Visible-Light-Driven Direct Oxidative Coupling Reaction Leading to Alkyl Aryl Ketones, Catalyzed by Nano Pd/ZnO

Article abstract of DOI:10.1002/ejoc.201900021

Direct alkyl sp³ C–H activation to form new C–C bonds is one of the major challenges in synthetic chemistry. Herein, for the first time, we represent a new method, using nano Pd/ZnO which plays both as photoredox and transition-metal catalyst, for C–C bond formations. By using this catalyst, we have accomplished an oxidative coupling reaction between aryl halides and tertiary amines to yield the corresponding naturally occurring alkyl aryl ketones by using visible light irradiation. Furthermore, the carbonylation process was carried out on a 10 gram scale, with visible light and thermal condition, and it was proved to be scalable, efficient, and economical.

Full text of DOI:10.1002/ejoc.201900021

A Journal of
Accepted Article
Title: Visible-Light-Driven Direct Oxidative Coupling Reaction Leading
Alkyl Aryl Ketones Catalyzed by Nano Pd/ZnO
Authors: Mona Hosseini-Sarvari and Zahra Bazyar
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201900021
Link to VoR: http://dx.doi.org/10.1002/ejoc.201900021
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10.1002/ejoc.201900021
European Journal of Organic Chemistry
COMMUNICATION
Visible-Light-Driven Direct Oxidative Coupling Reaction Leading
to Alkyl Aryl Ketones Catalyzed by Nano Pd/ZnO
Zahra Bazyar,[a] Mona Hosseini-Sarvari*[a]
Department of Chemistry, College of Science, Shiraz University, Shiraz 7194684795, I.R. Iran
Abstract: Direct alkyl sp3 C-H activation to form new C-C bonds is one of the major challenges. Here, for the first time, we represent a new
way using nano Pd/ZnO which plays both as photoredox and transition-metal catalyst for C-C bond formations. By using this catalyst, we
have accomplished an oxidative coupling reaction between aryl halides and tertiary amines to yield the corresponding naturally occurring alkyl
aryl ketones by using visible light irradiation. Furthermore, the carbonylation process was carried out on 10 gram scale, with visible light and
thermally condition, and it was proved to be scalable, efficient and economical.
oxidants.
Introduction
Also thermodynamically oxidation is highly favorable, the
Over the past decade, palladium-catalyzed carbonylation
reactions have become one of the most important reactions to
construct carbon-carbon and carbon-heteroatom bonds
formation such as ketones, esters, aldehydes, amides,
carboxylic acids and their derivatives.[1] Among these carbonyl
compounds, the synthesis of alkyl aryl ketones have attracted
significant interest because of their widespread use in fragrance,
pharmaceutical, agrochemical, dye, functional material
industries and in organic synthesis (Scheme 1a).[2] So,
considerable efforts have been made to extend capable
methods for alkyl aryl ketone synthesis. Traditionally, Friedel-
Crafts acylation employing acid halides or acid anhydrides have
been used for the synthesis of alkyl aryl ketones.[1-3] Low
regioselectivity, releasing large amounts of waste, harsh
reaction conditions, incompatibility with electron-deficient
functional groups (specially nitro aromatic compounds), and the
need for stoichiometric amounts of catalyst make this process
undesirable on large scale. Hence, the synthesis of alkyl aryl
ketones have been mainly based on the oxidation of
alkylbenzenes,[4] in the industrial processes. Synthesis of
pharmaceuticals and fine chemicals, stoichiometric oxidants
such as permanganate and dichromate were used. Strongly
exothermic reaction is the serious problem by using these
reaction is kinetically hindered so that the oxidations have been
often performed at high temperatures (175−225 °C).[5] Therefore,
these processes are undesirable in large scale. To overcome
the difficulties of traditional methods, palladium catalyzed
carbonylation reactions are virtually attractive. For the these
transformations, carbon monoxide (CO) has been mostly used
as the source of the carbonyl group.[6] It is a highly poisonous
and flammable gas.[7] Due to the improvement of safer and more
suitable sources of carbonyl group, metal carbonyl complexes
