Superparamagnetic copper ferrite nanoparticles catalyzed aerobic, ligand-Free, regioselective hydroboration of alkynes: Influence of synergistic effect

Article abstract of DOI:10.1016/j.apcata.2016.03.019

We discovered a general and comprehensive approach for the regioselective hydroboration of terminal and internal alkynes to synthesize vinylboronates using inexpensive and magnetically separable copper ferrite nanoparticles at low catalyst loading using Bis(pinacolato)diboron in the absence of ligand and additives, under mild and greener conditions. A diverse range of functional groups was tolerated in the reaction, including allene and enones, and the corresponding boronates were obtained in high yields under air. Moreover, the assynthesized alkenylboronates were used as precursors to prepare wide variety of vinylorgano chalcogenides regioselectively, in high yields. The present protocol enable the conversion of C_sp-H bonds to make C_sp²-B bonds via activation of B-B bond, followed by formation of C_sp²-Se (Te or S) bonds via activation of Se (Te or S)- Se (Te or S) bonds in a regioselective manner. Deuterium isotope labeling studies showed that the proton source of vinyl boronate stem from the solvent employed.

Full text of DOI:10.1016/j.apcata.2016.03.019

Applied Catalysis A: General 519 (2016) 78–84
Contents lists available at ScienceDirect
Applied Catalysis A: General
journal homepage: www.elsevier.com/locate/apcata
Superparamagnetic copper ferrite nanoparticles catalyzed aerobic,
ligand-Free, regioselective hydroboration of alkynes: Influence of
synergistic effect
Balaji Mohan, Kang Hyun Park∗
Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan 609-735, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
We discovered a general and comprehensive approach for the regioselective hydroboration of terminal
and internal alkynes to synthesize vinylboronates using inexpensive and magnetically separable copper
ferrite nanoparticles at low catalyst loading using Bis(pinacolato)diboron in the absence of ligand and
additives, under mild and greener conditions. A diverse range of functional groups was tolerated in
the reaction, including allene and enones, and the corresponding boronates were obtained in high yields
under air. Moreover, the assynthesized alkenylboronates were used as precursors to prepare wide variety
of vinylorgano chalcogenides regioselectively, in high yields. The present protocol enable the conversion
of Csp H bonds to make Csp B bonds via activation of B B bond, followed by formation of Csp Se (Te
or S) bonds via activation of Se (Te or S)- Se (Te or S) bonds in a regioselective manner. Deuterium isotope
labeling studies showed that the proton source of vinyl boronate stem from the solvent employed.
© 2016 Elsevier B.V. All rights reserved.
Received 10 November 2015
Received in revised form 8 March 2016
Accepted 17 March 2016
Available online 19 March 2016
Keywords:
Copper ferrite nanoparticles
Deuterium
Green synthesis
Hydroboration
Organochalcogenides
2
2
1. Introduction
copper catalyzed hydroboration of alkynes are considered to be
a cost-effective and straightforward approach to obtain alkenyl-
Suzuki-Miyaura coupling is the most widely used organic reac-
tion among synthetic chemists to form various kinds of bonds
especially C C, C O, and C N, so on [1–4]. Undoubtedly, C Se
(Te or S) bonds exhibit important biological properties, especially
antiviral, anticancer and antitumor properties [5–8]. Suzuki cou-
pling involves the use of boronic acids or analogues with different
partners and transition-metal catalysts, which allows for the syn-
thesis of a wide range of important organic molecules. The high
stability, nontoxic nature, easy of handling, and substrate com-
patibility of organoboron compounds make them powerful and
promising synthons in organic synthesis. Although numerous suc-
cessful catalytic processes to synthesize vinylboronates have been
established, attempts to increase the catalytic efficiency and to con-
trol reaction selectivity with broad substrate scope are still in place.
Borylation of carbon-carbon triple bonds, followed by protonation,
is one of the most attractive routes to generate vinylboronates with
high regioselectivity. So far, significant efforts have been made
to develop practical methods to synthesize this scaffold [9–14].
