Chemoselective Synthesis of N-arylbenzamides and Benzoyloxyacetanilides from Aryl Isocyanides: Styrene as Aryl and Arylcarboxymethylene Source

Article abstract of DOI:10.1002/adsc.201800107

Styrenes serve as unique aryl or arylcarboxymethylene source towards aryl isocyanides in the presence of Cu(II)/TBHP, and yield N-arylbenzamides or benzoyloxyacetanilides respectively. The chemoselectivity of the reaction is controlled by the nature of the substituents present on styrene ring. Whereas styrenes substituted with electron-releasing alkyl and alkoxy groups yield N-arylbenzamides, unsubstituted styrene and those with electron-withdrawing substituents furnish benzoyloxyacetanilides as the major product. With benzylamines as the substrate, N-arylbenzamides are formed exclusively as they act only as an aryl donor. TBHP serves as a promoter and oxygen source. Both the pathways are believed to proceed through an initial oxidative C?C bond cleavage of styrene. (Figure presented.).

Full text of DOI:10.1002/adsc.201800107

Title: Chemoselective synthesis of N-arylbenzamides and
benzoyloxyacetanilides from aryl isocyanides: Styrene as aryl
and arylcarboxymethylene source
Authors: Poonam Sharma and Nidhi Jain
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800107
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10.1002/adsc.201800107
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Chemoselective synthesis of N-arylbenzamides and
benzoyloxyacetanilides from aryl isocyanides: Styrene as aryl
and arylcarboxymethylene source
Poonam Sharmaa and Nidhi Jaina*
a Department of Chemistry, Indian Institute of Technology Delhi, New Delhi-110016 (India)
Fax: (+91-011-26581102), phone: (+91-011-26591562); e-mail:njain@chemistry.iitd.ac.in
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
that styrene could serve as an aryl source, and result
in an amidation reaction with isocyanides to yield N-
arylbenzamides.
Abstract. Styrenes serve as unique aryl or
arylcarboxymethylene source towards aryl
isocyanides in the presence of Cu(II)/TBHP, and
yield N-arylbenzamides or benzoyloxyacetanilides
respectively. The chemoselectivity of the reaction is
controlled by the nature of the substituents present on
styrene ring. Whereas styrenes substituted with
electron-releasing alkyl and alkoxy groups yield N-
arylbenzamides, unsubstituted styrene and those with
Scheme 1. Oxidative coupling reactions with
styrene/TBHP
electron-withdrawing
substituents
furnish
benzoyloxyacetanilides as the major product. With
benzylamines as the substrate, N-arylbenzamides are
formed exclusively as they act only as an aryl donor.
TBHP serves as a promoter and oxygen source. Both
the pathways are believed to proceed through an
initial oxidative C−C bond cleavage of styrene.
The traditional method for N-arylbenzamide
synthesis involves condensation reaction between
carboxylic acid and amine in presence of
stoichiometric amount of coupling reagent.[6] In
recent years, however, development of catalytic
and atom-economic approaches for amide bond
formation have gained a lot of impetus.[7] For
this, new reaction pathways from varied starting
materials using transition metals as catalysts are
being explored.[8] In this context, with aryl
isocyanides as an amide source; arenes
substituted with leaving groups like halide,[9]
diazonium ion,[10] boronic acid[11] and aldehyde[12]
have been employed as coupling partners
(Scheme 2 (i)). To the best of our knowledge,
styrenes have never been used as substrates for
the synthesis of N-arylbenzamides. Herein, we
present an unprecedented copper acetate/TBHP
catalyzed amidation reaction between styrenes
and aryl isocyanides (Scheme 2 (iii)).
Keywords: Styrene; Aryl isocyanide; N-
arylbenzamide; Benzoyloxyacetanilide;
chemoselectivity.
