Copper-catalyzed carbonylative Suzuki coupling of aryl iodides with arylboronic acids under ambient pressure of carbon monoxide

Article abstract of DOI:10.1039/c4ra08594a

An efficient and ligandless nanocopper-catalyzed carbonylative cross-coupling of aryl iodides with arylboronic acids at ambient CO pressure in poly(ethylene glycol), has been developed. This protocol is general, practical, and recyclable, and offers an attractive alternative to the corresponding palladium-mediated carbonylative Suzuki process for the construction of biaryl ketone scaffolds.

Full text of DOI:10.1039/c4ra08594a

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Copper-catalyzed carbonylative Suzuki coupling of
aryl iodides with arylboronic acids under ambient
pressure of carbon monoxide†
Cite this: RSC Adv., 2014, 4, 44312
Received 13th August 2014
Accepted 10th September 2014
Laijin Cheng, Yanzhen Zhong, Zhuchao Ni, Hongyan Du, Fengli Jin, Qi Rong
and Wei Han*
DOI: 10.1039/c4ra08594a
www.rsc.org/advances
An efficient and ligandless nanocopper-catalyzed carbonylative cross- reported iron replaced palladium to catalyze carbonylative
5
coupling of aryl iodides with arylboronic acids at ambient CO pressure Suzuki reaction and satisfactory results can be obtained.
in poly(ethylene glycol), has been developed. This protocol is general, However, this protocol is inefficient to catalyzed successive
practical, and recyclable, and offers an attractive alternative to the carbonylation of aryl diiodides.
corresponding palladium-mediated carbonylative Suzuki process for
Copper has a strong advantage in terms of cost and toxicity
compared to palladium. And copper has been widely applied
in organic synthesis and oentimes emerges as an alternative
to conduct established palladium-catalyzed cross-coupling
the construction of biaryl ketone scaffolds.
Cross-coupling of aryl halides, arylboronic acids and carbon
6
reactions. Copper-based catalysts have been broadly
1
monoxide (the carbonylative Suzuki reaction ) has been devel-
employed in oxidative carbonylation of alcohols with carbon
oped as a powerful tool for the construction of biaryl and het-
erobiaryl ketones. Moreover, these structural motifs are core
scaffolds that are found in a tremendous range of pharmaceu-
7
monoxide. Comparatively, copper-catalyzed carbonylation of
aryl halide is quite limited. Moreover, the limited examples of
8
9
aminocarbonylation and carbonylative sonogashira of aryl
iodide require high pressures of carbon monoxide and ligands
to ensure efficient catalysis. Copper-catalyzed carbonylation of
diphenyliodonium tetrauoroborate with arylboronic acids
for the synthesis of biaryl ketones was reported by Kang and
2
ticals, advanced organic materials, and photosensitizers.
Consequently, establishing a mild, practical, economical, and
efficient access to biaryl and heterobiaryl ketones is of great
signicance.
Since the rst example of carbonylative Suzuki reaction was
10
co-workers. Since diphenyliodonium tetrauoroborate is
1
reported by Suzuki et al. extensive work has been done to make
made from phenyl iodide, it would be advantageous to directly
carbonylate aryl iodides. Unfortunately, until to date no
general copper-catalyzed carbonylative Suzuki reaction of aryl
halide exists. We report here rst example of copper-catalyzed
carbonylative Suzuki reaction of aryl iodide with arylboronic
acid under atmospheric pressure of carbon monoxide. Our
previous work demonstrated palladium nanoparticles cata-
lyzed carbonylative Suzuki reaction of aryl iodide with a high
level of efficacy even in the absence of a ligand in PEG-400
the transformation more efficient and to widen its substrate
3
scope. However, the overwhelming majority of the reported
methods requires a high pressure (oen $5 bar). Although few
examples of carbonylative Suzuki coupling of aryl iodides under
4
ambient pressure of carbon monoxide have been reported,
palladium remains the metal of choice in almost all cases,
causing several shortcomings, particularly from the perspective
of its pragmatic application because of the high cost, toxicity of
the metal, and the necessity of utilizing expensive ligands. To
address these issues, the development of more sustainable,
economical, and eco-friendly protocol for the aforementioned
transformation is particularly desirable. Very recently, we rst
[
4
poly(ethylene glycol) with an average molecular weight of
00 Da]. This work prompts us to search for nanocopper-
4a
catalyzed carbonylative Suzuki reaction without the assis-
tance of an additional ligand.
