Carbonylative Suzuki cross-coupling reaction catalyzed by bimetallic Pd-Pt nanodendrites under ambient CO pressure

Article abstract of DOI:10.1016/j.catcom.2017.06.005

Pd-catalyzed reactions between aryl boronic acids and aryl halides have undergone rapid development since the pioneering work of Suzuki and co-workers in 1979. In this paper, we described a high-efficient and cost-effective bimetallic Pd-Pt nanodendrites catalyst based on a ligand-free strategy to synthesize diaryl ketones via CO direct insertion to boronic acids and aryl halides. A variety of aryl boronic acids and aryl halides were investigated, which showed great functional group tolerance and versatile aryl ketone products in high yield.

Full text of DOI:10.1016/j.catcom.2017.06.005

Accepted Manuscript
Carbonylative Suzuki cross-coupling reaction catalyzed by
bimetallic Pd-Pt nanodendrites under ambient CO pressure
Zheng-Jun Wang, Xue-Yan Wang, Xia Wang, Zhi-Wu Liang,
Xinhua Xu
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DOI:
Reference:
S1566-7367(17)30236-4
doi: 10.1016/j.catcom.2017.06.005
CATCOM 5071
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19 April 2017
8 June 2017
9 June 2017
Please cite this article as: Zheng-Jun Wang, Xue-Yan Wang, Xia Wang, Zhi-Wu Liang,
Xinhua Xu , Carbonylative Suzuki cross-coupling reaction catalyzed by bimetallic Pd-
Pt nanodendrites under ambient CO pressure. The address for the corresponding author
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ACCEPTED MANUSCRIPT
Carbonylative Suzuki Cross-coupling Reaction
Catalyzed by Bimetallic Pd-Pt Nanodendrites
under Ambient CO Pressure
Zheng-Jun Wang,a,1 Xue-Yan Wang,a,1 Xia Wang,a Zhi-Wu Liang,a
Xinhua Xua, b*
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and
Chemical Engineering, Hunan University, Changsha 410000, China
b
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle,
Nanchang Hangkong University, Nanchang 330063, China
[Corresponding Authors:aTel./Fax:+86 731 8882-1546; e-mails: xhx1581@hnu.edu.cn]
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Abstract: Pd-catalyzed reactions between aryl boronic acids and aryl halides have
undergone rapid development since the pioneering work of Suzuki and co-workers in
1979. In this paper, we described a high-efficient and cost-effective bimetallic Pd-Pt
nanodendrites catalyst based on a ligand-free strategy to synthesize diaryl ketones via
CO direct insertion to boronic acids and aryl halides. A variety of aryl boronic acids
and aryl halides were investigated, which showed great functional group tolerance and
versatile aryl ketone products in high yield.
Keywords: Pd-Pt NDs catalysts; Bimetallic nanocrystals; CO insertion; Ligand-free; Suzuki
reaction
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Introduction
Aryl ketones are vital structural building blocks in a huge variety of molecules, including
natural products [1], pharmaceutical drugs [2], photosensitizer [3], and organic materials [4]
(SI, Scheme S1). Pd-catalyzed reactions between aryl boronic acid s and aryl halides
have undergone rapid development since the pioneering work of Suzuki and
co-workers in 1979 [5]. The carbonylative Suzuki cross-coupling reaction of boronic acids
and aryl halides by directly inserting CO is one of the most facile, effective and
atom-economy synthetic method for achieving asymmetric aryl ketones [6]. Many
great-documented synthetic approaches have been reported. For instance, Cai and his
co-workers used MCM-41-supported bidentate phosphane palladium(II) complex
(MCM-41-2P-PdII) to build unsymmetrical biaryl ketones in good yield by carbonylative
Suzuki–Miyaura cross-coupling reaction [7]. Hoven et al. described a novel chemo- and
regioselective way to obtain 4-carbaldehydepyrrolin-2-ones in desirable yield by the
zwitterionic rhodium complex with triphenyl phosphate assisted catalyzed
cyclohydrocarbonylation/CO insertion of trisubstituted acetylenic imines [8]. Fairlamb and
his co-workers established a palladacycle catalyzed methoxy- and amidocarbonylation
reactions of aryl halides, which applied superior source of Pd, such as Pd(OAc)2 and
(PhCN)2PdCl2 [9]. Wu et al developed a practical and convenient synthetic method for
diarylketones through palladium-catalyzed carbonylative Suzuki coupling reactions with
formic acid as the CO source [10]. But regrettably, some challenges still exist in the typical
carbonylation reactions [11]. On the one hand, they generally require relatively high loadings
of catalyst (more than 10 mol%) and ligands [12], elevated temperatures and high pressures of
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CO, which dramatically limit the utility because of the need for specialized pressure reactors
and the dangers related with handling pressurized CO [13]. On the other hand, most of them
are homogeneous catalysis, in which the catalysts are difficult to separate from the reaction
system and thus can not be recycled [14]. Regarding the difficulty of the reaction operating,
reaction costs and environmental aspects, these challenges severely impede
the industrialization process of these kind reactions.