Among these, several methods based on transition-metal catalysis
have been reported during the past decade [15–39]. In particular,
boronic esters with high regioselectivity. However, most of the
copper catalyzed reactions are homogeneous and require high cata-
lyst loading, ligands, and long reaction times to furnish high yields
and selectivity. Recycling of the catalyst is highly desirable, as it
can contribute significantly to cost reduction and the environment
protection. Recently, Li and co-workers reported that micro cop-
per powder promoted heterogeneous version of hydroboration of
alkynes under inert atmosphere [40]. It is known that reducing the
size from micro to nano could lead to different properties. Because
of their large surface area, nano particles can adsorb a greater num-
ber of reactant molecules, which in turn undergo effective collisions
to furnish the desired products in high yields, even at low catalyst
loading. Our literature survey showed that very few nanoparticle
catalysts have been used for the preparation of vinylboronates in
the absence of phosphine ligands and those protocols require high
temperature to accomplish high conversion [22,41].
During the past decade, significant improvements have been
made in the field of nanotechnology and nano science, which have
led to the design and production of new nanostructured catalytic
systems. Among these catalytic systems, transition-metal nanopar-
ticles (NPs) have attracted much attention because of their larger
surface areas and higher density of active sites as compared to their
bulk-metal equivalents; such properties enable their use for cat-
alytic applications in various organic transformations [42–45]. NPs
∗
Corresponding author.
E-mail address: chemistry@pusan.ac.kr (K.H. Park).
http://dx.doi.org/10.1016/j.apcata.2016.03.019
0926-860X/© 2016 Elsevier B.V. All rights reserved.

B. Mohan, K.H. Park / Applied Catalysis A: General 519 (2016) 78–84
79
are promising heterogeneous catalysts that are effective even at
low concentrations, allows easy isolation of the product, ligand free,
and can be easily recovered and recycled. These intriguing features
of NPs are highly desirable in the context of environmental and
industrial concerns. In addition, it has been reported that supported
metal NPs should have inherent advantages over their counterparts
because of easy dissolution under experimental conditions, effi-
cient recycling, aggregation, metal dispersion, synergistic effects
between the metal and support, so on. Among various metal sup-
ports for NPs, magnetic materials have drawn much attention
because the easy and complete recovery makes them for sev-
eral recycles after the reaction by using external magnet and also
eliminate metal contamination with products that are especially
biologically important molecules [46–56]. Copper ferrite (CuFe2O4)
NPs with a spinel structure have been used widely in batteries, fuel
cells, biology and catalytic studies owing to their advantages such
as environment friendliness, moisture insensitivity, high disper-
sity, and easy recovery using an external magnetic field [57–63].
However, to the best of our knowledge, the composition-effect of
the copper ferrite nanocatalysts on the catalytic performance for
hydroboration of alkynes has not been reported.
with anhydrous magnesium sulfate followed by filtration and
rotary evaporation of the solvent and the residue obtained was
analyzed by GC–MS.
2.4. Typical procedure for the synthesis of phenylvinyl selenides
from phenylselenium chloride
To a schlenk tube, phenylselenium chloride (1 eq.) and pentenyl-
boronate (1.2 eq.) were charged followed by 1 mL of BMIM.BF4 and
the mixture was stirred at RT for 24 h. After stirring, the reaction
mixture was extracted with diethyl ether and washed with water
several times until complete removal of ionic liquid has achieved.
The combined ether extracts were dried with anhydrous magne-
sium sulfate, filtered and rotary evaporated. The residue obtained
was analyzed by GC–MS.
2.5. Recycle test
A 10 mL aluminium capped vial equipped with a stir bar was
charged with a mixture of alkyne (1 mmol), bis(pinacoloto)diboron
(1.2 mmol), 0.5 mol% CuFe2O4, potassium tert-butoxide (10 mol%)
and methanol (2 mL). The mixture was stirred at 50 ◦C for 12 h in
air. After the reaction, the catalyst was recovered by an external
magnetic field followed by washing with methanol and dried in a
vacuum for 12 h. The recovered nanoparticle was then reused four
times in subsequent reactions under identical conditions without
any significant loss of catalytic activity.
Herein, we report the hydroboration of alkynes with
a
bis(pinacoloto)diboron using CuFe2O4 NPs as catalyst to prepare
vinylboronates regioselectively in high yield under air. We demon-
strate that the catalyst is selective, efficient and the synergistic
effect is the key parameter to its high catalytic activity. One-pot syn-
thesis of biologically important arylchalcogenide derivatives was
also demonstrated.
3. Results and discussion
2. Experimental
3.1. Optimization of reaction conditions
2.1. Materials and instrumentation
In continuation of our studies on copper-catalyzed transforma-
tions and exploration of new nanocatalytic systems [64–69], we
report commercially available [70] CuFe2O4 NPs catalyze hydrobo-
ration of alkynes in the presence of bis(pinacolato)diboron (B2Pin2)
and base, under mild conditions. B2Pin2 is an environmental
friendly, benchmark reagent and more stable towards oxygen and
moisture compared to other boron sources that cannot be handled
in air owing to oxidative and hydrolytic reactions of the B H bonds.
