Aerobic oxidative acylation of nitroarenes with arylacetic esters under mild conditions: Facile access to diarylketones

Article abstract of DOI:10.1039/c7ob02865b

A facile and regioselective base-mediated aerobic oxidative acylation of nitroarenes to access diarylketones under mild conditions has been developed. It features the use of bench-stable and readily available arylacetates as acyl surrogates, and the absence of transition-metals and synthetic oxidants. This protocol involves a cascade CDC/oxidative decarboxylation process.

Full text of DOI:10.1039/c7ob02865b

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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PAPER
Aerobic oxidative acylation of nitroarenes with arylacetic esters
under mild conditions: Facile access to diarylketones
Received 00th January 20xx,
Accepted 00th January 20xx
Jiang-Sheng Li,a* Qian Yang, a‡ Fan Yang,b,a‡ Guo-Qin Chen,a Zhi-Wei Li,a Yin-Jie Kuang,a Wei-Jing
Zhanga and Peng-Mian Huang a
DOI: 10.1039/x0xx00000x
A facile and regioselective base-mediated aerobic oxidative acylation of nitroarenes to access diarylketones under mild
conditions has been developed. It features the use of bench-stable and readily available arylacetates as acyl surrogates,
www.rsc.org/
and the absence of transition-metals and synthetic oxidants. This protocol involves
decarboxylation
a
cascade CDC/oxidative
process.
mediated TM-free aerobic CDC indolylation of nitroarenes with
indoles in an open flask, enabling the facile access to -(2/4-
Introduction
β
nitroaryl)-indoles under mild conditions (scheme 1).5i
Following this work, they have further presented the synthesis
of unsymmetrical diaryl acetamides through TM-free CDC
reactions of nitroarenes sp2 C-H and amides sp3 C-H bonds
(scheme 1).5j However, there seem few reports concerning the
direct CDC version of nitroarenes with arylacetates under TM-
free and aerobic conditions.6
The cross-dehydrogenative coupling (CDC) reaction is of
fundamental importance in organic synthetic community,
which readily enables the efficient construction of C-based
chemical bonds, especially C-C bonds.1 Due to the superior
sustainability and environmental compatibility, significant
progress in the CDC chemistry has flourished mostly in the last
decade.2 These reactions can undergo catalytically using
transition-metals (TMs) such as copper3 or iron salts4
combined with synthetic oxidants or elemental oxygen.
Nevertheless, one of the challenging difficulties encountered
in practical industrial applications is to efficiently remove trace
amounts of transition-metal residues from coupled products,
especially pharmaceuticals. Accordingly, tremendous efforts
have been devoted to developing novel TM-free CDC
reactions,5 but aerobic CDC reactions without TM catalysts are
still very limited.5c-k Most of them relates to the acid-catalysed
aerobic C-C bond-forming reactions centring on the benzylic
The incorporation of an acyl substituent into arenes is of
central importance in organic transformations due to the
extensive applications of arylketones in synthesis, materials
and pharmaceuticals.7 Thus the numerous methods have been
8
developed.7a,
Remarkably,
the
direct
acylative
functionalization of electron-deficient arenes including
nitroarenes is a great challenge. To our knowledge, the direct
and efficient acylation reactions of electron-deficient
nitroarenes sp2 C-H bonds without any directing group have
not been reported. Continuing our effort of t-BuONa-mediated
TM-free autoxidative carbonylation of diarylmethylenes,9
herein, we present a TM-free aerobic formal acylation reaction
of simple nitroarenes with readily available and bench-stable
arylacetic esters under very mild conditions through a cascade
CDC/oxidative decarboxylation process (scheme 1).