Pd nanoparticles (Pd NPs) have been widely used as catalysts in C-C bonds formation
[15], and particularly bimetallic Pd-based nanocrystals have been under the spotlight on
account of reducing the amount of noble metals and possessing superior performance in
catalytic reactions [16]. What’s more, bimetals can synergistically combine the relevant
monometallic counterparts’ activity [16c]. In recent decades, great advances have been
achieved in their preparation and practical applications. Xia and co-workers prepared a
cost-effective ORR catalyst based on Pd-Pt bimetallic core-shell icosahedra in the presence of
uniform Pd nanocrystal seeds in an aqueous solution [17]. Wang et al. developed a Pd-Cu
bimetallic nanocrystals to catalyze the Suzuki–Miyaura reaction [18].
Based on these excellent works and we previously reported the Pd-Pt nanodendrites
(NDs) catalyzed Suzuki cross-coupling reaction under mild conditions [19], we herein
propose a facile and efficient strategy by applying the Pd-Pt NDs to catalyze ligand-free
carbonylative Suzuki cross-coupling for synthesis of asymmetric biaryl ketones via CO
insertion under gentle conditions. This strategy shows highly enhanced reaction efficiency
and provides an effective and simple approach to obtain a series of diphenyl ketone and their
derivatives.
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Results and discussion
Optimization of the reaction conditions
Initially, we selected bromobenzene 1a and phenylboronic acid 2a as the model reaction
to explore the viability of the process in the presence of CO (1 atm) (Table 1). Several
commercially available Pd-based catalysts were screened due to their robust performance in
traditional carbonylation reactions [20]. Such as, PdCl2, Pd(OAc)2, Pd/C, Pd(PPh3)4 and
(DBA)3Pd2 were tested, the results illustrate that commercial Pd-based catalysts is not
effective towards this transformation, probably because that the activity of the catalysts is
strongly hindered by CO poisoning on its surface (SI, Table S1, entries 1-5) [21]. While the
Pd-Pt NDs show much higher catalytic ability towards this carbonylative Suzuki reaction
(Table 1).
It is noteworthy to point out that the significant decreases in yield of 3a were observed
when reducing the amount of Pd-Pt NDs to 3 mg (46%) and 1 mg (16%) (SI, Table S1,
entries 10 and 11, respectively), indicating the concentration of catalyst has great influence on
the reaction. As known, solvent plays an important role in determining the conversion rate. In
consequence, a series of solvents were tested, such as 1,4-dioxane and CH3CN, (Table 1,
entries1 and 2), which are found with poor efficiency for this reaction. Using inorganic polar
H2O (Table 1, entry 3) as the solvent, the desired product of 3a is trace, possibly because of
the poor solubility of reactants in H2O [22]. Luckily, DMF afforded desired carbonylative
product 3a with the yield of 81% (Table 1, entry 4), which is superior to the other polar
solvents, such as EtOH and DMSO (Table 1, entries 5 and 6). This result probably owns to its
high electron transfer rate constants for the corresponding cross-coupling reactions [23].