In addition, lower catalyst loadings of an inexpensive catalyst,
no phosphine or NHC-ligands, effective conversion of challenging
alkynes, high yields, excellent regioselectivity, heterogeneous etc.,
are important factors in the context of green chemistry.
All commercial reagents and starting materials were pur-
chased from Sigma-Aldrich and TCI and used without further
purification. Methanol-d4 was procured from Acros Organics. The
products reported are known and their mass splitting pattern
were consistent with the preceding literature. The mass spectra
were determined by using Shimadzu GCMS-QP 2010 Ultra (Pusan
National University). The NMR spectra were recorded on an Agilent
300 MHz spectrometer.
2.2. General procedure for the synthesis of vinylboronates
So, keeping these aspects in mind, we initiated our studies
by investigating the hydroboration of 4-tolylacetylene (1a) as the
model substrate in the presence of B2Pin2 (2a, 1.2 equiv) and base,
using CuFe2O4 NPs as the catalyst, to optimize the reaction condi-
tions. Initially, the base (potassium tert-butoxide) and temperature
(50 ◦C) were kept constant while the other parameters were varied.
The solvents acetonitrile, toluene, tetrahydrofuran, and dimethyl
sulfoxide afforded less satisfactory results (Table 1, entries 1–4),
whereas methanol produced the highest yield (Table 1, entry 5) of
the borylated product (3aa). A drop in yield was observed when the
reaction was performed at room temperature (Table 1, entry 6). A
control experiment with no catalyst has failed to increase the rate
of the reaction and as a consequence, the yield was diminished
(Table 1, entry 7). Among the bases tested, potassium carbon-
ate and potassium hydroxide were less effective as compared to
potassium tert-butoxide (Table 1, entries 8 and 9). The hydrob-
oration could also be carried out successfully in the absence of
base with a satisfactory yield (Table 1, entry 10). To the best of
our knowledge, this is the first report of a heterogeneous catalyzed
hydroboration of terminal alkynes to obtain high product yields in
the absence of a base, at low catalyst copper loading. Interestingly,
CuFe2O4 nanoparticles were much more catalytically active than
A 10 mL aluminium capped vial equipped with a stir bar was
charged with a mixture of alkyne (1 mmol), bis(pinacoloto)diboron
(1.2 mmol), 0.5 mol% CuFe2O4, potassium tert-butoxide (10 mol%)
and methanol (2 mL). The mixture was stirred at 50 ◦C for 12 h in
air. Afterwards, the mixture was diluted with diethyl ether, fil-
tered through celite bed, and extracted with water three times.
The combined organic extract was dried with anhydrous magne-
sium sulfate followed by filtration and rotary evaporated of the
solvent, the residue obtained was subjected to analyze GC–MS and
the crude product was purified by column chromatography on silica
with hexane as eluent.
2.3. Typical procedure for the synthesis of unsymmetrical vinyl
chalcogenides from alkenylboronates and diaryl chalcogenides
To a 10 mL sealed aluminium capped glass vial with septum,
charged diphenyl dichalcogenide (0.55 eq.), phenylvinyl boronate
(1eq.), DMSO:H2O (2:1) and CuFe2O4:bpy (5 mol%). The mixture
was heated at 100 ◦C under vigorous magnetic stirring for 12 h.
After stirring for appropriate time, mixture was cooled to RT,
diluted with diethyl ether, filtered through celite bed, and extracted
with water three times. The combined organic extract was dried

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B. Mohan, K.H. Park / Applied Catalysis A: General 519 (2016) 78–84
Table 1
Optimization studies of CuFe2O4 nanoparticles catalyzed hydroboration of 4-tolylacetylenea.
Entry
Solventb
Base
Yield of 3aa (%)c
1
2
3
4
5
6
7
8
acetonitrile
toluene
thf
t-BuOK
t-BuOK
t-BuOK
t-BuOK
t-BuOK
t-BuOK
t-BuOK
K2CO3
27
4
9
18
dmso
methanol
methanol
methanol
methanol
methanol
methanol
methanol
methanol
methanol
90 (87)d
73e
14f
83
9
KOH
83
10
11
12
13
79g
61h
77i
80j
t-BuOK
t-BuOK
t-BuOK
a
Optimized reaction conditions: 4-tolylacetylene (1 mmol), B2Pin2 (1.2 mmol), 0.5 mol% of CuFe2O4 nanoparticles with respect to 4-tolyl acetylene, 10 mol% of t-BuOK
with respect to 1a, T = 50 ◦C, t = 12 h.
b
2 mL of solvent was used.
