPs) over the
polymeric surface (Figure 2a and 2b). The histogram
represented the particle size distribution and average particle
size found in between 1-4 nm (Figure 2c).
[a]
[b]
C. Bal Reddy, Shankar Ram, Ajay Kumar, Richa Bharti and Dr.
Pralay Das
Natural Product Chemistry & Process Development Division, CSIR-
Institute of Himalayan BioresourceTechnology, Palampur 176061,
HP, India
E-mail: pdas@ihbt.res.in;
Academy of Scientific & Innovative Research, New Delhi 110025,
India.
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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COMMUNICATION
Table 1. Optimisation of reaction condition for aminocarbonylation reactiona
O
catalyst
H
I
N
base
N
+
O
CO source
MeO
MeO
O
solvent, 130 o
C, 20 h
2a
S. NO
base
yieldb
solvent
DMF
CO source
Catalyst (mol% Pd)
Pd@PS (3 mol%)
2H
2O
K2CO3
1
75
68
35
(COOH)2
2H
2O
K3PO4
Et3N
2
3
Pd@PS (3 mol%)
Pd@PS (3 mol%)
DMF
DMF
(COOH)2
Figure 2. (a) TEM image of Pd@PS catalyst at 20 nm. (b) TEM image at 5 nm.
2H
2O
(COOH)2
(c) Particle size distribution histogram calculated from a.
2H
2O
4
5
Pd@PS (3 mol%)
Pd@PS (3 mol%)
DABCO
Cs2CO3
DMF
DMF
40
56
80
(COOH)2
2H
To investigate the reaction set up, we have carried out the
aminocarbonylation reaction between iodobenzene and aniline
by using (COOH)2. 2H2O as CO source under Pd@PS catalyzed
conditions. In our initial experiment using oxalic acid as in situ
CO source in one pot, the desired product 1a was obtained in
lower yield along with 1b and 1c as side products. When we
altered the protocol to double-layer-vial (DLV) single vessel with
screw cap using oxalic acid in outer cell as ex situ CO source
and reaction mixture with catalyst in inner cell, gratifyingly, this
modification delivered 1a in 73% yield (Scheme 2).
2O
(COOH)2
2H
2O
Na2CO3
Na2CO3
Na2CO3
6
7
8
Pd@PS (3 mol%)
Pd@PS (3 mol%)
Pd@PS (3 mol%)
DMF
DMF
DMF
(COOH)2
85
nd
(COOH)2
H
2O
(COOK)2
nd
Na2CO3
Na2CO3
Na2CO3
9
Pd@PS (3 mol%)
Pd@PS (3 mol%)
Pd@PS (3 mol%)
DMF
DMF
DMA
n
(HCHO)
HCOOH
10
11
9
2H
2H
2H
2H
2H
2O
2O
2O
2O
2O
62
(COOH)2
(COOH)2
(COOH)2
(COOH)2
(COOH)2
Na2CO3
Na2CO3
Na2CO3
Na2CO3
45
20
12
13
Pd@PS (3 mol%)
Pd@PS (3 mol%)
Pd@PS (3 mol%)
Pd@PS (3 mol%)
NMP
DMSO
dioxane
DMF
14
55
41
15c
NHCHO
Pd@PS
2H
(COOH)2
In situ CO
34
37
16d
17e
18
(COOH)2
(COOH)2
2O
2O
Na2CO3
Na2CO3
Pd@PS (2 mol%)
Pd@PS (3 mol%)
Pd(OAc)2
DMF
DMF
DMF
DMF
1a
+
+
2H
Na2CO3, DMF
10%
NH2
130 o
C
I
Na
2CO3
2CO3
56
83
(COOH)2
(COOH)2
1b, major
1c
+
Pd(OAc)2/dppb
Na
19
Pd@PS
O
(COOH)2
a4-Iodoanisole (0.22 mmol, 1 equiv.), morpholine (0.32 mmol, 1.5 equiv.), Na2CO3 (0.42 mmol, 2 eq.), oxalic
acid (1.3 mmol, 6 equiv.), Pd@PS (3 mol% Pd). b
N
Isolated yields. cReaction at 120 oC. dReaction using 2 mol%
Ex situ CO
H
Na2CO3, DMF
130 oC
Pd@PS. eRecation using 3 equiv. of oxalic acid
1a, 73%
Scheme 2. In situ and ex situ reaction set up investigation
The scope of the aminocarbonylation reaction was explored by
treating different aryl halides with morpholine under optimized
reaction conditions. Electron neutral aryl iodide such as
iodobenzene reacted well with morpholine to give the desired
amide 2b in good yield. Electron withdrawing functionalities such
as cyano, keto, aldehyde, ester and fluoro substituents were
also found very reactive to produce corresponding amides 2c-g
in 77-86% yields. The p-Cl substituent was tolerated under the
reaction conditions to produce 2h in good yield. In addition, 1-
iodonaphthalene gave the desired amide 2i in excellent yield.
