Recyclable heterogeneous palladium-catalyzed carbonylative Sonogashira coupling under CO gas-free conditions

Article abstract of DOI:10.1080/00397911.2020.1762092

A convenient, efficient and practical heterogeneous palladium-catalyzed carbonylative Sonogashira coupling of aryl iodides with terminal alkynes under CO gas-free conditions has been developed by using an MCM-41-supported bidentate phosphine palladium ace

Full text of DOI:10.1080/00397911.2020.1762092

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: https://www.tandfonline.com/loi/lsyc20
Recyclable heterogeneous palladium-catalyzed
carbonylative Sonogashira coupling under CO gas-
free conditions
Zebiao Zhou, Jianying Li, Zhaotao Xu & Mingzhong Cai
To cite this article: Zebiao Zhou, Jianying Li, Zhaotao Xu & Mingzhong Cai (2020): Recyclable
heterogeneous palladium-catalyzed carbonylative Sonogashira coupling under CO gas-free
conditions, Synthetic Communications, DOI: 10.1080/00397911.2020.1762092
To link to this article: https://doi.org/10.1080/00397911.2020.1762092
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https://doi.org/10.1080/00397911.2020.1762092
Recyclable heterogeneous palladium-catalyzed
carbonylative Sonogashira coupling under CO
gas-free conditions
Zebiao Zhoua, Jianying Lib, Zhaotao Xua, and Mingzhong Caia
aKey Laboratory of Functional Small Organic Molecule, Ministry of Education and Department of
b
Chemistry, Jiangxi Normal University, Nanchang, China; School of Biology and Environmental
Engineering, Jingdezhen University, Jingdezhen, China
ABSTRACT
ARTICLE HISTORY
Received 14 December 2019
A convenient, efficient and practical heterogeneous palladium-cata-
lyzed carbonylative Sonogashira coupling of aryl iodides with ter-
minal alkynes under CO gas-free conditions has been developed by
using an MCM-41-supported bidentate phosphine palladium acetate
complex as catalyst. Here, formic acid was used as the CO source
with dicyclohexylcarbodiimide (DCC) as the activator and a wide var-
iety of alkynyl ketones were generated in moderate to high yields.
This heterogeneous palladium catalyst can be easily recovered via a
simple filtration process and recycled up to 8 times without apparent
loss of activity.
KEYWORDS
Palladium; carbonylative
Sonogashira coupling;
alkynyl ketone; formic acid;
heterogeneous catalysis
GRAPHICAL ABSTRACT
Introduction
Alkynyl ketones are important structural motifs present in various biologically active
molecules,[1] and play a crucial role as key intermediates in the synthesis of natural
products[2] and numerous heterocyclic compounds[3] due to their multifunctional prop-
erties. The traditional method for the preparation of alkynyl ketones involves the acyl-
ation reaction of acid chlorides with terminal alkynes[4] or alkynyl metals.[5] However,
acid chlorides are corrosive and moisture-sensitive, and they are usually only accessible
CONTACT Mingzhong Cai
caimzhong@163.com
Key Laboratory of Functional Small Organic Molecule, Ministry of
Education and Department of Chemistry, Jiangxi Normal University, Nanchang, China.
Supplemental data for this article can be accessed on the publisher’s website.
ß 2020 Taylor & Francis Group, LLC