Initially, we employed copper nanoparticles for the catalysis
of carbonylative Suzuki reaction of 4-iodonitrobenzene with
phenylboronic acid and carbon monoxide (1 atm) to identify
optimum reaction conditions. Selected results are summarized
Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Jiangsu
Key Laboratory of Biofunctional Materials, Key Laboratory of Applied
Photochemistry, School of Chemistry and Materials Science, Nanjing Normal
University, Wenyuan Road no. 1, 210023 Nanjing, China. E-mail: whhanwei@gmail. in Table 1. On the basis of our previous work of developing PEG-
com; Fax: +86-25-8589-1455
based ligand-free transition metal-catalyzed cross coupling
†
Electronic supplementary information (ESI) available. See DOI:
0.1039/c4ra08594a
4a,5,11
reactions,
we performed the model reaction in PEG-400
1
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a
Table 1 Nanocopper-catalyzed carbonylative Suzuki reaction of 1a with 2a
0
0
Yield of 3aa
Yield of 3a a
Entry
Acid
Base
Solvent
(%)
(%)
1
2
3
4
5
6
7
8
9
—
K
K
K
K
K
Na
KF
TBAF
AcOK
3
3
3
3
2
PO
PO
PO
PO
4
4
4
4
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-200
PEG-2000
Ethylene glycol
PEGDM-190
PEG-400
PEG-400
PEG-400
73
90(75)
14
<5
<5
Trace
43
b
t-BuCOOH
CH
CF
3
COOH
COOH
25
43
55
82
72
5
21
82
5
10
8
82
45
47
3
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
t-BuCOOH
CO
3
2
CO
3
8
Trace
—
Trace
10
—
89
<5
<5
Trace
Trace
10
11
12
13
14
15
16
K
3
K
3
K
3
K
3
K
3
K
3
K
3
PO
PO
PO
PO
PO
PO
PO
4
4
4
4
4
4
4
c
d
e
a
Reaction conditions (unless otherwise stated): 1a (0.5 mmol), 2a (0.75 mmol), CO (balloon), base (1.0 mmol), acid (0.25 mmol), nanocopper (20
ꢀ
b
c
d
e
2
mol%), solvent (2.0 mL), 80 C. Nanocopper (10 mol%). Cu O (20 mol%). CuCl (20 mol%). CuBr (20 mol%).
3 4
with K PO as a base. Consequently, the desired product 3aa that the addition of KF (0.5 equiv.) can ensure effective catal-
ꢀ
can be obtained in 73% yield, whereas the side product form ysis at an elevated temperature (100 C) (Table 2). The car-
Suzuki coupling was also formed in 14% yield (Table 1, bonylative Suzuki reactions of aryl iodides with phenylboronic
entry 1). Very recently, we reported pivalic acid effectively acid demonstrated that electron-decient as well as electron-
suppressed Suzuki coupling and favored carbonylative Suzuki rich aryl iodides worked well. And the electronic nature of
4
a
coupling. As expected, in the presence of the pivalic acid an the aryl iodides had a minor impact on the observed yields.
excellent yield of 3aa was generated with a little amount of the Fluoro- and triuoromethyl-substituted aryl iodides were
side product (<5%) (Table 1, entry 2). Other acids such as reactive and afforded the corresponding products in 75–91%
CH
entries 3 and 4). Successively, other various bases were tested. for the synthesis of pharmaceuticals and advanced materials.
Na CO and KF showed superior results compared with other Sterically hindered 2-iodotoluene also proceeded smoothly
bases such as K CO , TBAF, and AcOK (Table 1, entries 5–9), (Table 2, entry 9). We were pleased to nd that a heterocyle 4-
albeit with less efficiency in terms of yields than K PO . Of the iodo-3,5-dimethylisoxazole (1o) and 1-iodonaphthalene were
3 3
COOH and CF COOH just gave poor results (Table 1, yields (Table 2, entries 2, and 4–6), which are potentially useful
1
2
2
3
2
3
3
4
solvents evaluated, PEG-400 gave the best results (Table 1, suitable substrates and provided the expected products in 90%
entry 2). Notably, ethylene glycol and poly(ethylene glycol) and 87%, respectively (Table 2, entries 15 and 14). Intriguingly,
dimethyl ether (PEGDM-190) were found to be ineffective 1,4-diiodobenzene (1p) and 1,3-diiodobenzene (1q) could
(
Table 1, entries 12 and 13), suggesting that the unique undergo successive carbonylation effectively and furnish cor-
structure of PEG-400 bearing both hydroxyl groups and a responding diketones that are important intermediates for
2
a,2d
polyether chain played a critical role in this reaction. Other advanced functional materials,
catalysts, such as Cu O, CuCl, and CuBr were examined and respectively (Scheme 1).
were observed to be less effective than nanocopper catalyst
Table 1, entries 14–16).