sp3
C-H
bonds
in
5f
xanthenes,5e
acridines,5e
tetrahydroisoquinolines5e, and glycine derivatives5g in the
absence of metal catalysts. Very recently, the TM-free aerobic
CDC reactions have been disclosed to accomplish the C-C bond
formation of nitroarenes sp2 C-H bonds mediated by bases
such as tertiary butoxides.5h-j In 2013, the group of Ess
reported a t-BuONa-mediated TM-free aerobic CDC alkylation
of nitroarenes with ketones, allowing regiospecific synthesis of
Previous work
alkylation or arylation
NO2
Nu
NO2
t-BuOM (M= K, Na)
momo-
α
-arylated ketones under open-to-air conditions
R
R
+
NuH
R
DMSO
H
(scheme 1).5h Later, Kumar et al has developed a t-BuOK-
O
H
R2
NR1R2
R1
Ar
N
H
H
O
(2013, Ess)
(2015, Kumar)
(2016, Kumar)
This work
O
acylation
NO2
t-BuONa/air
H
H
Ar
R
+
R
DMSO
Ar
CO2R'
O2N
Scheme 1 Previous and current studies.
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reaction under O2 balloon instead of open air didn’t improve
the yield of the desired ketone 2a (entry 20, Table 1). After the
further optimization with respect to the equivalents of base,
nitrobenzene and the concentration (please see ESI), the
optimum acylation conditions were established: NaOtBu (2.0
equiv)-mediated acylation of 1a (2.0 equiv) with 2a (0.2 mmol)
Results and discussion
Table 1 Optimization of the oxidative acylation conditionsa
o
in dry DMSO (0.5 ml) in open flask at 45 C, providing 3aa in
Entry
Base
Solvent
Time (h) T (oC)
Yieldb (%)
the isolated 80% yield.
1
2
3
4
5
6
7
8
NaOtBu
NaOtBu
NaOtBu
NaOtBu
NaOtBu
NaOtBu
K2CO3
KOtBu
NaH
KOH
NaOH
DBU
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
CH3CN
DMF
CH3OH
CH2Cl2
THF
EtOAc
DMSO
DMSO
12
12
12
8
3
3
8
3
3
3
3
8
3
3
8
3
8
3
25
15
10
35
45
60
45
45
45
45
45
45
45
45
45
45
45
45
45
45
70
65
50
77
80
56
N.R.
75
65
20
50
N.R.
25
35
N.R.
10
40
10
65
76
With the optimized reaction conditions in hand, we set out
to study the scope of the methyl arylacetic esters used in this
TM-free base-mediated autoxidative acylation reaction, and
the results are listed in Table 2. In general, all the methyl
arylacetates except 2k tested smoothly underwent the
oxidative acylation to give their corresponding ketones
moderate to good yields when nitrobenzene 1a was used as
reaction partner (3aa 3aj). The introduction of the substituent
to the benzene ring of the arylacetate remarkably resulted in
the efficiency loss (3ab 3aj). Moreover, the electron-donating
3 in
9
10
11
12
13
14
15
16
17
18
19c
20d
-
2
NaOtBu
NaOtBu
NaOtBu
NaOtBu
NaOtBu
NaOtBu
NaOtBu
NaOtBu
-
groups (-Me, -OMe) seemed to more disfavor the acylation
occurrence than the electron-withdrawing one (-Cl). However,
the group CF3 delivered only 38% yield (3aj). The steric effects
of the substituents on the reaction were observed. Surprisingly,
the steric hindrance of the group accelerated this oxidative
acylation to some extent. For example, the groups such as -Me,
-OMe and -Cl, at the ortho-position resulted in the higher
yields than at the para-position. It should be pointed out that
2f led to the formation of complex system under standard
conditions, and yielded and isolated the acylation product 3af
(22%) at 0 oC. Besides, methyl 2,6-dichlorophenylacetate 2k
3
3
a
Reaction was performed using 1a (0.4 mmol), 2a (0.2 mmol), base (0.4 mmol),
dry solvent (0.5 mL) in open flask unless otherwise stated. b Isolated yield.