such as Mo(CO)6, Co2(CO)8, have been were used. However,
the main problem is, their high cost, toxicity and un-stability.[8] In
the last two decades, cheaper organic carbonyl compounds
such as dimethylformamide, formates, acid halides, formic
anhydride, chloroform, aldehydes, and formic acid derivatives
have been also reported in carbonylative reactions.[9] In 2011, Li
and co-workers reported a new procedure by using palladium
which catalyzed oxidative coupling of aryl iodides and
trialkylamines for the synthesis of alkyl aryl ketones. It was the
first and the only report in the literature, using trialkylamines in
water as carbonyl sources (Scheme 1b).[2a] The literature studies
have revealed that there is no report of using a photoredox
catalysis in visible light for the synthesis of alkyl aryl ketones by
using a trialkylamine as carbonyl source. Tertiary amines which
have highly stable C-N bond, the activation of this bond is an
important challenge in organic synthesis. So, to the best of our
knowledge, use of stable tertiary amines as the carbonyl source
[a] Prof. Dr. M. Hosseini-Sarvari. Department of Organic Chemistry,
College of Sceince, Shiraz University, Shiraz 7194684795, I. R. Iran
E-mail: hossaini@shirazu.ac.ir; http://chem.shirazu.ac.ir/?page_id=546
for this transformation by using
unprecedented (Scheme 1c).
a
photocatalyst is
1
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Solvents are important in photocatalysis reactions, so we used
some commonly solvents while other reaction conditions were
maintained unchanged. The solvents such as DMF, CH3CN,
dioxane and EtOH were used for 24 h, and then the reaction
mixture was worked up with H2O and the desired ketone (3a)
was obtained (Table S1, entries 1-6). To improve the reaction
condition, we decided to remove aqueous work up and instead
use water as solvent. In the presence of water as sole solvent
the yield of (3a) decreased (Table S1, entry 5) but we found that
a mixture of CH3CN and water improved the reaction (Table 1,
entry 2 and Table S1, entries 7-13). Afterwards, selection of
some additives, were further investigated (Table S2). The results
showed that the excess amount of ZnO or mixture of both TBAB
and ZnO were more effective and the yield of (3a) was
increased sharply to 71% (Table 1, entries 3, 4 and Table S2,
entries 8, 13). So excess amount of ZnO (4 mmol) for further
investigations was chosen. It is noteworthy that the yield was
sharply reduced when reaction was investigated under argon
atmosphere, whereas under air and O2 the yield was increased
up to 76%, which demonstrated that O2 was necessary for this
transformation (Table 1, entry5 and Table S3, entries 5, 6).
Scheme 1. (a) Selective bioactive molecules bearing carbonyl group. (b-c)
Synthesis of alkyl aryl ketones.
Zinc oxide (ZnO), has possessed significant attention for a long
time as a kind of capable photocatalyst. Only 3-7% of the total
solar light reaching Earth’s surface is UV light, and particularly
photocatalytic processes using visible light by ZnO photocatalyts
in behalf of broad band gap and great excitation binding energy
is difficult.[10] Hence, research groups have focused on the
improvement of ZnO as photocatalysts. One approach for
achieving these goals is, to load noble metals (such as Au, Pd,
Pt) nanoparticles on the surface of ZnO nanostructures.[11] Noble
metals exhibit strong visible-light absorption characteristics
because of localized surface plasmon resonance (LSPR) which
are located on semiconductor-based photocatalysts.[12] A new
nano sized Pd doped on ZnO as a catalyst for the C-C and C-N
bonds formation, under thermally condition have been reported
by us.[13] We also reported its photocatalytic activity in Suzuki
reaction.[14] So, considering that nano Pd/ZnO showed excellent
results as photocatalyst, it encouraged us to use it for the
synthesis of alkyl aryl ketons. Notably, this is the first example
for the synthesis of alkyl aryl ketones using trialkylamines as
carbonyl source under visible light irradiation at ambient
temperatures. Herein, we report an efficient and scalable
process for the formation of alkyl aryl ketons.