in 87% and 75% yields,
2
To further explore the scope, we extensively surveyed the
carbonylative Suzuki reactions of various aryl iodides with
(
Next, we investigated the rst copper-catalyzed method for representative arylboronic acids under the optimized condi-
carbonylative Suzuki reactions of various aryl iodides. tions (Scheme 2). In general, unsubstituted, para-, meta-, and
However, we observed that more unactivated substrates ortho-substituted arylboronic acids afforded desired products in
compared with 4-iodonitrobenzene were unsuitable to the good to excellent yields. The electronic nature of the arylboronic
above-established reaction conditions. In the Table 1, KF as a acids was observed to be loosely correlated with their reactivity.
base gave a better selectivity than K
3 4
PO , albeit with moderate The reaction conditions were compatible with methyl, methoxy,
efficiency (entry 3). Aer a concise reevaluation, we found out aldehyde, cyano, uoro, and chloro groups. Treatment of
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Table 2 Nanocopper-catalyzed carbonylative Suzuki reaction of 2a naphthalen-2-ylboronic acid (2k) with 1n produced desired
a
with various aryl iodides
product (3nk) in 82% yield. To our delight, a heterocyclic
boronic acid 2m was quite effective and provided desired
product 3km in 90% yield [eqn (1)].
b
Entry
Aryl iodide
Product
Time (h)
5
Yield (%)
c
1
90
To check the reusability of PEG-400 and nanocopper catalyst,
the model reaction of 4-iodonitrobenzene (1a) with phenyl-
boronic acid (2a) and carbon monoxide (1 atm) was tested
2
3
4
9
75
89
91
(Fig. 1). The reaction mixture was extracted with diethyl ether,
and then, the nanocopper-PEG-400 proceeded to the second run
by charging with the same substrates under carbon monoxide
12
12
(1 atm). Gratifyingly, the catalytic system can be recycled up to
ten times with good yields (Fig. 1). And Cu leaching in the
5
6
7
12
4
90
91
80
9
8
9
5
95
93
Scheme
diiodobenzenes.
1
Successive
carbonylative
Suzuki
reactions
of
24
1
1
1
0
1
2
9
9
9
81
91
92
1
1
3
4
12
12
83
87
1
5
9
90
Scheme 2 Carbonylative Suzuki reactions of aryl iodides with aryl-
boronic acids. Reaction conditions (unless otherwise stated):
1
(
(
3 4
0.5 mmol), 2 (0.75 mmol), CO (balloon), K PO (0.5 mmol), KF
a
Reaction conditions (unless otherwise stated): 1a (0.5 mmol), 2a (0.75
PO (0.5 mmol), KF (0.25 mmol), tBuCOOH
0.25 mmol), nanoCu (20 mol%), PEG-400 (2.0 mL), 100 C. Yield of
0.25 mmol), tBuCOOH (0.25 mmol), nano-Cu (20 mol%), PEG-
mmol), CO (balloon), K
(
isolated product aer column chromatography. 1a (0.5 mmol), 2a
3
4
ꢀ
ꢀ
b
400 (2.0 mL), 100 C. Yield of isolated product after column chro-
matography was given. 1g (0.5 mmol), 2g (0.75 mmol), CO (balloon),
K
a
c
3
PO
4
(1.0 mmol), tBuCOOH (0.25 mmol), nanocopper (20 mol%),
(
0.75 mmol), CO (balloon), K
3
PO
4
(1.0 mmol), tBuCOOH (0.25 mmol),
ꢀ
ꢀ
nanocopper (20 mol%), PEG-400 (2.0 mL), 80 C.
PEG-400 (2.0 mL), 80 C.
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Scientic Research Start-up Foundation of Nanjing Normal
University (2011103XGQ0250), the SRF for ROCS, SEM, and the
Priority Academic Program Development of Jiangsu Higher
Education Institutions.
Notes and references
1
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(
3 4
0.75 mmol), CO (balloon), K PO (1.0 mmol), tBuCOOH (0.25 mmol),
ꢀ
nanocopper (20 mol%), PEG-400 (2.0 mL), 80 C.
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3
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13
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14
4
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carbonylative Suzuki reactions of aryl iodides with arylboronic
acids, which affords the best product yields in the absence of a
ligand and under atmospheric pressure of carbon monoxide.
The transformation tolerates a variety of functional groups on
both coupling partners. Diiodobenzenes such as 1,4-diiodo-
benzene (1p) and 1,3-diiodobenzene (1q) can also undergo
successive carbonylative Suzuki reactions. Notably, the catalytic
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the reactions.
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The work was sponsored by the Natural Science Foundation of
China (21302099), the Natural Science Foundation of Jiangsu
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