DMSO was not dried. d Under O2 balloon. N.R. = No reaction.
c
Our initial investigation on this acylation chemistry
commenced by the treatment of nitrobenzene 1a with methyl
phenylacetate 2a using the strong base NaOtBu (2.0 equiv) in
dry DMSO under open air atmosphere at room temperature
(entry 1, Table 1). Delightedly, the acylation product 4-nitro-
diphenylketone 3aa was formed regioselectively and isolated
in 70% yield, with a concomitant normal CDC product 2-
arylated phenylacetic ester. Decreasing the reaction
temperatures diminished the yields of 3aa, while elevating the
temperatures significantly increased those of 3aa (entries 2, 3
vs 4, 5, Table 1). However, the higher temperature of 60 oC
gave rise to the dramatic fall in the yield (entry 6, Table 1).
Therefore, the reaction at 45 oC was preferred, wherein the
ketone 3aa was isolated in 80% yield. The other inorganic
bases such as K2CO3, KOtBu, NaH, KOH, and NaOH were
screened (entries 7-11, Table 1). It was found that the strong
bases delivered better yields, while the weak base K2CO3 could
not initiate the reaction with the materials recovered. Likewise,
the organic base DBU was ineffective for this chemistry (entry
12, Table 1). Typically, DMSO has been used as best solvent in
base-mediated autoxidative reactions reported previously.5h-j, 9
Nevertheless, the other solvents were further considered,
including CH3CN, DMF, CH3OH, CH2Cl2, THF, and EtOAc (entries
13-18, Table 1). The results showed that all the
aforementioned solvents furnished worse efficiencies than
DMSO. Noteworthy, the protic solvent CH3OH afforded no
product, due to its strong acidity disfavoring the formation of
2a carbanion (entry 15, Table 1). Similarly, a trace amount of
water in the undried DMSO imposed an adverse effect on the
reaction yield (entry 19, Table 1). Additionally, performing the
Table 2 Oxidative acylation of different 2-arylacetates with nitrobenzenea
O
R1
NO2
CO2Me
R2
R2
4
O2N
1a
2a-k
3
O
O
O
O2N
O2N
O2N
3ac 37%
3ab 38%
3aa 80%
O
O
OMe
O
OMe
O2N
OMe
O2N
O2N
3af 22%b
3ad 41%
3ae 43%
O
Cl
O
O
Cl
O2N
O2N
O2N
Cl
3ag 63%
3ah 60%
3ai 55%
O
CO2Me
Cl
O2N
CF3
O2N
Cl
4ak 30% (35%b)
3aj 38%
a
Conditions: nitrobenzene 1a (0.4 mmol), arylacetates
2
(0.2 mmol), t-
b
BuONa (0.4 mmol), dry DMSO (0.5 mL), 45 oC for 3 h in open-to-air flask.
Performed at 0 oC for 2 h. Isolated yields.
2 | J. Name., 2012, 00, 1-3
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generated only the CDC ester 4ak, whether at 45oC (30% yield) carbonylation reaction preferably occurred by the replacement
or at 0 oC (35% yield). This may be due to the difficulties in the of the Cl moiety instead of hydrogen atom, whereby the same
formation of 4ak carbanion by the hindered base NaOtBu, and products with those derived from 1a were obtained in
in the autoxidative transformation with molecular O2.
moderate to good yields (3fa & 3fc). It is disappointed to find
Next, we turned our attention to the nitroarene reaction that 2-nitrobenzonitrile 1g and 2-nitrotoluene 1h are bad
partners, as shown in Table 3. 3-Chloro-4-nitrobenzene 1b was substrates. 1g was almost fully converted, but no
found to produce its expected acylation products
3. Its corresponding ketone detected. 1h was recovered
reaction with 2a afforded the desired ketone 3ba in 90% yield, quantitatively after workup.
