Stable and Reusable Binaphthyl-Supported Palladium Catalyst for Aminocarbonylation of Aryl Iodides

Article abstract of DOI:10.1002/adsc.201500642

A binaphthyl-supported Pd nanoparticles (Pd-BNP)-catalyzed aminocarbonylation of aryl iodides in the presence of carbon monoxide and amines for the synthesis of amides has been developed. This methodology provides an efficient route for the synthesis of a COX-2 enzyme inhibitor having anti-inflammatory activity.

Full text of DOI:10.1002/adsc.201500642

UPDATES
DOI: 10.1002/adsc.201500642
Stable and Reusable Binaphthyl-Supported Palladium Catalyst for
Aminocarbonylation of Aryl Iodides
Nidhi Sharmaa and Govindasamy Sekara,*
a
Department of Chemistry, Indian Institute of Technology Madras, Chennai, Tamil Nadu – 600036, India
Fax: (+91)-44-2257-4202; e-mail: gsekar@iitm.ac.in
Received: July 4, 2015; Revised: October 16, 2015; Published online: January 5, 2016
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500642.
Abstract: A binaphthyl-supported Pd nanoparticles
(Pd-BNP)-catalyzed aminocarbonylation of aryl io-
dides in the presence of carbon monoxide and
amines for the synthesis of amides has been devel-
oped. This methodology provides an efficient route
for the synthesis of a COX-2 enzyme inhibitor
having anti-inflammatory activity.
ide as an in situ source of generating the carbonyl
moiety has increased using homogeneous palladium
catalysts.[7,8] On the other hand, transition metal nano-
particles as catalyst have attracted great interest be-
cause of their unique properties, such as small particle
size, high surface area, higher interaction with the
substrate, increased reactivity and selectivity, easy pu-
rification and easy separation.[9]
Recently, we have developed an easily reusable
form of Pd nanoparticles (Pd-BNP) stabilized by a bi-
naphthyl backbone through Pd Cðsp2Þ sigma bonds for
the synthesis of polysubstituted olefins, benzonitriles
and for different types of carbon-carbon bond form-
ing reactions.[10] In order to contribute to the existing
few reports on the usage of heterogeneous catalysts
Keywords: aminocarbonylation; binaphthyl-sup-
ported palladium catalyst; carboxylic amides;
carbon monoxide insertion; reusable catalyst
À
The amide bond constitutes one of the most essential for aminocarbonylation,[11,12] and to explore the devel-
parts in organic synthesis and has a specific role in oped Pd-BNP catalyst for the same, we herein, report
chemical and pharmaceutical industries.[1] The amide the usage of easily reusable Pd nanopartcles (Pd-
bond is the main chemical bond linkage in peptides BNP) as catalyst for the synthesis of amides from
and proteins as well. Various important marketed easily available carbon monoxide, aryl iodides and
drugs such as diltiazem,[1e] atorvastatin, and itopride amines through aminocarbonylation (Scheme 1).[13]
have an amide bond in their backbone (Figure 1).[2]
Recently, applications of amide group-containing mol-
ecules have increased in the areas of pharmaceuticals,
agrochemicals, polymers and materials.[3,4] This has
served to stimulate efforts towards the development
of a more economic and catalytic methods for amide
synthesis.
Traditionally, amides are synthesized from acid
chlorides and amines or by condensation of carboxylic
acids with amines using coupling reagents.[5] Later on,
several methods using alcohols or aldehydes under
oxidative amidation conditions have been developed
for amide synthesis.[6]
Aminocarbonylation of alkyl or aryl halides is an
efficient alternative method for amide synthesis, in
which the required intermediate carbonyl moiety can
be accessed in situ, in one step, from the readily avail-
able feedstock carbon monoxide and aryl halides.
Heck and co-workers have opened a new platform for
amide synthesis, since then the use of carbon monox- biologically active molecules.