Heterocyclic iodo compound also found to be good substrate for
this conversion to give the anticipated amide 2j in considerably
good yield. In addition, the reaction of 4-bromoacetophenone
and 4-bromobenzaldehyde with morpholine gave the desired
amides 2d' and 2f' in 75 and 78% yield respectively under
With these initial results, we further optimize the protocol using
4-iodoanisole and morpholine as model substrates under
various key reaction parameters. Different bases and solvents
were screened to obtain the highest yield of the product and
Na2CO3 as base in DMF solvent was found to be the best
conditions (Table 1, entries 1-7 and 11-14). Subsequently,
replacing oxalic acid with (CO2K)2. 2H2O, HCO2H and (HCHO)n
didn’t gave the desired product 2a under Pd@PS catalyzed
condition (Table 1, entries 8-10). Moreover, the use of
anhydrous oxalic acid gave the desired amide with an increase
of 85% yield (Table 1, entry 7). The temperature effect was also
tested and found that 130 oC is the desired temperature.
Lowering the temperature (120 oC), catalyst loading (2 mol% Pd)
and oxalic acid (3 equiv.) produced albeit lower yield of product
(Table 1, entries 15-17). The same reaction with Pd(OAc)2 gave
the anticipated amide in moderate yield (Table 1, entry 18). The
use of dppb as ligand along with Pd(OAc)2 gave the desired
product 2a also in 83% yield (Table 1, entry 19).
prolonged
reaction
times.
The
generality
of
the
aminocarbonylationreaction was further explored to various aryl
halides and amine nucleophiles. The reaction of 4-
iodoacetophenone with different amines such as aniline,
pipyridine,
cyclohexylamine,
benzylamine
and
2-
phenylethylamine gave the desired amides 2k-2o in 75-88%
yields. The aminocarbonylation reaction of iodobenzene with
primary and secondary amines such as pipyridine, n-butylamine
and benzylamine produced the expected amides 2p-2r in good
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Table 2. Substrate scope for aminocarbonylation of aryl halides with aminesa
Table 3. Pd@PS catalyzed carbonylative cyclization reaction for the synthesis
of isoindolinonesa
O
Pd@PS
X
R1
O
Pd@PS
(COOH)2
N
R2
I
R
HNR1R2
(COOH)2
R
+
, DMF
H2NR1
+
N
R1
Na2CO3
130 oC, 20 h
CH3
Na2CO3
DMF, 130 oC, 20 h
2b-2w
OH
H3C
O
3a-m
O
O
O
O
O
N
O
N
N
N
H
3C
O
O
O
O
O
N
N
X= I, 84%
NC
2b,
77%
2d,
OMe
OMe
75%
O
2c,
OH
OH
H3C
68%
OH
2d',X= Br, 75%
H3C
H3C
O
3c,
55%
3b
OMe
, 75%
3a,
O
N
MeO
N
O
O
O
N
O
O
OHC
N
MeOOC
N
N
F
2f, X= I,
2f', X= Br, 78%
86%
2g,
OMe
OMe
2e,
82%
77%
OH
OH
OH
H3C
3e,
O
H3C
H3C
51%
Me
Cl
45%
, 43%
3f
O
N
O
O
3d,
O
O
O
N
N
S
N
H
3C
O
O
N
N
N
Cl
87%
76%
2k,
O
Cl
Cl
OCF3
2h,
O
2j, 73%
2i,
95%
OH
47%
OH
H3C
OH
H3C
H3C
OCF3
O
O
O
CH3
, 47%
, 52%
3i
O
3h
3g,
N
H
N
H
N
H
O
O
N
O
H
3C
H
3C
F
H
3C
75%
N
88%
83%
N
N
2l,
2m,
2n,
O
O
O
OH
OH
CH3
CH3
HO
H3C
HO
H3C
O
O