Transition metal catalyzed oxidative cross-couplings
for C-C and C-O bond formations have made some
major advancements in the last few decades. In these
reactions, oxidants play an important role in
activating inert C-H bonds.[1] With TBHP as the
oxidant, terminal alkenes particularly styrene is
known to produce useful reaction intermediates. It
behaves as an aroyl surrogate; and has been used for
aroylation of coumarins, azenes and hetero(arenes)
under metal-free or palladium catalyzed conditions as
shown in (Scheme 1(i)).[2] Recently, Patel et al
demonstrated that styrene could also serve as an
arylcarboxy surrogate in a copper acetate/TBHP
catalyzed ortho-benzoxylation of 2-phenylpyridines
(Scheme 1(ii)).[3] It has also been reported as a source
of aryl radical in the presence of TBHP under metal-
free conditions, and has been used for coupling with
arenes to form biaryls (Scheme 1(iii)).[4] Inspired by
these pioneering works and pursuing our research
towards development of new oxidative coupling
protocols,[5] we decided to investigate the reaction of
styrenes with aryl isocyanides as coupling partners in
presence of copper acetate and TBHP. We anticipated
Interestingly, our investigations divulged that the
reaction exhibits a unique chemoselectivity, and
yields
benzoyloxyacetanilides
either
N-arylbenzamides
or
A
selectively.
multicomponent Passerini reaction assembling alkyl
isocyanide, aldehyde and carboxylic acid is the only
1
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10.1002/adsc.201800107
Advanced Synthesis & Catalysis
dimethyl styrene (2a, 2 equiv) in presence of
copper acetate (20 mol%) and TBHP (5 equiv) in
chlorobenzene at 120 oC. As expected, the
formation of 2,5-dimethyl-N-(p-tolyl)benzamide
available route to access acyloxyacetanilides but does
not work for benzoyloxy derivatives (Scheme 2
(ii)).[13] In this work, we report for the first time that
styrenes can act as an arylcarboxymethylene source
in presence of copper acetate/TBHP and can be used
for direct synthesis of benzoyloxyacetanilides.
(
3a) was seen after 8 h (Table 1, entry 1).
The reaction was optimized with respect to solvent,
oxidant, catalyst and temperature. Replacing
chlorobenzene with solvents like dioxane, ACN, THF
and H2O decreased the yield (entries 2-5) while it
remained same under solvent-free conditions (entry
6). Control experiments in the absence of copper
catalyst (entry 7) and TBHP (entry 8) did not give
any product showing that both were essential for the
reaction to proceed. With CuI, yield lowered to 70%
(entry 9) while with Cu(OTf)2, only traces of 3a were
seen (entry 10). Employing other oxidants like
hydrogen peroxide, potassium peroxodisulphate and
DTBP (entry 11-13) did not give any product
suggesting that TBHP was very specific, and might
not only be serving as an oxidant but also furnishing
hydroxyl group in the amide. The product yield
stayed unaffected when the reaction was performed
under N2 or O2 atmosphere (entry 14).
Scheme 2. Isocyanide as precursor for synthesis of N-
arylbenzamide and acyloxyacetanilide
Scheme 3. Amidation: Scope with aryl isocyanides and
styrenes
Table 1. Optimization of the Reaction Conditionsa
Entry Solvent
Oxidant Catalyst
Cu(OAc)2
Yield (%)b
1
Chlorobenzene TBHP
79
2
Dioxane
ACN
THF
H2O
-
TBHP
TBHP
TBHP
TBHP
TBHP
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
-
69
aReaction conditions: 1 (0.5 mmol, 1 equiv), 2 (1.0 mmol,
2 equiv), Cu(OAc)2 (20 mol%), TBHP (5 equiv), 0.2 ml
chlorobenzene at 120 oC for 8 h.
3
37
4
62
5
65
Further, reducing the amounts of copper acetate
or TBHP resulted in lower product yields (entries
15 and 16). Thus, the best optimized conditions
were found with 20 mol% copper acetate and 5
6
75
7
Chlorobenzene TBHP
Chlorobenzene
-
8
-
Cu(OAc)2
CuI
-
o
equiv TBHP in chlorobenzene at 120 C. The
9
Chlorobenzene TBHP
Chlorobenzene TBHP
Chlorobenzene H2O2
Chlorobenzene K2S2O8
Chlorobenzene DTBP
Chlorobenzene TBHP
Chlorobenzene TBHP
Chlorobenzene TBHP
70
scope of amidation was explored by taking
various aryl isocyanides substituted with 4-
methyl, 4-chloro and 3-nitro groups as shown in
scheme 3. With 2,5-dimethyl substituted styrene
10
11
12
13
14
15
Cu(OTf)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Trace
-
-
-
(
2a), the corresponding amides (3a-3c) were
79c,d
72e, 67f
68g, 56h, 47i
formed in moderate yields (72-76%). The
reaction of 2a with 2-phenyl and 2-naphthyl
substituted phenyl isocyanides also went
smoothly, and furnished amides (3d-3f) in good
yields. With monosubstituted 2-methyl, 4-tert-
butyl, and 4-methoxy styrene, the corresponding
amides (3g-3k) were obtained in 65-75% yields.