Table 1. Selected optimization data for synthesis of alkyl aryl ketones under
visible-ligh irradiation.[a]
Entry
1
Additive (mmol)
TBAB (1)
Solvent (mL)
DMSO
Yield[b] (%)
60
66
71
71
76
0
2
TBAB (1)
CH3CN/H2O (2:1)
CH3CN/H2O (2:1)
CH3CN/H2O (2:1)
CH3CN/H2O (2:1)
CH3CN/H2O (2:1)
3
TBAB (1)/ZnO (1)
ZnO (1)
4
5[c]
6[d]
ZnO (1)
TBAB (1)
[a] Reaction conditions: 1a (1 mmol), 2a (1 mmol), nano Pd/ZnO (0.006g),
solvent (3 mL) at room temperature, 11 W white LED (wavelength in the range
450-750 nm), 24 h. [b] isolated product. [c] O2 atmosphere. [d] Dark condition.
Results and Discussion
Initially, we focused on the reaction between triethylamine (1a)
To better understand the enhancement of the catalytic
performance that occurs through light irradiation of the Pd/ZnO
NPs, the dependence of the catalyzed reaction on the light’s
wavelength and intensity were investigated. As shown in Figure
S1a, increasing the light intensity white LED resulted in an
almost linear increase in the conversion of the carbonylation
coupling reaction catalyzed by the Pd/ZnO NPs. It can be seen
that the higher the light intensity, the greater the contribution due
to light irradiation to the overall conversion rate.
and 1-iodo-4-nitrobenzene (2a) as a model compound.
A
solution of (1a) and (2a) in DMSO was irradiated by 11 W white
LED in the attendance of nano Pd/ZnO as photocatalyst and
TBAB for 24 h at room temperature. Then the reaction mixture
was worked up by H2O and the desired ketone (3a) was
obtained in 60% yield (Table 1, entry1). This promising result
inspired us to improve the reaction. So, we changed a lot of
factors, including solvent, photocatalyst loading, additive, light
source, atmosphere, and also reaction time (Tables S1-S4).
2
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Table 2. Visible-light photoredox carbonylation of aryl halids (2) with
triethylamine (1a) using nano Pd/ZnO.[a, b]
We also used different wavelengths including red (620-750 nm),
green (495-570 nm) and blue (450-495 nm). The yield improved
to78% when the reaction was under irradiation by 11 W blue
LED instead of white LED, Figure S1b. All the light intensities
were strictly the same (0.4 W/cm2) in every wavelength region.
The dependence of photocatalytic activity on light intensity and
wavelength indicates that energetic electrons excited by light
absorption are responsible for the observed photocatalytic
activity. Since the reaction rate is expected to depend on the
population of electrons with sufficient energy to initiate the
reaction of the reactant molecules, one can increase the number
of energetic electrons by applying higher light intensity. Tuning
the irradiation wavelength can also increase the number of
energetic electrons and may also assist us to understand the
mechanism of the reactions.
Outdoor proficiency under sunlight was also investigated. This
was executed on a winter day, in January, in Shiraz with the sun
°
at 68.5° zenith angles and temperature 10-15 C ranges. This
result shows that the nano Pd/ZnO catalyst has excellent
sunlight applicability (Figure S2). In order, to find the recycling
ability of nano Pd/ZnO photocatalyst it was used for five runs
without any remarkable loss of yield or increase of the reaction
time (Figure S3). After optimization of the reaction conditions,
the substrate scope was examined (Table 2). All the reactions
were carried out in air atmospheres using CH3CN:H2O (2:1) as
solvent, nano Pd/ZnO (0.006 g) as photocatalyst and ZnO (4
mmol) as additive at room temperature by using blue LED. The
yield of the carbonylation reaction depends on the type of the
aryl halide. The results disclosed that both electron-donating and
electron-withdrawing groups of aryl iodides were suitable for the
reaction, but aryl chlorides and bromides showed little reactivity
and lower conversion in comparison with the similar iodides.