Yield and selectivity were determined by GC–MS, ␤ = 100%.
Isolated yield in parenthesis.
Reaction at room temperature.
Reaction without catalyst.
Reaction in the absence of base.
Copper oxide nanopowder (544868, aldrich).
CuO hollow structures.
c
d
e
f
g
h
i
j
Cu2O nanocubes.
the commercial CuO nanopowder, which had a detrimental effect
on the reaction outcome (Table 1, entry 11). CuO hollow struc-
tures and Cu2O nanocubes were also synthesized [71–73] from
our previously reported publications, and their catalytic activities
were compared. It was found that they were less productive under
standard experimental conditions (Table 1, entries 12 and 13). The
enhanced catalytic activity of bimetallic CuFe2O4 NPs might be due
to their physical and chemical properties resulting from synergistic
effects between the two metals [74–79]. Very recently, despite the
synergistic effect, Ranu and co-workers demonstrated the role of
iron present in copper ferrite NPs in the synthesis of unsymmetrical
1,3-diynes [55].
material, and the corresponding vinylboronate was obtained with
retention of ␤-selectivity. Phenyl propyne and phenyl propargyl
ether also afforded the corresponding vinylboronates in good yields
(Table 2, entries 3ai and 3aj).
Extending the synthetic utility of the reaction to challenging
aliphatic alkynes, including sterically demanding, cyclic, long chain
alkynes gave the desired yields: the reactions proceeded in good
to moderate yields with enhanced selectivity. To the best of our
knowledge, there has been no extensive study on the high ␤-
selectivity of hydroboration of these types of substrates, using a
very low catalyst loading of heterogeneous copper catalysts in air,
without a ligand and additives. Excellent yield and selectivity were
achieved with 1-ethynyl cyclohexene (Table 2, entry 3ak). The same
yield and selectivity were observed with alkynes having cyclo-
propyl and methyl propargyl units (Table 2, entries 3al and 3am).
Highly sterically hindered alkynes such as 1-octyne, isopropeny-
lacetylene, dimethylethynyl carbinol, and 1-pentyne were also
tolerated, with a slight detrimental effect on yields; however, the
selectivity remains excellent (Table 2, entries 3an–3aq). CuFe2O4
NPs exhibits complete chemoselectivity towards the monobory-
lation of alkynes in the presence of alkenes (Table 2, entry 3ao).
Internal alkynes such as diphenylacetylene, 1-phenyl-1-propyne
and 3-hexyne were also participated in the reaction, and the
products were obtained in moderate yields with unchanged selec-
tivity (Table 2, entries 3ar–3at). Remarkably, our protocol could be
extended to enones and allenes as well; for example, 3-methyl-
2-cyclohexenone could be efficiently hydroborated as per the
anti-Markovnikov rule (Table 2, entry 3au), while the treatment
of cyclohexylallene, led to a mixture of products (Table 2, 3av); the
same observation was made by Yoshida and co-workers [39]. The
results summarized in Table 2 indicate that this protocol allows
easy access to a wide variety of valuable vinylboronates synthon.
3.2. Substrate scope
The final optimized reaction conditions for hydroboration of
alkynes were found to be 0.5 mol% copper ferrite NPs, 10 mol%
of potassium tert-butoxide, and 2 mL of methanol as solvent at
50 ◦C to afford the vinyl boronate product in 90% yield (Table 1,
entry 5). With a highly catalytically active system in hand, we
examined the scope of the hydroboration of a variety of alkynes
under these optimized conditions. The reaction of 2a with a variety
of alkynes proceeded smoothly, demonstrating the compatibil-
ity of 2a with the reaction conditions. Aromatic alkynes bearing
electron-donating or electron-withdrawing substituents, includ-
ing ortho-substitution, were amenable to this protocol with high
␤- selectivity (Table 2, entries 3ab–3af). Heteroalkynes, including
3-ethynyl thiophene and 2-ethynyl pyridine, were well tolerated,
providing excellent yields and selectivities (Table 2, entries 3ag and
3ah). The reaction of 3-ethynyl thiophene initially was sluggish
at 50 ◦C and showed only 38% conversion (not shown); however,
refluxing for 12 h ensured complete consumption of the starting

B. Mohan, K.H. Park / Applied Catalysis A: General 519 (2016) 78–84
81
Table 2
Substrate scope of CuFe2O4 nanoparticles catalyzed hydroboration of alkynesa.
aReaction conditions: Alkyne (1 mmol), B2Pin2 (1.2 mmol), 0.5 mol% catalyst, 10 mol% of t-BuOK,
T = 50 ◦C, t = 12 h.
bYield and ␤-selectivity were determined by GC–MS.