Figure 1. Representative examples of amide bond-containing
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Stable and Reusable Binaphthyl-Supported Palladium Catalyst
Table 1. Optimization of the reaction conditions for the ami-
nocarbonylation.[a]
Scheme 1. Aminocarbonylation of aryl iodide using Pd-BNP
catalyst.
The initial study was carried out using 4-iodoto-
luene 1a and 4-methoxyaniline 2a as model substrates
with 2 equiv. of K2CO3 in the presence of 2 mol% of
Pd-BNP at 1108C in dry toluene in the presence of
CO. To our delight, the reaction was completed
within 24 h and afforded a 74% yield of the corre-
sponding amide N-(4-methoxyphenyl)-4-methylbenz-
amide 3a as product (Table 1, entry 1).
To improve the efficiency of this Pd-BNP-catalyzed
aminocarbonylaion, various bases, such as NEt3,
Na2CO3, 1,4-diazabicyclo[2.2.2]octane (DABCO) etc.
were screened. As expected, product 3a was isolated
in 95% yield by employing DABCO as base at 1108C
within 16 h (entry 4) and the results are summarized
in Table 1.
To improve the efficiency of this reaction, several
solvents were screened. Solvents other than toluene
such as THF, dioxane, methanol and water gave infe-
rior results (entries 6–9). The yield of 3a was reduced
when the reaction temperature was lower than 1108C
(entry 10). We also screened different equivalents of
amine 2a and DABCO used (entry 11–15). It was
found that 2 equiv. of 2a and 2 equiv. of DABCO
were necessary for the completion of this transforma-
tion (entry 4).When 2 mol% of Pd/C were used as cat-
alyst instead of Pd-BNP, a 45% yield of product 3a
was isolated (entry 19).
Using the optimized reaction conditions, the scope
of the Pd-BNP-catalyzed aminocarbonylation for the
synthesis of amides 3 was investigated using various
substituted aryl iodides 1 with amines 2 and the re-
sults are summarized in Table 2.
[a]
Reaction conditions: 0.5 mmol of 1a, 1.0 mmol of 2a,
2 mol% of Pd-BNP (10.6 mg, 10 wt% by ICP-OES analy-
sis) and 4 mL of solvent.
Isolated yield.
nr=no reaction.
1 equiv. of 2a.
1.5 equiv. of 2a.
1 equiv. of DABCO.
1.5 equiv. of DABCO.
3 equiv. of DABCO.
1 mol% of Pd-BNP.
In the absence of Pd-BNP.
In the absence of DABCO.
[b]
[c]
[d]
[e]
[f]
[g]
[h]
[i]
It was observed that when any electron-donating
group is present in the aromatic ring of either aryl io-
dides or aromatic amines, the reaction worked better
and good to excellent yields of the amides were isolat-
ed (3a–3g and 3n–3s) than when electron-withdrawing
[j]
[k]
[l]
2 mol% of Pd/C used.
groups were present in either of the two aromatic of anilines, formation of the corresponding amide did
rings (3h–3k and 3t). In the case of aliphatic secon- not take place even a trace amount. Heteroaryl io-
dary amines such as piperidine and morpholine, the dides such as 2-iodothiophene and 3-iodo-1-methyl-
reactions were very slow and low yields of the corre- 1H-indole were unreactive under the standard reac-
sponding amide were isolated (3u and 3v). Primary tion condition (3aa–3ab). The less reactive aryl bro-
amines such as phenylethylamine, benzylamine, pro- mides such as 4-bromotoluene and 4-bromoanisole
pylamine and n-butylamine also provided moderate had given poor yields, 9% and 11%, respectively, and
yields of the corresponding products (3w–3z). Also, aryl chlorides 4-chlorotoluene and 4-chloroanisole
when any ortho-substitution was present in the aro- were also remain unreactive under the optimized con-
matic ring of either aryl iodide or amines, no product dition employed. When 1,2-diiodobenzene was used
formation was observed. With substituents such as with 4-methoxyaniline 2a, double carbonylation took
acetyl and amide groups present in the para-position place and the N-substituted phthalimide 2-(4-methox-
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Nidhi Sharma and Govindasamy Sekar
Table 2. Substrate scope for aminocarbonylation using the Pd-BNP catalyst.[a,b]
[a]
Reaction conditions: 0.5 mmol of 1, 1.0 mmol of 2, 4 mL of PhMe.