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Z. ZHOU ET AL.
with a limited scope of functional groups. The palladium-catalyzed carbonylative
Sonogashira cross-coupling reaction is a viable alternative for the construction of
alkynyl ketones since this methodology employs readily available aryl halides (or pseu-
dohalides) and terminal alkynes as starting materials and displays good functional group
tolerance.[6] Since the first palladium-catalyzed carbonylative Sonogashira cross-coupling
reaction was reported by Kobayashi and Tanaka in 1981,[6a] significant efforts have
been made to improve this particular transformation. However, most of these methods
suffer from difficult recovery and non-recyclability of expensive homogeneous palladium
catalysts and employ gaseous carbon monoxide as the CO source. Although gaseous CO
has some advantages, it is a toxic, flammable, colorless and odorless gas whose inhal-
ation even in ppm amounts can be lethal, which prevents extended applications of these
methods in organic synthesis.
Over the past decades, various CO surrogates, including metal carbonyls, formic acid,
aldehydes, formamides, and oxalyl chloride have been developed and utilized in carbon-
ylation reactions.[7] Wu and coworkers reported the first palladium-catalyzed carbonyla-
tive Sonogashira coupling reaction with formic acid as the CO source and acetic
anhydride as the activator.[8] However, pre-preparation of acetic formic anhydride and
the use of a large excess amount of Et3N to neutralize the in situ formed acetic acid
were required. Dicyclohexylcarbodiimide (DCC) is a readily available, inexpensive and
good dehydrating reagent in organic synthesis. Recently, Wu and coworkers developed
a convenient and efficient carbonylative Sonogashira coupling reaction using Pd(OAc)2/
2PPh3 as the catalyst with formic acid as the CO source and DCC as the activator,[9]
but the difficult separation and recovery from the reaction mixture and non-recyclability
of the homogeneous Pd(OAc)2/2PPh3 system are still the main drawbacks. Therefore,
developing a convenient, efficient, and practical route to alkynyl ketones is
highly desirable.
In recent years, microporous and mesoporous materials have found wide applications
in catalysis science and immobilization of homogeneous catalysts on heterogeneous sup-
ports.[10] Mesoporous silica MCM-41 has been widely utilized as a powerful support for
anchoring homogeneous catalysts due to its outstanding advantages, including extremely
high surface area, large and defined pore size, and big pore volume in comparison with
other solid supports.[11] So far, some palladium complexes anchored onto MCM-41
have been successfully used as highly efficient and recyclable catalysts in organic reac-
tions.[12] However, to our knowledge, no example of carbonylative Sonogashira coupling
catalyzed by an MCM-41-supported palladium complex with formic acid as the CO
source has been reported until now. We herein report our newly developed heteroge-
neous palladium-catalyzed carbonylative Sonogashira coupling with HCOOH as the CO
source and DCC as the activator by using an MCM-41-supported bidentate phosphine
palladium acetate complex [MCM-41-2P-Pd(OAc)2] as catalyst (Scheme 1). The reaction
Scheme 1. Heterogeneous palladium-catalyzed carbonylative synthesis of alkynyl ketones with formic
acid as the CO source.

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Scheme 2. Preparation of the MCM-41-2P-Pd(OAc)2 complex.
was conducted in a one-step, one-pot manner; a wide variety of alkynyl ketones were
produced under mild conditions in moderate to high yields with good functional group
tolerance. Compared with the methodology reported by Wu et al. using Pd(OAc)2/
2PPh3 as the catalyst with formic acid as the CO source and DCC as the activator,[9]
the present protocol has the advantages of easy separation of the expensive palladium
catalyst from the product and the catalyst recycling for eight times without apparent
loss of activity.
Results and discussion
The MCM-41-2P-Pd(OAc)2 catalyst was easily prepared according to our previously
reported procedure,[13] as shown in Scheme 2. Firstly, the reaction of mesoporous silica
MCM-41 with N,N-bis((diphenylphosphino)methyl)-3-(triethoxysilyl)propan-1-amine in
toluene at reflux for 24 h, followed by treatment with Me3SiCl at room temperature for
24 h afforded a bidentate phosphino-modified MCM-41 material (MCM-41-2P). The lat-
ter was then coordinated with Pd(OAc)2 in acetone at reflux for 48 h to give the MCM-
41-supported bidentate phosphine palladium acetate complex [MCM-41-2P-Pd(OAc)2]
as a light yellow powder with palladium content of 0.36 mmol/g. The structure of the
catalyst was characterized by FT-IR, XRD, EDS, TGA, SEM, TEM, BET and XPS ana-
lysis (see the Supporting Information).
The MCM-41-2P-Pd(OAc)2 complex was then used as a catalyst for carbonylative
Sonogashira coupling of aryl iodides with terminal alkynes with formic acid as the CO
source and DCC as the activator. Initial experiments with iodobenzene 1a and phenyla-
cetylene 2a were carried out to optimize the reaction conditions, and the results are
summarized in Table 1. Firstly, the effect of various bases on the model reaction was
evaluated with toluene as solvent at 30 ꢀC (entries 1–6). Among tertiary amine bases
tested, Et3N gave an excellent yield of 95% (entry 3), while other organic bases such as
i-Pr2NEt, DBU, n-Bu3N and pyridine were substantially less effective and inorganic
bases such as K2CO3 was ineffective. Reducing the amount of Et3N to 1.0 equiv. gave a
lower yield of 73% (entry 7). Replacement of toluene with other solvents such as DMF,
THF, dioxane and MeCN led to a decreased yield (entries 8–11). We next examined the