3.3. Mechanistic studies with deuterium labelling
First, subjecting 1-deuterio-2-phenylacetylene and B2Pin2 to
the catalytic reaction in methanol-d4 under argon atmosphere lead
to exclusive formation of the vinylboronate with deuterium at
internal and terminal carbon as well (m/z 232, Scheme 1a). Next,
same experiment in methanol afforded vinyl boronate with pro-
ton at internal carbon and deuterium at terminal carbon remain
intact stem from the starting material phenylacetylene-D and
cannot be exchanged with internal carbon under our experimen-
tal conditions (m/z 231, Scheme 1b). Furthermore, a reaction of
phenylacetylene in CD3OD showed incorporation of deuterium
was observed at internal carbon whereas proton can be seen at
In order to confirm the source of proton introduced in the
vinyl boronate products, we performed a series of control experi-
ments such as deuterium isotope labeling studies and progress of
the reaction was analyzed with the aid of in-situ GC–MS. All in-
situ mechanistic investigation experiments were carried out in the
absence of base in order to prevent choke during GC–MS analysis.
The samples were taken from the reaction mixture after stirring
stopped for 15 min and external magnetic field was used to avoid
catalyst contamination from the sample.

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B. Mohan, K.H. Park / Applied Catalysis A: General 519 (2016) 78–84
Scheme 1. In situ GC–MS mechanistic investigations.
Scheme 2. Intermolecular competition.
terminal carbon (m/z 231, Scheme 1c). At last, an experiment with
phenylacetylene in methanol gave a desired product with hydrogen
at both internal and terminal carbons (m/z 230, Scheme 1d). Fur-
thermore, intermolecular competition between 4-ethynyltoluene
and 1-deuterio-2-phenylacetylene in methanol-d4 showed that no
exchange of proton was observed on product B (Scheme 2a) and
similarly, Scheme 2b also depicts the same reaction in methanol
confirms the proton generated from solvent solely.
the carbon was adsorbed on the surface of the catalyst (IV) affording
the expected vinyl boronate product regioselectively, V.
3.5. Recycle test
To evaluate the reusability of the catalyst, the reaction of 4-
ethynyl toluene with B2Pin2 was examined. The recovered NPs
could be reused efficiently four times (90, 86, 81, 77%) respectively,
with slight decrease of catalytic activity (Scheme 4).
The all above results from the control experiments revealed the
proton source arise from the solvent used in the reaction (see Sup-
porting information for GC–MS chromatograms).
3.6. Scope of vinylboronates in the synthesis of vinyl
chalcogenides
3.4. Plausible catalytic cycle
It is well-known from the preceding literature that the
boronic acids and their analogs have been widely used in the
Suzuki-Miyaura coupling reaction. Recently, Abell and co-workers
have used aryl boronates, sources for the in situ generation of
azides and have “clicked” them with alkynes, afforded biologi-
cally important triazoles [85]. Similarly, herein we demonstrate
the vinylboronates can be effectively used as synthons for
Se (S or Te)-Csp2 bond formation through the cross-coupling
reaction of diphenyl dichalcogenides and phenylvinylboronates,
For a possible reaction mechanism we have proposed a catalytic
cycle that is in accordance to the hydroboration of alkynes [40]
(Scheme 3). First, reaction of Me3COK with B2Pin2 and CuFe2O4
generates I and II followed by adsorption of alkyne with I gives
intermediate III, which subsequently transformed to IV. At last,
the catalyst was regenerated (recovered by external magnetic field)
after a source of proton (from the solvent methanol) replaces where

B. Mohan, K.H. Park / Applied Catalysis A: General 519 (2016) 78–84
83
Scheme 3. Proposed mechanism.
Scheme 4. Reusability of the catalyst in the reaction of 4-ethynyl toluene with B2Pin2.