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Next, the base-screening study was commenced. It can be found that K2CO3, CsF and
Na2CO3 lead to the mediate yield with corresponding product of 81%, 43% and 62% (Table 1,
entries 4, 7 and 8). Organic bases, like 2-aminoethanol (ETA, 26%) and Et3N (33%), give low
yield of 3a (Table 1, entries 9 and 10). NaHCO3 was found to be the most effective one for
this reaction, which provides a product yield of 94% to get the desired product (Table 1, entry
14).
Then, the impact of reaction temperature and time for reaction efficiency were
investigated. From the experimental results, we can obviously find both of them making a
great influence on the corresponding product yield. Along with reaction temperature dropped
o
o
from 120 C to 60 C, the yields severely curtail from 86% to 31% as keeping the other
conditions constant (Table 1, entries 11-14). Time-dependent control experiments were
conducted as well. As reaction time prolonged, the product yields increase largely until 6 h
(Table S1, entries 6-9). Therefore, the optimal reaction conditions have been confirmed. The
phenylboronic acid (1 mmol, 1 equiv), aromatic halides (1.2 mmol, 1.2 equiv), catalyst (Pd-Pt
NDs, 6 mg) and NaHCO3 (2 mmol, 2 equiv) were added into a 50 mL two-necked flask
containing DMF (5 mL) solution under CO atmosphere, along with sealed the reaction flask
by a rubber stopper and CO (1 atm) was injected into it with a stainless steel gas flowmeter.
Synthesis ofBiaryl Ketones
With the optimized conditions in hand, a range of aryl halides were subjected to the
standard conditions (Table 2), regardless of their electronic properties and steric effects.
These reactions were executed smoothly, giving the corresponding products in 66−88% yield.
Electron-withdrawing aryl halides, such as reactants containing –Cl, aryl-B, aryl-I, –CHO,
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–COOC2H5, –CF3 (Table 2, entries 3-6) and –NO2 (Table 2, entry 8) groups are compatible
well and obtain the corresponding products in good yield, while the aryl-Cl gives undesired
yield, because of the most strong strengths of the aryl-Cl bond in them (Table 2, entries 2
and 6) [14]. The –OCH3 (Table 2, entry 2), –CH3 (Table 2, entry 7), and –Ph (Table 2, entry
8) aryl halides were also determined as electron-donating substrates with well yield. Next, the
di-methyl (Table 2, entry 10) in the ortho-position and tert-butyl (Table 2, entry 11) in the
para-position on benzene display the decreasing product yield, suggesting that steric
effects can significantly affect the reaction rate [24]. The reaction of heterocyclic halogenated
aromatic was examined, which is the most common S-heteroaryl units in pharmaceutically
active compounds, giving the desired product in moderate yield (Table 2, entry 12) [25].
Furthermore, the scopes and limitations of this carbonylative Suzuki cross-coupling
reaction for boronic acids were explored under the optimized conditions. Primarily, strong
electron-donating groups, such as –OCH3 and -NH2 (Table 2, entries 13 and 14), afford the
desired products in satisfactory yields. Then, we investigated the effect of substituent
positions on the reaction efficiency with methyl as the reference (Table 2, entries 16 and 18).
The results distinctly illustrate the reactivity of mono–substituted boronic acids in this
reaction is high coincided with the sequence: para > meta > ortho, probably due to the
different steric hindrance effects in the rate-determining transmetalation step [19]. To our
delight, great deals of electron-withdrawing groups were employed in this reaction,
demonstrating good reactivity and provided high products yields in 73-86% (Table 2, entries
19 and 20, 22-25). 2-methoxyl (Table 2, entry 14), 2,6-dimethyl (Table 2, 21), 2,4,6-trifluoro
(Table 2, entry 22) phenyl boronic acids with bromobenzene are obtained with corresponding
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sterically hindered diaryl ketones in 85%, 78% and 72% yield, respectively. N-heteroaryl
ketones (Table 2, entry 27) could be synthesized via this approach in moderate yield, which
could be attributed to the partial carbonization of substrates leading to lower electron density
and dropping the reaction efficiency [26].
The scope of the cross-coupling was further examined by carrying out the reaction of
bromobenzene with various of boronic esters, which possess electron-rich and withdrawing
groups (Table S2). The reactions were executed smoothly, giving the corresponding products
in moderate yield of 38−70%.