and with 2j delivered 3bj in 69% yield. In two cases of 3ba and
Surprisingly, when it came to 2-CF3-nitrobenzene 1i, the
3bj, the efficiencies are higher compared to those of 3aa and cascade oxidative reaction yielded an abnormal product 3ia via
3aj. With regard to 2f, the CDC product 4bf was obtained in 39% the subsequent nucleophilic displacement of the nitro group
yield at 0 oC. Likewise, 3-bromo-4-nitrobenzene 1c readily by the -OMe group generated in the oxidative decarboxylation
reacted with 2a and 2c, providing the expected ketones 3ca step (scheme 2, 1i).10 In the case of 3-nitrotoluene 1j, the
and 3cc in 74% and 43% yields, respectively. However, the abnormal reaction occurred in the same manner, affording the
reaction of 1,3-dinitrobenzene 1d with 2a gave only the CDC 4-methoxylated ketone 3ja in 34% yield (scheme 2, 1j). More
ester 4da in 40% yield under standard conditions. 1- interestingly, the use of 4-nitroanisole 1k gave rise to the 51%
Nitronaphthalene 1e is an effective coupling partner. Its yield of a denitro-coupling product 3ka, where the nitro group
reaction with 2a generated our desired product 3ea, along was formally displaced by an acyl group (scheme 2, 1k).
with the intermediate 4ea unconverted even for the prolonged
time, while with 2e only the ketone 3ee was isolated in 25%
yield. When 4-chloronitrobenzene 1f was used instead, no
ortho-nitro ketones were detected.
A competitive SN-
Ar/oxidative decarboxylative
Table 3 Oxidative acylation of 2-arylacetates with different nitroarenes a
Scheme 2 Exceptional examples related to the nitro displacement.
O
NO2
R1
CO2Me
R1
R2
R2
4
X
O2N
Besides, we changed the alkyl groups in phenylacetates
used in this transformation, to scrutinize their effect on
oxidative acylation efficiency (scheme 3). It was found that the
ethyl ester 2l led to the notably lower yield of 3aa than the
methyl version 2a, and moreover the iso-propyl and tert-butyl
1b-g
2
3
Cl
O
Cl
O
Cl
O
OMe
O2N
O2N
O2N
variants (2m
& 2n) can’t realize such acylation reaction under
3ba 90% (X = H)
3bc 35% (X = H)
3be 40% (X = H)
the standard conditions.
Br
O
Cl
O
Cl
CO2Me
O
NO2
O2N
O2N
CF3 O2N
OMe
CO2R
-BuONa (2 equiv)
t
4bf 39%b (X = H)
3ca 74% (X = H)
3bj 69% (X = H)
DMSO, 45 oC, 3 h
open flask
NO2
1a (2 equiv)
2
(0.2 mmol)
3
O
NO2 CO2Me
Br
O
2l R = Et
2m R = i-Pr
2n R = t-Bu
3aa 60%
3aa N.R.
3aa N.R.
O2N
O2N
O2N
Scheme 3 The effect of the alkyl groups in phenylacetates (N.R.= No reaction).
4da 40% (X = H)
3ea 22% (X = H)
3cc 43% (X = H)
O
O
CO2Me
OMe
To figure out the mechanism of this oxidative acylation
chemistry, a variety of control experiments were carried out,
as shown in scheme 4. From the experiments for reaction
temperature optimization, we realized that the reaction
probably underwent the CDC process and that the low
reaction temperature may favour the formation of the CDC
product without the further conversion to the acylation
product. Thus, we strived to obtain 4aa by performing the
O2N
O2N
O2N
3fa 80% (X = Cl)
4ea 18% (X = H)
3ee 25% (X = H)
O
O
O
NC
O2N
O2N
O2N
3ha 0% (X = H)
3ga 0% (X = H)
3fc 56% (X = Cl)
o
reaction at 0 C wherein 4aa was isolated in 30% yield. Then
a Conditions: nitroarenes 1 (0.4 mmol), arylacetates 2 (0.2 mmol), t-BuONa (0.4
mmol), dry DMSO (0.5 mL), 45 oC for 3 h in open-to-air flask. b Performed at 0 o
the CDC product 4aa as precursor was fully converted under
the standard conditions, and the ketone 3aa isolated in 92%
yield (scheme 4,
C
for 2 h. Isolated yields.