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Z. ZHOU ET AL.
Table 1. Optimization of the reaction conditions.a
Entry
Base
Solvent
Temp. (ꢀC)
Yield (%)b
1
2
3
4
i-Pr2NEt
DBU
Et3N
n-Bu3N
pyridine
K2CO3
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DMF
THF
dioxane
MeCN
toluene
toluene
toluene
toluene
toluene
toluene
toluene
30
30
30
30
30
30
30
30
30
30
30
60
80
100
30
30
30
30
11
20
95
56
27
0
73
39
61
81
78
79
32
11
76
54
96
97
5
6
7c
8
9
10
11
12
13
14
15d
16e
17f
18g
aReaction conditions: 1a (1.0 mmol), 2a (2.0 mmol), MCM-41-2P-Pd(OAc)2 (3 mol%), base (2.0 mmol), HCOOH (2.0 mmol),
DCC (2.0 mmol), solvent (4 mL), 30 ꢀC, 24 h.
bIsolated yield.
cEt3N (1.0 mmol) was used.
dHCOOH (1.5 mmol) and DCC (1.5 mmol) were used.
e1 mol% catalyst was used.
f5 mol% catalyst was used.
gPd(OAc)2 (3 mol%) and PPh3 (6 mol%) were used as the catalyst.
effect of reaction temperatures on the reaction (entries 12–14). When the reaction was
conducted at a higher temperature, the yield of 3a reduced significantly, which may be
due to the decreased solubility of CO in toluene at high temperatures. The use of 1.5
equiv. of HCOOH and DCC also resulted in a decreased yield (entry 15). Finally, the
amount of the catalyst was screened. Reducing the amount of the catalyst to 1 mol% led
to a significant decrease in the yield of 3a (entry 16), whilst increasing the amount of
the catalyst to 5 mol% did not improve the yield obviously (entry 17). When homoge-
neous Pd(OAc)2 (3 mol%)/PPh3 (6 mol%) system was used as the catalyst, the desired
3a was also isolated in 97% yield (entry 18), indicating that the catalytic efficiency of
MCM-41-2P-Pd(OAc)2 was comparable to that of Pd(OAc)2/PPh3 system. Therefore,
the optimal reaction conditions are the use of MCM-41-2P-Pd(OAc)2 (3 mol%) in tolu-
ene with Et3N as base at 30 ꢀC for 24 h (entry 3).
With the optimal conditions in hand, we began to study the substrate scope of this
heterogeneous palladium-catalyzed carbonylative Sonogashira coupling reaction. First, a
variety of aryl iodides were successfully applied to this reaction, and the results are sum-
marized in Table 2. para- or meta-Substituted iodobenzenes 1b–h bearing electron-
donating or electron-withdrawing groups could undergo the carbonylative Sonogashira
coupling smoothly with phenylacetylene to give the corresponding alkynyl ketones 3b–h

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Table 2. Heterogeneous Pd-catalyzed carbonylative Sonogashira coupling of various aryl iodides
with phenylacetylene 2a.a,b
aReaction conditions: 1 (1.0 mmol), 2a (2.0 mmol), MCM-41-2P-Pd(OAc)2 (3 mol%), Et3N (2.0 mmol), HCOOH (2.0 mmol),
DCC (2.0 mmol), toluene (4 mL), 30 ꢀC, 24 h.
bIsolated yield.
in moderate to high yields. Generally, electron-rich aryl iodides displayed a slightly
higher reactivity than electron-poor ones. Moreover, aryl iodides 1f–h bearing strong
electron-withdrawing groups delivered the desired products 3f–h in relatively lower
yields because of the formation of byproducts derived from the direct coupling reaction.
In addition, rigid 4-iododiphenyl 1i and bulky 1-iodonaphthalene 1j were also good
substrates and afforded the expected products 3i and 3j in 78–89% yields. The sterically
hindered methyl 2-iodobenzoate 1k gave the target product 3k in only a 60% yield.
Notably, heteroaryl iodides such as 2-iodothiophene 1l and 6-iodoquinoline 1m were
compatible with the standard conditions and provided the corresponding products 3l
and 3m in high yields. A wide range of functional groups such as methyl, methoxy,
chloro, cyano, trifluoromethyl and ester were well tolerated in this heterogeneous palla-
dium-catalyzed carbonylative coupling reaction. We also performed the carbonylative
Sonogashira coupling reaction of aryl bromides with phenylacetylene under the opti-
mized conditions, unfortunately, aryl bromides were not reactive in this transformation,
even if some active aryl bromides such as 4-bromonitrobenzene and 4-bromobenzalde-
hyde were used as substrates at 30 or 60 ꢀC, no desired products were produced.
Subsequently, we turned our attention to examining the generality of the alkyne cou-
pling partner with various terminal alkynes. As shown in Table 3, the electron-rich