Scheme 5. Synthetic utility of alkenylboronates in the cross-coupling reaction with diorgano dichalcogenides.
Scheme 6. Extension of substrate scope of pentenylboronate with phenylselenium chloride.
employing the same CuFe2O4 NPs along with the bipyridyl ligand to
afford diphenyl vinylchalcogenides in excellent yields (Scheme 5)
[80–82]. The obtained diphenylvinyl selenides, tellurides and sul-
fides are observed in yields of 85, 100, 82% and trans-selectivities
99, 100 and 100% respectively (see Supporting information).
(55%) under mild and transition-metal free conditions (Scheme 6)
[83,84].
4. Conclusions
In summary, we have described how the synergistic effect of
CuFe2O4 NPs can be exploited for the efficient hydroboration of sev-
eral challenging alkynes taking using bis(pinacoloto)diboron. This
protocol represents the first borylation reaction via heterogeneous
catalysis at low catalyst loading. The as-synthesised vinylboronates
undergo cross-coupling with diorganodichalcogenides, affording
variously substituted diorgano vinylchalcogenides in excellent
yields with high regioselectivity. The robustness of the catalytic
system is demonstrated over four recycling experiments.
3.7. Extension of substrate scope
Furthermore, the scope of the vinylboronates was estab-
lished again upon extending in a reaction with electrophilic
phenylselenium chloride under metal-free conditions employ-
ing butylimidazolium tetrafluoroborate (BMIMBF4) ionic liquid
as catalyst and solvent to generate phenylvinyl selenides as an
alternative procedure to obtain unsymmetrical vinylselenides

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[37] A.L. Moure, R.G. Arrayas, D.J. Cardenas, I. Alonso, J.C. Carretero, J. Am. Chem.
Acknowledgements
Soc. 134 (2012) 7219–7222.
[38] A.L. Moure, P. Mauleon, R.G. Arrayas, J.C. Carretero, Org. Lett. 15 (2013)
2054–2057.
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education (Nos. NRF-2015R1D1A1A02060684
and 2013R1A1A1A05006634). K.H.P thanks to the TJ Park Junior
Faculty Fellowship and LG Yonam Foundation.
[39] H. Yoshida, I. Kageyuki, K. Takaki, Org. Lett. 16 (2014) 3512–3515.
[40] J. Zhao, Z. Niu, H. Fu, Y. Li, Chem. Commun. 50 (2014) 2058–2060.
[41] V.S. Rawat, B. Sreedhar, Synlett 25 (2014) 1132–1136.
[42] T. Jin, M. Yan, Y. Yamamoto, ChemCatChem 4 (2012) 1217–1229.
[43] A. Fihri, M. Bouhrara, B. Nekoueisharaki, J.-M. Basset, V. Polshettiwar, Chem.
Soc. Rev. 40 (2011) 5181–5203.
[44] Z. Yinghuai, K. Chenyan, A.T. Peng, A. Emi, W. Monalisa, L.K.-J. Louis, N.S.
Hosmane, J.A. Maguire, Inorg. Chem. 47 (2008) 5756–5761.
[45] Z.-C. Zhang, B. Xu, X. Wang, Chem. Soc. Rev. 43 (2014) 7870–7886.
[46] V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.-M. Basset, Chem.
Rev. 111 (2011) 3036–3075.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.apcata.2016.03.
019.
[47] K. Swapna, S.N. Murthy, M.T. Jyothi, Y.V.D. Nageswar, Org. Biomol. Chem. 9
(2011) 5989–5996.
[48] R. Zhang, J. Liu, S. Wang, J. Niu, C. Xia, Sun, ChemCatChem 3 (2011) 146–149.
[49] S. Kameoka, T. Tanabe, A.P. Tsai, Catal. Lett. 100 (2005) 89–93.
[50] Y. Zhao, G. He, W. Dai, H. Chen, Ind. Eng. Chem. Res. 53 (2014) 12566–12574.
[51] A. Bazgir, G. Hosseini, R. Ghahremanzadeh, ACS Comb. Sci. 15 (2013) 530–534.
[52] J. Feng, L. Su, Y. Ma, C. Ren, Q. Guo, X. Chen, Chem. Eng. J. 221 (2013) 16–24.
[53] N. Panda, A.K. Jena, S. Mohapatra, Appl. Catal. A-Gen. 433 (2012) 258–264.
[54] D.K. Dumbre, P.R. Selvakannan, S.K. Patil, V.R. Choudhary, S.K. Bhargava, Appl.