Lower yields of 3i and 3j (65% and 68%
respectively) were probably due to steric effects
of tert-butyl group in styrene.
16
a
Reaction conditions: 4-Methylphenylisonitrile 1a (0.25
mmol, 1 equiv), 2,5 dimethylstyrene 2a (0.5 mmol, 2
equiv), Catalyst (0.05 mmol, 20 mol%), Oxidant (1.25
mmol, 5 equiv), 120 C, 8 h; b HPLC yield based on %
o
conversion; c N2 atmosphere; O2 atmosphere; Cu(OAc)2
d
e(0.037 mmol, 15 mol%), (0.025 mmol, 10 mol%); TBHP
f
g(0.75 mmol, 3 equiv, h(0.5 mmol, 2 equiv), i(0.25 mmol, 1
equiv)
In a surprising revelation, when the reaction of 2-
isocyano-1,1'-biphenyl (1d) was carried out with
The work initiated with the reaction of 4-
methylphenylisonitrile (1a, 1 equiv) and 2,5
2
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10.1002/adsc.201800107
Advanced Synthesis & Catalysis
active depsipeptides etc.[15] Though useful, the
reaction suffers from inherent limitations of giving
complex product mixtures due to the presence of
multi-intermediates in the MCR,[13b,13d] its
sluggishness in organic solvents giving low product
yields, and unsuitability with aryl isocyanides as
substrates.[16-17] Under the prevailing shortcomings,
our strategy promises to offer an efficient route to
synthesize benzoyloxyacetanilides directly starting
from styrene and aryl isocyanide.
Scheme 4. Synthesis of Benzoyloxyacetanilides
To understand the reaction mechanism, several
control experiments were carried out as shown in
scheme 5. The involvement of free-radical
species in the reaction was ascertained by
performing quenching studies with a radical
aReaction conditions: 1 (0.5 mmol, 1 equiv), 2 (1.0 mmol,
2 equiv), Cu(OAc)2 (20 mol%), TBHP (5 equiv), 0.2 ml
o
chlorobenzene at 120 C for 8h. Molecular structure of
scavenger
(2,2,6,6-tetramethylpiperidin-1-
compound 4a obtained from single crystal X-ray
analysis.[14] ORTEPS for C, N and S were set at 40%
probability (see the supporting Information for details).
yl)oxidanyl (TEMPO). It was found that under
optimized conditions, the reaction of 1a with 2a
in presence of TEMPO gave the corresponding
product 3a in 23% yield with 2 equiv of TEMPO;
while the reaction quenched completely with 5
equivalents (Scheme 5(1a)). The inhibitory effect
of TEMPO suggested the reaction to proceed via
radical intermediate(s). Even with unsubstituted
styrene (2e), the reaction quenched completely
with 5 equiv of TEMPO, and formation of the
corresponding benzoyloxyacetanilide (4b) was
not seen (Scheme 5(1b)). To ascertain the
the unsubstituted styrene (2e), the desired amide was
not obtained. Instead, 2-([1,1'-biphenyl]-2-ylamino)-
2-oxoethyl benzoate (4a) formed unexpectedly as a
single product in 78% yield. Single-crystal X-ray
analysis confirmed the structure of 4a.[14] Exploring
further, we found that even with 4-methyl isocyanide
(1a);
2e
yielded
the
corresponding
benzoyloxyacetanilide derivative 4b as the major
product (70%). Intrigued by this, we investigated
the scope with 4-chlorostyrene, and treated it with hydroxyl source for isocyanide hydrolysis;
reaction of 1a with 2a was performed in the
presence of added D2O. No incorporation of
deuterium in 3a suggested that there was no
involvement of moisture or water in the amide
bond formation (Scheme 5(2)).