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Z. ZHOU ET AL.
Table 3. Heterogeneous Pd-catalyzed carbonylative Sonogashira coupling of various terminal alkynes
with iodobenzene 1a.a,b
aReaction conditions: 1a (1.0 mmol), 2 (2.0 mmol), MCM-41-2P-Pd(OAc)2 (3 mol%), Et3N (2.0 mmol), HCOOH (2.0 mmol),
DCC (2.0 mmol), toluene (4 mL), 30 ꢀC, 24 h.
bIsolated yield.
cThe reaction was conducted at 60 ꢀC.
arylacetylenes 2b–e showed a similar reactivity with phenylacetylene 2a and delivered
the corresponding coupling products 3n–q in excellent yields. By contrast, electron-defi-
cient arylacetylenes 2f–h showed a slightly lower reactivity and gave the desired prod-
ucts 3r–t in 80–89% yields. 4-Fluorophenylacetylene 2f provided a better yield of
product than 4-chlorophenylacetylene 2g and 4-bromophenylacetylene 2h. This may be
due to the stronger electron-withdrawing effect of fluorine, which aids in the reaction
of the alkyne with the acylpalladium intermediate. In addition, heteroarylacetylenes
such as 3-ethynylpyridine 2i and 3-ethynylthiophene 2j underwent this reaction at a
relatively higher temperature and furnished the expected products 3u and 3v in moder-
ate yields. Notably, a conjugated enyne, 1-ethynylcyclohexene 2k reacted well in this
transformation at 60 ꢀC, delivering the target product 3w in 82% yield. Moreover, cyclo-
alkyl alkynes such as cyclohexylacetylene 2l and cyclopropylacetylene 2m were success-
fully transformed into the corresponding products 3x and 3y at 60 ꢀC in good yields.
But, 1-octyne 2n was a poor substrate and afforded the desired product 3z in only
20% yield.
To confirm whether the observed catalysis was due to the heterogeneous catalyst
MCM-41-2P-Pd(OAc)2 or a soluble Pd species leached from MCM-41-2P-Pd(OAc)2,

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Scheme 3. Proposed catalytic cycle.
the heterogeneity of the catalyst was further confirmed by hot filtration experiment.[14]
For this, we carried out the carbonylative Sonogashira coupling of iodobenzene 1a with
cyclohexylacetylene 2l, and removed the palladium catalyst from the reaction mixture
by filtration at 60 ꢀC at approximately 40% conversion of 1a. The catalyst-free filtrate
was then allowed to react further at 60 ꢀC for 12 h with the addition of HCOOH (1.0
equiv.) and DCC (1.0 equiv.). It was found that no increase in conversion of 1a was
observed in the filtrate, which rules out the contribution to the observed reaction from
a leached Pd species in the solution, indicating the heterogeneous nature of this
transformation.
A possible mechanism for this heterogeneous palladium-catalyzed carbonylative
Sonogashira coupling reaction is outlined in Scheme 3. Firstly, the MCM-41-2P-
Pd(OAc)2 complex is reduced by CO, generated in situ from formic acid and DCC to
the MCM-41-2P-Pd(0) complex.[15] Oxidative addition of Ar-I (1) to the MCM-41- 2 P-
Pd(0) complex generates an MCM-41-anchored arylpalladium(II) complex (A), which is
followed by migratory insertion of carbon monoxide yielding an MCM-41-anchored
acylpalladium(II) complex (B). Subsequent reaction between intermediate B and ter-
minal alkyne (2) with the aid of Et3N gives intermediate C. Finally, reductive elimin-
ation of intermediate C affords the desired alkynyl ketone (3) and regenerates the
MCM-41-2P-Pd(0) complex to complete the catalytic cycle.