Isolated yield.
4-Bromotoluene as aryl halide.
4-Bromoanisole as aryl halide.
Reaction carried out in a Schlenk pressure tube.
1,2-Diiodobenzene as the aryl iodide.
[b]
[c]
[d]
[e]
[f]
yphenyl)isoindoline-1,3-dione 5a was isolated in 65% action completed within 24 h and 90% yield of the
yield.[14]
corresponding amide 2-(4-methoxyphenyl)isoindoline-
After successfully completing the intermolecular 1,3-dione 5a[15] was isolated (Table 3, entry 1).
aminocarbonylation, the intramolecular aminocarbo- In order to explore the scope of the Pd-BNP cata-
nylation under the optimized reaction using 2-iodo-N- lyst, intramolecular aminocarbonylation was carried
(4-methoxyphenyl)benzamide 4a was carried out. Re- out using various 2-iodo-N-arylbenzamides 4 under
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UPDATES
Stable and Reusable Binaphthyl-Supported Palladium Catalyst
Table 3. Substrate scope for intramolecular aminocarbonyla-
tion using Pd-BNP catalyst.[a]
Scheme 2. Synthesis of a COX-2 inhibitor using Pd-BNP.
Scheme 3. Gram scale synthesis of amide 3a.
dotoluene 1a and 4-methoxyaniline 2a with 2 mol%
of Pd-BNP under the optimized reaction conditions
and the result is summarized in Figure 2.
We have recovered the catalyst for up to five cycles
and in all cycles, the Pd-BNP was quantitively recov-
ered. It is important to mention that in all the five
cycles, the recovered Pd-BNP catalyst gave more than
90% of isolated yield of product. TEM analysis of the
recovered catalyst after the fifth cycle showed that
there was hardly any change in particle size of the Pd-
BNP catalyst (Figure 3).[17]
[a]
Reaction conditions: 0.5 mmol of 4, 4 mL of PhMe.
Isolated yield.
[b]
the optimized reaction condition, which provided N-
substituted isoindoline-1,3-dione derivatives 5 in ex-
cellent yield (Table 3).
To check the applicability of Pd-BNP catalyst, we
also have synthesized a cyclooxygenase (COX-2) in-
hibitor, 5-methyl-2-(3,4,5-trimethoxyphenyl)isoindo-
line-1,3-dione 5h, having a half maximal inhibitory
concentration of IC50 =0.4 mM (Scheme 2).[2b] Cyclo-
oxygenase inhibitors are known to have anti-inflam-
matory activity and help to relieve pain.[16]
A gram scale experiment was performed by em-
ploying 1.09 g (5 mmol) of 1a under the optimized re-
action conditions to show the reliability of this syn-
thetic protocol. Aminocarbonylation proceeded
smoothly to afford 3a in 83% yield (Scheme 3).
To check the recyclability and reusability of the Pd-
BNP catalyst, the reaction was carried out using 4-io- Figure 2. Recycling of the Pd-BNP catalyst.
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Nidhi Sharma and Govindasamy Sekar
Figure 3. HR-TEM images of Pd-BNP catalyst before (left) and after the fifth catalytic cycle (right).