As known, 4,4′-difluoro diphenylmethanone (3q) is a very important organic fluorine
intermediates for a series of optical recording and electric imaging agent, polymerization
initiator, and medicine [27]. Although, there are many strategies for synthesis of 3q (Scheme
1), most of them bring some drawbacks, including complex synthetic steps, low atom
utilization and un-environment friendly. Encouraging by the experimental results, we
attempted using this method to synthesize 4,4′-difluoro diphenylmethanone on a gram scale
for demonstrating its utility. The result is displayed in eq3. Compared with the traditional
ways, this approach successfully gives a more atom- and step- economic and eco-friendly
way to build unsymmetric aryl ketones.
Moreover, Pd-Pt NDs displayed excellent stability in the carbonylative Suzuki reaction,
showing no obvious decrease in catalytic efficiency after five cycles by simple filtration
(Figure. 1(A)). In addition, judging by the TEM results (Figure. 1 (B) and (C)), the
morphology of Pd-Pt NDs was well maintained after being utilized in the ligand-free
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carbonylative Suzuki reaction, further confirming its good stability during the catalytic
reaction.
Reaction mechanism
To understand the mechanism of the reaction, some control experiments were conducted
(Scheme 3). When 3 equiv of 2,2,6,6-tetramethyl-1-piperidinoxyl (TEMPO) or
2,6-di-tert-butyl-4-methylphenol (BHT) as the radical scavengers were injected into the
reaction system under the standard conditions, the corresponding product is not decreasing
and give 93% and 92% isolated yield, respectively (SI, Scheme S2). The results imply that the
reaction does not involve the single-electron transfer process. On the basis of the
experimental results and pervious reports [6, 28], a plausible mechanism is brought
forward (Scheme 2). At first, the oxidative addition of Ar-X to Pd-Pt NDs complexes
provided the Ar-Pd-Pt-X (i), which is followed by migratory insertion of CO and
leaded to formation of ArCO-Pd-Pt-X (ii). Next, transmetalation occurred between (ii)
and arylboronic acid with the aid of NaHCO3, and reductive elimination of ketone 3
from (iii) regenerated the Pd-Pt NDs species. However, we have no other visualized
evidence to support this suggestion at this moment. Ongoing studies will further be
conducted to make the mechanistic details more clear.
Conclusion
In summary, an efficient and ligand-free strategy was proposed to fabricate symmetrical
or unsymmetrical aryl ketones by the Pd-Pt NDs catalyzed carbonylative Suzuki
cross-coupling of arylborinic acids with aryl halides, along with the CO acted as an insertion
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precursor. Compared with the previous works, this work shows higher vitality considering the
following two aspects. The one is without using ligands in the synthesis, which are bad to
environment and increases the cost of reaction. The other one is the lower CO pressure of the
reaction system, which cloud be very helpful to realize its industrialization.
Experimental Section
The process of Pd-Pt NDs catalyzed ligand-free carbonylative Suzuki cross-coupling
General procedure: a 50 mL flask equipped with a magnetic stir bar was charged with
aryboronic acid (1 mmol, 1 equiv), aromatic halides (1.2 mmol, 1.2 equiv), catalyst (2 mol%),
base (2 mmol, 2equiv), DMF (5 mL) solution under CO (1 atm) atmosphere, along with
sealed the reaction flask by a rubber stopper and CO was injected into it with a stainless steel
gas flowmeter. The mixture was then stirred at 120 oC for the indicated time (SI, Figure S1).
After being allowed to cool to room temperature, the reaction mixture was diluted with 5 mL
water and extracted with diethyl ether (3 × 5 mL). The organic phases were combined, and
the volatile components were evaporated in a rotary evaporator. The residue was purified by
column chromatography on silica gel.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China
(Nos.21536003).
References
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Figures
Scheme 1. Synthetic route to 4,4′-difluoro diphenylmethanone.
a) Classical Fiedel-Craft reaction.
b) Oxidation reaction benzylic compound.
c) This work: Pd-Pt NDs catalyzed directed CO Suzuki carbonylative reaction.