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Z. ZHOU ET AL.
Table 4. Recycle of the MCM-41-2P-Pd(OAc)2 catalyst.a
Entry
MCM-41-2P-Pd(OAc)2
Yieldb (%)
Entry
MCM-41-2P-Pd(OAc)2
Yieldb (%)
1
2
3
4
Fresh
95
94
94
93
5
6
7
8
Recycle 4
Recycle 5
Recycle 6
Recycle 7
92
93
92
91
Recycle 1
Recycle 2
Recycle 3
aReaction conditions: 1a (1.0 mmol), 2a (2.0 mmol), MCM-41-2P-Pd(OAc)2 (3 mol%), Et3N (2.0 mmol), HCOOH (2.0 mmol),
DCC (2.0 mmol), toluene (4 mL), 30 ꢀC, 24 h.
bIsolated yield.
For a heterogeneous precious metal catalyst, it is important to investigate its ease of
separation from the product and reusability. We next examined the recyclability of the
MCM-41-2P-Pd(OAc)2 catalyst in the carbonylative Sonogashira coupling reaction of
iodobenzene 1a with phenylacetylene 2a. After the reaction was completed, the reaction
mixture was diluted with ethyl acetate and filtered. The catalyst was washed with DMF,
distilled water and ethanol, and dried at 80 ꢀC in vacuo for 1 h. The recovered catalyst
can be used directly in the next cycle with the same substrates under the identical con-
ditions. As shown in Table 4, this heterogeneous palladium catalyst could be recycled
up to eight times with almost consistent catalytic activity. The excellent reusability of
the MCM-41-2P-Pd(OAc)2 catalyst may arise from the stronger chelation action
between the bidentate phosphine ligand and palladium, which prevents palladium leach-
ing effectively.
Conclusions
In summary, we have developed a convenient, economic and practical method for the
construction of alkynyl ketones under carbon monoxide gas-free conditions. Through
the heterogeneous palladium-catalyzed carbonylative Sonogashira coupling reactions of
aryl iodides with terminal alkynes, with formic acid as the CO source, a wide range of
alkynyl ketones could be produced in moderate to high yields. Importantly, this hetero-
geneous palladium catalyst can be easily recovered via a simple filtration process and
recycled at least eight times without apparent loss of activity. Our system not only
avoids the usage of gaseous CO, but also solves the basic problems of palladium catalyst
recovery and reuse. Thus, the present method represents the first example of both using
formic acid as a liquid CO source and an MCM-41-supported palladium complex as a
recyclable catalyst for the carbonylative Sonogashira coupling reaction.
Experimental
All reagents were purchased from different commercial sources and used as received
without further purification. All solvents were dried and purified by distillation prior

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9
to use. All reactions were performed under an atmosphere of argon. The products were
purified by flash column chromatography on silica gel. A mixture of light petroleum
1
ether and ethyl acetate (v/v ¼ 19:1) was generally employed as eluent. H NMR and 13C
NMR spectra were recorded on a Bruker Avance 400 NMR spectrometer (400 MHz or
100 MHz, respectively) in CDCl3 as solvent with TMS as internal reference. Melting
points were determined on a Beijing Tech Instrument Co., LTD X-6 melting point
apparatus and are uncorrected. HRMS spectra were recorded on a Q-Tof spectrometer
with micromass MS software using electrospray ionization (ESI). The MCM-41-2P-
Pd(OAc)2 complex was prepared according to our previously reported procedure,[13] the
content of palladium was measured to be 0.36 mmol/g based on ICP-AES analysis.
General procedure for the heterogeneous palladium-catalyzed
carbonylative synthesis of alkynyl ketones
MCM-41-2P-Pd(OAc)2 (3 mol%) was transferred into an oven-dried reaction tube under
Ar. Then aryl iodide (1.0 mmol), alkyne (2.0 mmol), formic acid (2.0 mmol), and toluene
(4 mL) were added to the reaction tube. After DCC (2.0 mmol) and Et3N (2.0 mmol)
were added, the tube was sealed, and the reaction mixture was stirred at 30 ꢀC for 24 h.
After completion of the reaction, the reaction mixture was diluted with ethyl acetate
(10 mL) and filtered. The catalyst was washed with DMF (2 ꢁ 5 mL), distilled water
(2 ꢁ 5 mL), ethanol (2 ꢁ 5 mL), and dried at 80 ꢀC in vacuo for 1 h and reused in the
next run. The filtrate was concentrated under vacuum and the residue was purified by
chromatography on silica gel (eluent: light petroleum ether/ethyl acetate ¼ 19:1) to
afford the alkynyl ketone product 3.
Full experimental detail, characterization data of all compounds. This material can be
found via the “Supplementary Content” section of this article’s webpage.
Funding
We thank the National Natural Science Foundation of China [No. 21462021], the Natural
Science Foundation of Jiangxi Province of China [No. 20161BAB203086] and Key Laboratory of
Functional Small Organic Molecule, Ministry of Education [No. KLFS-KF-201704] for finan-
cial support.
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