Catal. A-Gen. 476 (2014) 54–60.
[55] S. Ahammed, D. Kundu, B.C. Ranu, J. Org. Chem. 79 (2014) 7391–7398.
[56] A.T. Nguyen, L.T.M. Nguyen, C.K. Nguyen, T. Truong, N.T.S. Phan,
ChemCatChem 6 (2014) 815–823.
[57] R. Indhrajothi, I. Prakash, M. Venkateswarlu, N. Satyanarayana, RSC Adv. 4
(2014) 44089–44099.
[58] Y. Dong, Y.-S. Chui, R. Ma, C. Cao, H. Cheng, Y.Y. Li, J.A. Zapien, J. Mater. Chem.
A 2 (2014) 13892–13897.
[59] F.-X. Ma, P.-P. Wang, C.-Y. Xu, J. Yu, H.-T. Fang, L. Zhen, J. Mater. Chem. A 2
(2014) 19330–19337.
[60] J. Zheng, Z. Lin, W. Liu, L. Wang, S. Zhao, H. Yang, L. Zhang, J. Mater. Chem. B 2
(2014) 6207–6214.
[61] M. Li, B. Li, H.-F. Xia, D. Ye, J. Wu, Y. Shi, Green Chem. 16 (2014) 2680–2688.
[62] H. Zhang, S. Gao, N. Shang, C. Wang, Z. Wang, RSC Adv. 4 (2014) 31328–31332.
[63] A.S. Kumar, B. Thulasiram, S.B. Laxmi, V.S. Rawat, B. Sreedhar, Tetrahedron 70
(2014) 6059–6067.
References
[1] N. Miyaura, A. Suzuki, Chem. Rev. 95 (1995) 2457–2483.
[2] L. Yin, J. Liebscher, Chem. Rev. 107 (2007) 133–173.
[3] A. Molnar, Chem. Rev. 111 (2011) 2251–2320.
[4] A.J.J. Lennox, G.C.L. Jones, Chem. Soc. Rev. 43 (2014) 412–443.
[5] G. Mugesh, W.-W. Mont, H. Sies, Chem. Rev. 101 (2001) 2125–2179.
[6] C.W. Nogueira, G. Zeni, J.B.T. Rocha, Chem. Rev. 104 (2004) 6255–6285.
[7] Y. Morzherin, P.E. Prokhorova, D.A. Musikhin, T.V. Glukhareva, Z. Fan, Pure
Appl. Chem. 83 (2011) 715–722.
[8] G. Perin, E.J. Lenardao, R.G. Jacob, R.B. Panatieri, Chem. Rev. 109 (2009)
1277–1301.
[9] C.E. Tucker, J. Davidson, P. Knochel, J. Org. Chem. 57 (1992) 3482–3485.
[10] D. Devaprabhakara, P.D. Gardner, J. Am. Chem. Soc. 85 (1963) 1458–1460.
[11] A. Bonet, C.P. Ulldemolins, C. Bo, H. Gulyas, E. Fernandez, Angew. Chem. Int.
Ed. 50 (2011) 7158–7161.
[12] G.A. Molander, N.M. Ellis, J. Org. Chem. 73 (2008) 6841–6844.
[13] M. Lombardo, S. Morganti, M. Tozzi, C. Trombini, Eur. J. Org. Chem. (2002)
2823–2830.
[14] H.E. Ho, N. Asao, Y. Yamamoto, T. Jin, Org. Lett. 16 (2014) 4670–4673.
[15] I. Beletskaya, A. Pelter, Tetrahedron 53 (1997) 4957–5026.
[16] K. Burgess, M.J. Ohlmeyer, Chem. Rev. 91 (1991) 1179–1191.
[17] K. Burgess, W.A. Donk, S.A. Westcott, T.B. Marder, R.T. Baker, J.C. Calabrese, J.
Am. Chem. Soc. 114 (1992) 9350–9359.
[18] J.-E. Lee, J. Kwon, J. Yun, Chem. Commun. (2008) 733–734.
[19] H.R. Kim, I.G. Jung, K. Yoo, K. Jang, E.S. Lee, J. Yun, S.U. Son, Chem. Commun. 46
(2010) 758–760.
[20] M.G. McLaughlin, M.J. Cook, Chem. Commun. 47 (2011) 11104–11106.
[21] H.R. Kim, J. Yun, Chem. Commun. 47 (2011) 2943–2945.