Interestingly, when two different halides are presented in a
substrate, chemoselectivity between these halo groups was
observed (entry 3d, 3e). Furthermore, when using the substrates
supporting an ortho-group on the aryl halides, the yield was
decreased, this can be explained by the steric effect.
Surprisingly, free NH2 and OH groups on the substrate did not
cause affected serious problem and the desired product was
obtained in moderate yield. However, to comparison with other
substrates the yields were decreased. Moreover, nitrogen and
sulfur containing heteroarenes, such as pyridines (3k-3n), and
thiophene (3j), were amenable to this carbonylation reaction,
affording a satisfying outcome. The synthesis of some new
biologically active β-lactams (3k-3l), were treated and the
desired alkyl aryl ketones were obtained.[15]
[a] Reaction conditions: 2 (1 mmol), 1 (1 mmol), ZnO (4 mmol), CH3CN (2 mL),
water (1 mL), nano Pd/ZnO (0.006g), 11
W blue LED irradiation, room
temperature, air atmosphere, 24 h. [b] Isolated product.
Nitroaromatic compounds are one of the important group of
industrial chemicals in use today. Many pharmaceuticals are
emanating from nitroaromatic compounds. For example, many
substituted nitroaromatic compounds are used to synthesize
various indole derivatives which are bioactive member of many
drugs and agrochemicals. Among these, nitroacetophenones
have been commonly used in the synthesis of chemical and
pharmaceutical compounds. 4-Nitroacetophenone is recently
identified as a class of anti-trypanosomal drug candidates.[2d] 2-
Nitroacetophenone is used as an intermediate for the synthesis
of cinoxacin that is prescribed medication in adults for urinary
tract infections.[2c] 3-Nitroacetophenone is used as intermediate
for flurbiprofen synthesis which is managed for the treatment of
inflammation and arthritis pain. Chalcones which are important
compounds with pharmacological activity (anti-inflammatory,
anti-ulcerative, antibacterial, antifungal and antimalarial) are
synthesized from 3-nitroacetophenone as an intermediate
3
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10.1002/ejoc.201900021
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COMMUNICATION
compound.[2] Due to the low price of the reagents and low
amount of catalyst loadings, we started up to accredit the
viability of our procedure on gram scale (Scheme 2). A
preparative scale reaction on 10 g of 1-iodo-4-nitrobenzene, 1-
iodo-3-nitrobenzene iodobenzene, 1-iodo-2-nitrobenzene and
iodobenzene afforded the Products 3a-3c and 3i in good yields
of 69%, 64%, 60% and 65%, respectively (Scheme 2a). The
results exhibited that the conversion was similar to those
observed in the corresponding bench scale experiments. Also,
the reaction could be started thermally by heating to 90 °C for 15
hours in the absence of light, again providing similar yield (69%)
(Scheme 2b). These results show that the method is potentially
suitable to large-scale production.
Entry
1
Amine
Product
Yield[b](%)
62
(n-Pr)3N
1b
3o
3a
2
3
17
34
1c
1d
3a
4
Trace
3p
1e
[a] Reaction conditions: 2 (1 mmol), 1 (1 mmol), ZnO (4 mmol), CH3CN (2 mL),
water (1 mL), nano Pd/ZnO (0.006g), 11 W blue LED irradiation, room
temperature, air atmosphere, 24 h. [b] Isolated product.
To attain deeper knowledge into a possible mechanism, a set of
control reactions were managed. Addition of triethanolamine and
ammonium oxalate (hole scavengers) gave only trace and 12%
of product 3a, respectively, denoting the participation of holes.