The next challenge was to identify the source of
methylene unit in 4. We envisaged that methylene
insertion could be via in situ generation of
formaldehyde and benzoyloxy precursors from
styrene, followed by coupling with aryl
isocyanide. While styrene is known to be an Ar[4]
and ArCOO[3] surrogate; its potential as an
ArCOOCH2 equivalent is yet undiscovered. To
confirm our belief, 1a was reacted with
formaldehyde and benzoic acid; both in the
presence and absence of copper catalyst. We
found that under both conditions, the desired
product 4b was formed in similar yields (Scheme
5(3a)). In fact, even with electron rich 4-(tert-
aryl isocyanides substituted with 2-methyl, 2-
phenyl, 2-naphthyl and 4-fluoro groups.
Interestingly, we found that with all these
substrates,
the
corresponding
benzoyloxyacetanilides formed exclusively (4c-
4f, 69-74%), and only traces of the amide product
were seen along with 4c and 4d. Apparently, these
observations suggested that somehow the electronics
of styrene was involved in controlling the product
selectivity. Next, we tried it with 4-fluorostyrene; and
found that both with 1e and 1a, the corresponding
fluoro-substituted benzoyloxy derivatives 4g and 4h
derivatives were formed in 72 and 65% yields
respectively. Changing the position of fluoro group
did not affect the product yield, and 4i was obtained
in 67% yield on reaction of 1e with 3-fluorostyrene.
The reaction was extended to heterocyclic styrenes
such as 4-vinyl pyridine and 3-vinyl thiophene. The
reaction of 1e with 4-vinyl pyridine gave 2-([1,1'-
biphenyl]-2-ylamino)-2-oxoethyl isonicotinate (4j) in
76% yield; and 3-vinylthiophene reacted with 1a to
give 4k in 74% yield. Unfortunately, the reaction
failed with styrenes substituted with strong electron-
withdrawing 4-NO2, 4-COCH3, and 4-CN groups,
and no product formation was seen. It is important to
reiterate that the Passerini reaction is the only
reported way to synthesize acyloxyacetanilides
present in many natural products, pharmacologically
butyl)benzoic
acid,
the
corresponding
benzoyloxyacetanilide (4l) was obtained which
did not form otherwise on starting with 4-tert-
butyl styrene as the precursor, and gave the amide
instead (Scheme 5(3b)). Moreover, the reaction
between 1a and 2e in the absence of copper
catalyst did not yield 4b, suggesting that copper
was required for generation of formaldehyde and
benzoyloxy precursors from styrene (Scheme
5(3c)). Further with CD2O, the deuterated analog
3
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10.1002/adsc.201800107
Advanced Synthesis & Catalysis
of 4b-D2 was obtained which showed residual
methylene protons at 4.95 ppm (Scheme 5(3d)).
Scheme 5. Experiments for mechanistic investigation
desired products 3s and 3t in 75% and 67% yields
respectively.
On the basis of these experimental findings and
the available literature,[3,18]
a
plausible
mechanism for the reaction has been proposed
(see Figure S1 in the Supporting Information).
Scheme 6. Amidation: Scope with benzylamines
aReaction conditions:
mmol, 2 equiv), Cu(OAc)2 (20 mol%), TBHP (5
1 (0.5 mmol, 1 equiv), 5 (1.0
o
b
equiv), 0.2 ml chlorobenzene at 120 C for 8h, 4-
c
Methoxybenzyl alcohol as substrate, 4-Chlorobenzyl
alcohol as substrate.
Additionally, the reaction of 1a with benzoic acid
did not afford 4b, reassuring that formaldehyde
generated in situ from styrene was the only
source of methylene unit in 4b (Scheme 5(3e)).
Further, that styrene is the source of
formyl/methylene unit also became evident when
In summary, we illustrate the first time use of styrene
as the surrogate for arylcarboxymethylene group
(ArCOOCH2) in presence of Cu(OAc)2 and TBHP,
and
employ
it
for
the
synthesis
of
benzoyloxyacetanilides on coupling with aryl
isocyanides. A unique chemoselectivity is exhibited
by virtue of the substituents present on benzene ring
of styrene. On reaction with aryl isocyanides, it acts
either as an Ar or ArCOOCH2 source furnishing N-
the reaction of aryl isocyanides (
out with benzylamines ( ) instead of styrenes (
(Scheme 6). It was found that irrespective of the
nature of the substituent on the aryl ring of , aryl
amides ( ) formed exclusively in all cases. This
1) was carried
5
2)
5
arylbenzamides
or
benzoyloxyacetanilides
3
respectively. Benzylamines yield N-arylbenzamides
exclusively irrespective of the nature of substituents
present on benzene ring, thus acting only as an Ar
source. The reaction is believed to proceed through
two alternative pathways involving radical
intermediates. More detailed investigations to probe
into the mechanism are under way.