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oxidized into a peroxide anion VII in the presence of base and
O2. Then two possible pathways may exist in next
transformation.11a,11b One possible route involves a sequential
hydrolysis-decarboxylation-hydroperoxy
bond
cleavage
process11a,11b (pathway A). This may explain why the reaction
gave better yield under open air than under pure O2. That may
be because a trace amount of water from the environment
helps promote the base-catalysed hydrolysis of IV. The minor
competitive alternative implicates intramolecular ester
exchange of VII to in situ generate a dioxetanone IX, and
subsequent decarboxylation to the product 3aa, along with
peroxide cleavage11a (pathway B).
Scheme 4 Control experiments.
Conclusions
a). Furthermore, 4aa was observed and isolated in 28% yield
o
when the mixture of 1a and 2a were treated at 45 C under
In conclusion, we have demonstrated a facile TM-free base-
mediated aerobic oxidative acylation of nitroarenes with
bench-stable and readily available arylacetic acid esters under
mild conditions. This approach allows for the facile and
regioselective synthesis of 4-nitro-diarylketones, and obviates
the use of harsh conditions, TMs and Lewis acids. This
chemistry involves the in situ generation of 2-arylated arylacetic
acid esters via the CDC reaction, followed by the aerobic oxidative
decarboxylation mediated by base, and will supplement the
classical Friedel-Crafts acylation chemistry. In view of its
numerous advantages, it will provide an alternative and
powerful tool to access ketones, particularly containing the
nitro group in organic synthesis and pharmaceutical fields.
argon atmosphere after five freeze-pump-thaw cycles (scheme
4, b). This suggests that DMSO could play a role as hydrogen
acceptor in the CDC coupling step (please see SI, section 5).
However, the reaction of 4aa as precursor under argon
afforded nothing even for the prolonged time (8 h), but 4aa
fully recovered after neutralization under argon. This indicates
that the followed oxidative decarboxylation process
necessitates the involvement of molecular oxygen (O2). All
these results confirmed our hypothesis that the first step of
this chemistry involved a CDC reaction between nitroarenes
and arylacetic esters and the second step implicated an
aerobic oxidative decarboxylation mediated by base.
Based on our experimental observations and previous
reports,5h,
5i, 11
a tentative mechanism is proposed for this
Experimental
cascade oxidative acylation reaction (scheme 5). Firstly, 2a is
deprotonated by t-BuONa to generate a carbanion, which
undergoes sequential nucleophilic addition to 1a, O2-mediated
H-atom abstraction from II, radical combination and HOO-
dissociation to furnish a CDC product 4aa with a concomitant
hydroperoxide anion.5h In this stage ( II to 4aa), DMSO as an
oxidant can’t be ruled out. Secondly, the intermediate 4aa is
General information
All solvents and reagents were purchased from the suppliers
and used without further purification unless otherwise stated.
Yields reported are for isolated yields unless otherwise stated.
1H NMR (400 MHz) and 13C NMR (101 MHz) spectra were
recorded in CDCl3 at room temperature on Bruker Avance III
400 spectrometer using TMS as the internal reference. MS
spectra were performed on a Agilent 6890/5973 GC-MS (EI) or
Waters UPLC_Xevo_TQD (ESI). Elemental analyses were
measured on a Perkin Elmer 2400 series analyser. The melting
point (m. p.) was determined using an open glass tube. TLC
analyses were performed on silica gel plates and column
chromatography was conducted over silica gel (mesh 200-300)
at increased pressure.
CO2Me
t-BuONa
CO2Me
CO2Me
H
NO2
NO2
I
t-BuOH
HOO-
1a
2a
CO2Me
CO2Me
CO2Me
O
O
O2
OH
N
O
H
O
III
N
NO2
II
4aa
O
DMSO
Me2S
General procedure for synthesis of diarylketones
O
OH
O
OH
O
O
OMe
t-BuONa
H2O
To a predried 10 mL round-bottom flask were sequentially added
phenylacetates 1 (0.2 mmol), nitroarenes 2 (0.4 mmol), dry DMSO
(0.5 mL), and t-BuONa (0.4 mmol). The reaction system became
dark purple on adding the base. The resulting mixture was stirred at
45oC for the specific time (normally 3 h). Then it was cooled to
room temperature, to which added aqueous HCl (1 mol/L) to pH =
6-7, and the resulting mixture was extracted with ethyl acetate,
dried over anhydrous Na2SO4, and concentrated with rotary
evaporation. Then the resulting residue was subjected to column
O
O
NO2
NO2
3aa
MeO
V
NO2
VI
H2O or t-BuOH
pathway A (major)
CO2
t-BuOH
O
O
O
O
O
O
OMe
O
O
O
OMe
NO2
NO2
MeO-
NO2
IX
VII
VIII
pathway B (minor)
Scheme 5 Proposed pathways for the cascade oxidative reaction.