Addition of t-BuOH (OH• radical scavenger) did not change the
yield of product 3a, indicating that OH• radical was not presented
in the photocatalytic process. And finally addition of TEMPO
(O2•-, radical scavenger) or NaN3 (singlet 1O2 scavenger) gave
product 3a in trace and 10% yield, respectively. The deficiency
of any reaction in the dark declared that the alkyl aryl ketones
formation activated and deactivated by visible light. To find this
"On-Off" visible light irradiation experiment was operated. These
preparative result only show that radical-chain propagation in
this transformation is not a key step (Figure S4). So, according
to control experiments a detailed depiction of our proposed
mechanism is defined in Figure 1. We assumed that irradiation
of nano Pd/ZnO photocatalyst by visible light, electrons in Pd
nanoparticle according to LSPR are excited and then transferred
to the CB of ZnO. So an electron/hole (e-/h+) generated.[12]
Triethylamine (Eox= -0.88 V vs ) is oxidized to the corresponding
radical cation by a single-electron transfer to the hole generated
in Pd nanoparticles.[14] The iminium ion II has been formed by a
hydrogen (H•) abstraction of I by superoxide anion (O•¯) [16] which
Scheme 2. Gram-scale carbonylation.
In the next step, efforts were made to use other trialkylamines
(Table 3). The results indicated that tripropylamine (1b)
successfully underwent the carbonylation reaction with 1-iodo-4-
nitrobenzene (2a) in excellent yield (entry 1). Also, the steric
effect seemed to be important to the reaction, because when N-
cyclohexyl-N-ethylcyclohexanamine
(1c)
and
N-ethyl-N-
phenylaniline (1d) were used instead of triethylamine, lower
yields were obtained (entries 2, 3). Notably, other symmetric
tertiary amines, such as tribenzylamine (1e) did not afford the
desired product (entry 4).
Table 3. Visible-light photoredox carbonylation of aryl halids with
trialkylamines using nano Pd/ZnO. [a]
4
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•
was formed by electron transfer in CB of ZnO to O2 .
Contemporaneously with e-/h+ generated, nano Pd/ZnO could
play another role in this mechanism. We believed that oxidation
addition of the Pd (0) in nano Pd/ZnO photocatalyst into aryl
halide would generate the intermediate III (in a Pd catalytic
cycle),[13] the iminum ion II reacted with ArPdI from Pd catalytic
cycle to afford intermediate IV. Abstraction of a proton (H+) from
intermediate IV generated intermediate V, which was hydrolyzed
to produce the desired product. The production of H2O2 during
the reaction was indicated by test strip and 1HNMR (see SI).
The general procedure for the carbonylation of aryl halids.In
a typical reaction, the mixture of arylhalide (2, 1 mmol),
trialkylamine (1, 1 mmol) or one of its derivatives, ZnO (4 mmol),
deionized water (1 mL), CH3CN (2 mL) and 0.006 g of nano
Pd/ZnO catalyst were put into a Pyrex glass in which a 11 W
LED was used as a light source and the reactant mixture was
carried out under air atmosphere at room temperature. After the
reaction was complete, it was centrifuged to remove the catalyst
andthe mixture purified by column chromatography on
silicagel )Petroleumether:Ethyl acetate 10:2 v/v) to give the
desired product. The products were characterized with IR, 1H
NMR and 13C NMR.
Acknowledgements
This work was supported by the Shiraz University and financially
supported by the Iran National Science Foundation (Grant No.
96003604).
Keywords: alkyl aryl ketones • carbonylation • aldehydes •
lactams • nano Pd/ZnO
Figure 1. Proposed mechanism.
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In this work, we have shown the capability of nano Pd/ZnO as a
dual catalyst (both in absorption visible light irradiation as
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To the best of our knowledge this is the first example that a
catalyst plays two roles and we believe that it would open up a
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COMMUNICATION
Photoredox
We have been show the
capability of nano Pd/ZnO
as a dual catalyst. This
Zahra Bazyar, [a]Mona
Hosseini-Sarvari*[a]
method
example using
is
the
a
first
metal
Visible-Light-Driven Direct
Oxidative Coupling
Reaction Leading Alkyl
Aryl Ketones Catalyzed by
Nano Pd/ZnO
doped metal oxides, as a
dual photoredox and
transition-metal catalyst.
By employing this
heterogeneous
photocatalyst,
carbonylation reaction can
proceed under visible
light.
7
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