was not surprising since unlike styrenes,
benzylamines could not furnish HCHO during the
reaction which is required for the formation of
benzoyloxyacetanilides (4). The reaction of
unsubstituted benzylamine with various aryl
isocyanides substituted with p-methyl, p-chloro,
and p-fluoro groups as well as with naphthyl
substituent gave the corresponding amides (3l-3o)
in good yields. Furthermore, benzylamines
substituted with electron donating p-methyl and p-
methoxy groups behaved similarly, and the
corresponding products (3p-3i) were obtained in 69-
77% yields. Even with p-chloro and p-fluoro
substituted benzylamine, the corresponding amides
3t-3u were obtained in contrast to the styrene
reaction where benzoyloxyacetanilides were formed.
Experimental Section
Representative method for the synthesis of
benzamides (3a-3k):
1-Isocyano-4-methylbenzene (1a) (58.5 mg, 0.5
mmol) was added to a mixture of 2,5 dimethyl
styrene 2a (132 mg, 1.0 mmol), Cu(OAc)2 (18 mg, 20
mol%) and TBHP (70% in water) (321 µL, 5 equiv)
dissolved in 200 µL chlorobenzene and refluxed for 8
o
h at 120 C. The reaction mixture was monitored by
However,
with
strongly
withdrawing
p-
thin layer chromatography. The mixture was
extracted with ethyl acetate, dried over Na2SO4 and
evaporated under reduced pressure. The compound
was purified by column chromatography to give 3a
nitrobenzylamine, the reaction did not take place at
all. As anticipated, benzyl alcohols underwent a
similar oxidative reaction (Scheme 6). 4-methoxy,
and 4-chloro substituted benzyl alcohols yielded the
4
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10.1002/adsc.201800107
Advanced Synthesis & Catalysis
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(86 mg, 72%) as a white solid.
Representative method for the synthesis of
benzamides (3l-3u):
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1-Isocyano-4-methylbenzene (1a) (58.5 mg, 0.5
mmol) was added to a mixture of benzylamine (5)
(121 mg, 1.0 mmol), Cu(OAc)2 (18 mg, 20 mol%)
and TBHP (70% in water) (321 µL, 5 equiv)
dissolved in 200 µL chlorobenzene and refluxed for 8
o
h at 120 C. The reaction mixture was monitored by
thin layer chromatography. The mixture was
extracted with ethyl acetate, dried over Na2SO4 and
evaporated under reduced pressure. The compound
was purified by column chromatography to give 3l
(82 mg, 78%) as a white solid.
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Representative method for the synthesis of
benzoyloxyacetanilides (4a-4k):
2-Isocyano-1,1'-biphenyl (1e) (89.5 mg, 0.5 mmol)
was added to a mixture of styrene (2e) (104 mg, 1.0
mmol), Cu(OAc)2 (18 mg, 20 mol%) and TBHP
(70% in water) (321 µL, 5 equiv) dissolved in 200 µL
[8] a) M. B. Ibrahim, R. Suleiman, M. Fettouhi, B. E. Ali,
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o
chlorobenzene and refluxed for 8h at 120 C. The
reaction mixture was monitored by thin layer
chromatography. The mixture was extracted with
ethyl acetate, dried over Na2SO4 and evaporated
under reduced pressure. The compound was purified
by column chromatography to give 4a (129 mg, 78%)
as a white solid.
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Acknowledgements
P.S. thanks MHRD, IIT Delhi for her graduate fellowship. The
authors thank CSIR, India (02(180)/14/EMR-II) for financially
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and SCXRD facility at IIT Delhi.
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5
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10.1002/adsc.201800107
Advanced Synthesis & Catalysis
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This article is protected by copyright. All rights reserved.

10.1002/adsc.201800107
Advanced Synthesis & Catalysis
FULL PAPER
Chemoselective synthesis of N-arylbenzamides and
benzoyloxyacetanilides from aryl isocyanides:
Styrene as aryl and arylcarboxymethylene source
Adv. Synth. Catal.2018, Volume, Page – Page
Poonam Sharma, Nidhi Jain*
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