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Figure 1. Recyclability of Pd-Pt NDs for carbonylative Suzuki reaction (A); TEM
images of Pd-Pt NDs before and after five utilized in the carbonylative Suzuki
reaction ((B) and (C)).
100
A
80
60
40
20
0
1
2
3
4
5
Run numbers
B
C
20 nm
50 nm
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Scheme 2. Proposed mechanism of a CO-inserted ligand-free carbonylative Suzuki
coupling reaction catalyzed by the bimetallic Pd-Pt NDs.
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Table 1. Optimization of the conditions for the carbonylative Suzuki cross coupling
reaction.a
Entry
Solvent
Base
Temp. (oC)
Time (h)
Yield (%)b
1,4-dioxane
CH3CN
H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
120
120
120
120
120
120
4
4
4
4
4
4
43
51
1
2
3
4
5
6
Trace
81
DMF
EtOH
66
DMSO
71
7
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
CsF
120
120
120
120
60
4
4
4
4
4
4
4
4
43
62
26
33
31
77
93
94
8
Na2CO3
ETA
9
10
11
12
13
14
Et3N
NaHCO3
NaHCO3
NaHCO3
NaHCO3
80
120
100
a, Raction conditions: phenylboronic acid (1 mmol, 1 equiv), aromatic halides (1.2
mmol, 1.2 equiv), catalyst (Pd-Pt NDs, 6 mg) and base (2 mmol, 2 equiv) were added
into a 50 mL two-necked flask containing solvent (5 mL) solution under CO
atmosphere (1 atm); b, Isolated yield.
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a
Table 2. Synthesis of Biaryl Ketones.
Entry
1
X
R1
R2
3
Yield (%)b
Br
94
96
88
91
30
87
85
70
85
88
21
88
92
H (1a)
H (2a)
3a
I
Br
I
2
p-OCH3 (1b)
H (2a)
3ba
Cl
Br
I
3
4
5
m-Cl (1c)
p-CHO (1d)
H (2a)
H (2a)
H (2a)
3ca
3da
3ea
I
p-COOC2H5 (1e)
Br
I
6
p-CF3 (1f)
H (2a)
3fa
Cl
Br
I
7
p-CH3 (1g)
H (2a)
3ga
8
9
Br
I
p-NO2 (1h)
p-Ph (1i)
H (2a)
H (2a)
H (2a)
H (2a)
3ha
3ia
84
83
73
79
10
11
Br
I
2,6-dimethyl (1j)
p-tert-butyl (1k)
3ja
3ka
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
I
1 = thienyl (1l)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (2a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (2a)
p-OCH3 (2b)
o-OCH3 (2c)
p-NH2 (2d)
3la
3ab
3ac
3ad
3ae
3af
66
95
85
79
84
87
90
86
84
78
72
79
82
85
88
72
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
o-CH3 (2e)
m-CH3 (2f)
p-CH3 (2g)
3ag
3ah
3ai
p-NO2 (2h)
p-CN (2i)
2,6-dimethyl (2j)
2,4,6-trifluoro (2k)
3,5-difluoro (2l)
p-F (2m)
3aj
3ak
3al
3am
3an
3ao
3ap
p-Cl (2n)
2,4-difluoro (2o)
2 = pyridyl (2p)
a, Raction conditions: phenylboronic acids (1 mmol, 1 equiv), aromatic halides (1.2
mmol, 1.2 equiv), Pd-Pt NDs (6 mg) and NaHCO3 (2 mmol, 2 equiv) were added into
a 50 mL two-necked flask containing solvent (5 mL) solution under CO atmosphere
(1 atm); b, Isolated yield.
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Graphical Abstract
This paper describes a high-efficiency bimetallic Pd-Pt NDs catalyzed ligand-free
carbonylative Suzuki cross coupling reaction.
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Highlights
 Diarylketones were synthesized via direct CO insertion with Pd-Pt NDs
as catalyst.
 This work did not using any ligands in the synthesis.
 The synthesis was performed under lower CO pressure.
 The Pd-Pt NDs could be reused for at least five cycles.
20