O
OMe
, 54%
3j
, 52%
3m
3k
, 73%
3l,
63%
N
N
H
N
H
H
3C
82%
87%
2p,
79%
2q,
O
2o,
aReaction conditions: 2-Iodoacetophenone halide (1 equiv.), amine (1.5
equiv.), oxalic acid (6 equiv.), Na2CO3 (2 equiv.), Pd@PS (3 mol% Pd).
bIsolated yields.
O
O
O
MeO
N
H
N
N
H
Me
Me
72%
2r,
2s, 71%
2t, 76%
During the reaction of 4-iodoanisole with morpholine under
standard reaction conditions, we observed the presence of
partially soluble palladium species in the solution (4.84 ppm,
after 3 hrs reaction) as detected by ICP-AES analysis, while
after completion of the reaction, an inferior content of soluble
palladium species was detected in the resulting solution (0.03
ppm). These experiments demonstrated that during the reaction
the palladium species was partially dissolved into the solution
and furthermore, the soluble palladium species was re-deposited
onto the support after completion of the reaction.
O
O
O
N
H
HN
N
H
F
Me
3C
2v,
85%
2u,
80%
2w, 77%
aReaction conditions: Aryl halide (1 equiv.), morpholine (1.5 equiv.), oxalic acid
(6 equiv.), Na2CO3 (2 equiv.), Pd@PS (3 mol% Pd). bIsolated yield.
yields. N-Methyl aniline was also found to be good nucleophile
for the carbonylation reaction and reacts with 3-iodoanisole to
give 2s in 71% yield. Electron rich aryl iodides and 4-
iodobezotrifluoride also participated for the same reaction to give
corresponding products 2t and 2v in 76 and 85% yields. The
reaction of polycyclic iodo compounds (1-iodonapthalene and 2-
The recyclability of the catalyst was carried out by using 4-
iodoanisole and morpholine as model substrates. After
completion of the reaction, the catalyst was removed from the
reaction mixture and washed with water and acetone. The dried
catalyst was further used for another cycles. The catalyst was
recycled up to 4 times and considering the complex nature of
reactivity, this may be measured as good reusability (Figure 3a).
The TEM experiment of the collected catalyst after the four
cycles was carried out to determine the morphology of the
catalyst. The images showed some areas of agglomerated
palladium nanoparticles, which may be due to the reaction
environment. This observation could explain the loss of activity
that was seen after the fourth cycle (Figure 3).
iodofluorene)
with
benzylamine
and
cyclopentylamine
proceeded smoothly under the optimized condition and the
desired product 2u and 2w was formed in 80 and 77% yields
respectively (Table 2).
In extent, we have applied the carbonylative cyclization strategy
for the synthesis of isoindolinones in one-pot starting from 2-
iodoacetophenones and amines. Interestingly, the reaction of 2-
iodoacetophenone with benzylamine and methoxy/methyl
substituted benzylamines under the similar optimized conditions
ended with cyclized isoindolinone products 3a-3e in good yields.