We carried out the aminocarbonylation reaction ous substituted isoindoline-1,3-dione derivatives in ex-
under optimized condition using 20 equiv. of mercury, cellent yield. This methodology provides an efficient
complete inhibition of the reaction was observed; way for the synthesis of a COX-2 enzyme inhibitor
even on allowing the reaction to proceed for up to having anti-inflammatory activity. The catalyst has
48 h. This experiment suggests that the catalyst is het- been recovered and reused up to five times without
erogeneous in nature. A leaching experiment was also any loss in particle size and reactivity.
performed using the hot filtration test in which Pd-
BNP catalyst was separated from the reaction mix-
ture. The reaction was carried out under the opti- Experimental Section
mized condition. After 2 h, the reaction mixture was
centrifuged; filtered and Pd-BNP catalyst was re- Typical Experimental Procedure for
moved. A 9% yield of 3a was obtained and yield was Aminocarbonylation (3)
determined by 1H NMR using 1,3,5-trimethoxyben-
Aryl iodide (0.5 mmol), amine (1 mmol), Pd-BNP catalyst
zene as internal standard. The Pd-BNP-free mother
(10.6 mg, 2 mol%) and DABCO (2 equiv.) were charged in
liquor (filtrate) was than further used to carry out the
an oven-dried reaction tube equipped with magnetic pellet
aminocarbonylation reaction under the similar condi-
tions for 24 h. There progress of reaction was ob-
served and a 25% yield of 3a was obtained by
1H NMR. ICP-OES analysis of a liquid aliquot with-
drawn from the reaction mixture after 2 h of the ami-
nocarbonylation reaction showed that a minimal of
0.034 ppm (0.21 wt%) of Pd was present in the solu-
tion, which could be reason for the progress of the re-
action after separating the catalyst from the reaction
mixture.
and capped with septum. The reaction tube was evacuated
and freshly distilled toluene (4 mL) was added. The reaction
tube was refilled with CO using a balloon and stirred at
1108C until completion of the reaction as monitored by
TLC. The reaction mixture was then allowed to cool to
room temperature. Then the solvent was completely evapo-
rated on a rotary evaporator and the residue extracted with
ethyl acetate (3”10 mL). The organic phase was dried over
Na2SO4 and concentrated under vacuum. The resulting reac-
tion mixture was purified by column chromatography on
silica gel (hexanes:ethyl acetate) to get amide product 3.
In conclusion, an efficient, cost-effective binaphth-
yl-supported palladium (Pd-BNP) catalyst for the
aminocarbonylation of aryl iodides using carbon mon-
oxide and amines for the synthesis of amides has
been developed. The scope of the reaction has been
studied with regard to various aryl iodides and amines
to yield the corresponding amides in good yields. The
Pd-BNP catalyst was also successfully utilized for the
Typical Experimental Procedure for Intramolecular
Aminocarbonylation (5)
2-Iodo-N-arylbenzamide
4 (0.5 mmol), Pd-BNP catalyst
(10.6 mg, 2 mol%) and DABCO (2 equiv.) was charged in
an oven-dried reaction tube equipped with magnetic pellet
and capped with septum. The reaction tube was evacuated
intramolecular aminocarbonylation and yielded vari- and freshly distilled toluene (4 mL) was added. The reaction
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UPDATES
Stable and Reusable Binaphthyl-Supported Palladium Catalyst
tube was refilled with CO using a balloon and the mixture
stirred at 1108C until completion as monitored by TLC. The
reaction mixture was then allowed to cool to room tempera-
ture. Then the solvent was completely evaporated on
a rotary evaporator and the residue extracted with ethyl
acetate (3”10 mL). Then the organic phase was dried over
Na2SO4 and concentrated under vacuum. The resulting reac-
tion mixture was purified by column chromatography on
silica gel (hexanes: ethyl acetate) to get intramolecular ami-
nocarbonylated product, N-substituted isoindoline-1,3-dione
5.
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Acknowledgements
We thank DST nano mission (SR/NM/NS-1034/2012(G)) for
financial support. NS thanks CSIR, New Delhi for a senior
research fellowship.
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was prepared using our previously reported procedure.
The catalyst displays various properties such as air and
moisture stability, is easy to store, shelf stable, highly
active and reusable.
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[14] A 1H NMR study after completion of the reaction
showed 72% conversion and 28% of 1,2 diiodobenzene
remaining unreacted under the optimized reaction con-
[17] An average size of 4–5 nm for Pd-BNP was observed.
320
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Adv. Synth. Catal. 2016, 358, 314 – 320