4 | J. Name., 2012, 00, 1-3
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Gao, S. Tang, W. Li, R. Shi and A. Lei, Chem. Rev., 2015, 115
12138.
,
chromatography on silica gel using co-solvent (ethyl acetate/
petroleum ether=1/40, v/v) as eluent to give the corresponding
diarylketones 3. The representative ketones are listed here.
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o
1
80%), M. p. 132-134 C. H NMR (400 MHz, CDCl3) δ 8.34 (d, J = 8.6
Hz, 2H), 7.94 (d, J = 8.6 Hz, 2H), 7.80 (d, J = 7.7 Hz, 2H), 7.66 (t, J =
7.4 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ
194.8, 149.8, 142.9, 136.3, 133.5, 130.7 (2C), 130.1 (2C), 128.7 (2C),
123.6 (2C). MS (EI): m/z 227.1 [M]+•.
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(4-Chlorophenyl)(4-nitrophenyl)methanone (3ai).13 Yellow solid
(29 mg, 55%), M. p. 103-105 oC. 1H NMR (400 MHz, CDCl3) δ 8.35 (d,
J = 8.3 Hz, 2H), 7.92 (d, J = 8.3 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.51
(d, J = 8.1 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 193.6, 149.9, 142.5,
140.1, 134.6, 131.5 (2C), 130.6 (2C), 129.1 (2C), 123.7 (2C). MS (EI):
m/z 261.0 [M]+•, 263.0.
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Ueda, K. Yoshida and H. Tokuyama, Org. Lett., 2014, 16
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(2-Chloro-4-nitrophenyl)(phenyl)methanone (3ba).14 Yellow solid
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(46 mg, 90%), M. p. 93-94 oC. H NMR (400 MHz, CDCl3) δ 8.36 (s,
1H), 8.25 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 8.0 Hz, 2H), 7.67 (t, J = 7.4
Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H).13C NMR (101
MHz, CDCl3)δ193.3, 148.9, 144.5, 135.3, 134.6, 132.6, 130.0 (2C),
129.6, 129.0 (2C), 125.3, 121.9. MS (EI): m/z 261.0 [M]+•, 263.0.
(4-Nitronaphthalen-1-yl)(phenyl)methanone (3ea).15 Yellow solid
1
(12 mg, 22%). M. p. 85-87 oC. H NMR (400 MHz, CDCl3) δ 8.54 (d, J
= 8.8 Hz, 1H), 8.20 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 8.8 Hz, 1H), 7.84 (d,
J = 7.6 Hz, 2H), 7.76 (t, J = 7.8 Hz, 1H), 7.67 – 7.59 (m, 3H), 7.49 (t, J
= 7.4 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ 196.5, 148.0, 142.7,
136.9, 134.3, 131.9, 130.4 (2C), 129.7, 128.9 (2C), 128.4, 126.2,
125.3, 124.3, 123.3, 122.2. MS (ESI): m/z 278.0 [M+1].
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There are no conflicts to declare.
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We thank the National Natural Science Foundation of China
(21202010), Hunan Provincial Natural Science Foundation of
China (2017JJ2275 & 2015JJ3012), Scientific Research Fund of
Hunan Provincial Education Department (16B003), the Hunan
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A regioselective t-BuONa-mediated aerobic oxidative acylation of nitroarenes under mild conditions is
developed through a cascade CDC/oxidative decarboxylation process.