The strategy was also extended to chloro, dichloro and
trifluoromethoxy substituted benzylamines and offered the same
corresponding products 3f-3i in 43 to 52% yields. The fluoro
substituted acetophenone was also provided considerably good
reactivity with 54% yield of the product 3j. Phenethylamine also
participated in the same reaction and ended with isoindolinones
3k in 73% yield. Encouraged from the above observation, the
carbonylative cyclization strategy was applied for the various
alkylamines. These alkyl amines afforded good yields of the
corresponding isoindolinones 3l and 3m (Table 3).
Under the investigation of reaction mechanism, it was noticed
that the reaction is following traditional approaches, summarized
in supporting information (Figure S1, S17-18).
In conclusion, we have developed polystyrene supported
palladium (Pd@PS) NPs catalyzed aminocarbonyation reaction
of aryl halide with amines using low cost, sustainable and
abundantly available oxalic acid as CO source under simple
operational conditions. This protocol provides a facile method for
the synthesis of diverse range of amides from various
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Figure 3. (a) Recyclability of Pd@PS. (b) TEM image after 4 cycles. (c)
Histogram showing the particle size distribution.
haloarenes and amines. In addition, we have shown
a
[5]
Acyl chlorides: (a) P. Hermange, A. Lindhardt, R .Taaning, K. Bjerglund,
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straightforward protocol to synthesize isoindolinones starting
from 2-iodoacetophenones and aryl amines following
aminocarbonylative cyclization strategy. The catalyst is
recyclable and highly compatible with the developed process
and applicable under double-layer-vial (DLV) system for vast
substrate scope.
[6]
[7]
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Experimental Section
Typical
procedure
for
the
synthesis
of
(4-
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Methoxyphenyl)(morpholino)methanone (2a). In
a 2 mL vial 4-
iodoanisole (50 mg, 0.21 mmol), morpholine (27.4 mg, 0.32 mmol, 1.5
eq.), Na2CO3 (44.5 mg, 0.43 mmol, 2 eq.), Pd@PS (141 mg, 3 mol% Pd)
and DMF (1.5 mL) was added and this reaction vial was placed in a 5 mL
micro reaction vessel jointly mentioned as DLV which contained oxalic
acid (113.4 mg, 1.3 mmol, 6 eq.) and DMF (0.5 mL). The 5 mL reaction
DLV system was tighten with the solid top cap and heated at 130 oC for
required time. After completion of the reaction the inner vial was removed
and water was added, the organic layer was extracted with ethyl acetate.
The combined organic layer was dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The crude mixture was further
purified by silica gel column chromatography (hexane:ethyl acetate =
70:30), afforded 2a as gummy liquid (42 mg, 85%). 1H NMR (600 MHz,
CDCl3) δ = 3.05 (brs, 3H), 3.70 (brs, 6H), 3.83 (s, 3H), 6.89-6.92 (m, 2H),
7.37-7.40 (m, 2H), 13C NMR (150 MHz, CDCl3) δ = 55.30, 66.86, 113.74,
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12H16NO3+ is 222.1125 observed 222.1131
calculated for
C
Acknowledgements
We are grateful to the director CSIR-IHBT for providing
necessary facilities during the course of the work. We thank Dr.
G. Saini, AIRF, JNU, New Delhi, India and Biotechnology
Division, CSIR-IHBT, for TEM analysis; For financial support the
authors thank DST Nano Mission Project (SR/NM/NS-
1340/2014). C. B. R, S.R, A.K and R.B. thanks CSIR and UGC,
New Delhi for awarding fellowship. †IHBT communication no.
4322.
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Keywords: palladium nanoparticles (NPs) • aminocarbonylation•
oxalic acid • amides • isoindolinones
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C. Bal Reddy,[a,b] Shankar Ram,[a,b] Ajay
Kumar,[a] Richa Bharti [a,b] and Pralay
Das[a,b]*
Supported palladium nanoparticles
catalysed aminocarbonylation of aryl
halides with amines using oxalic acid
as sustainable CO source
This article is protected by copyright. All rights reserved.