[22] A. Grirrane, A. Corma, H. Garcia, Chem. Eur. J. 17 (2011) 2467–2478.
[23] J. Cid, J.J. Carbo, E. Fernandez, Chem. Eur. J. 18 (2012) 1512–1521.
[24] W. Yuan, S. Ma, Adv. Synth. Catal. 354 (2012) 1867–1872.
[25] R. Alfaro, A. Parra, J. Aleman, J.L.G. Ruano, M. Tortosa, J. Am. Chem. Soc. 134
(2012) 15165–15168.
[64] B. Mohan, H. Woo, S. Jang, S. Lee, S. Park, K.H. Park, Solid State Sci. 22 (2013)
16–20.
[65] B. Mohan, H. Kang, K.H. Park, Inorg. Chem. Commun. 35 (2013) 239–241.
[66] H. Woo, K. Lee, K.H. Park, ChemCatChem 6 (2014) 1635–1640.
[67] H. Woo, K. Lee, J.C. Park, K.H. Park, New J. Chem. 38 (2014) 5626–5632.
[68] H. Woo, J.W. Kim, M. Kim, S. Park, K.H. Park, RSC Adv. 5 (2015) 7554–7558.
[69] B. Mohan, C. Yoon, S. Jang, K.H. Park, ChemCatChem 7 (2015) 405–412.
[70] A copper ferrite nanoparticles was procured from Aldrich (catalogue no.
641723) and used without any pretreatment.
[71] J.Y. Kim, J.C. Park, H. Kang, H. Song, K.H. Park, Chem. Commun. 46 (2010)
439–441.
[72] J.C. Park, J. Kim, H. Kwon, H. Song, Adv. Mater. 21 (2009) 803–807.
[73] J.Y. Kim, J.C. Park, A. Kim, A.Y. Kim, H.J. Lee, H. Song, K.H. Park, Eur. J. Inorg.
Chem. (2009) 4219–4223.
[26] S. Desrat, C. Remeur, C. Geny, G. Riviere, C. Colas, V. Dumontet, N. Birlirakis,
B.I. Iorga, F. Roussi, Chem. Commun. 50 (2014) 8593–8596.
[27] C.-C. Ti, M.-S. Yu, Y.-L. Chen, W.-H. Chuang, T.-H. Lin, G.P.A. Yap, T.-G. Ong,
Chem. Commun. 50 (2014) 4344–4346.
[74] H.-L. Jiang, Q. Xu, J. Mater. Chem. 21 (2011) 13705–13725.
[75] F.M. Moghaddam, G. Tavakoli, A. Moafi, V. Saberi, H.R. Rezvani, ChemCatChem
6 (2014) 3474–3481.
[28] M. Haberberger, S. Enthaler, Chem. Asian J. 8 (2013) 50–54.
[29] J. Zheng, J.-B. Sortais, C. Darcel, ChemCatChem 6 (2014) 763–766.
[30] Y.D. Bidal, F. Lazreg, C.S.J. Cazin, ACS Catal. 4 (2014) 1564–1569.
[31] K.-N.T. Tseng, J.W. Kampf, N.K. Szymczak, ACS Catal. 5 (2015) 411–415.
[32] C. Gunanathan, M. Holscher, F. Pan, W. Leitner, J. Am. Chem. Soc. 134 (2012)
14349–14352.
[33] S.U. Pandya, S. Pinet, P.Y. Chavant, Y. Vallee, Eur. J. Org. Chem. (2003)
3621–3627.
[34] N. Praveenganesh, S. d’Hondt, P.Y. Chavant, J. Org. Chem. 72 (2007)
4510–4514.
[76] I. Beletskaya, V. Tyurin, Molecules 15 (2010) 4792–4814.
[77] A.K. Singh, Q. Xu, ChemCatChem 5 (2013) 652–676.
[78] N. Toshima, T. Yonezawa, New J. Chem. 22 (1998) 1179–1201.
[79] A. Honraedt, F.L. Callonnec, E.L. Grognec, V. Fernandez, F.-X. Felpin, J. Org.
Chem. 78 (2013) 4604–4609.
[80] D. Kundu, N. Mukherjee, B.C. Ranu, RSC Adv. 3 (2013) 117–125.
[81] N. Taniguchi, J. Org. Chem. 72 (2007) 1241–1245.
[82] B. Mohan, S. Hwang, H. Woo, K.H. Park, Tetrahedron 70 (2014) 2699–2702.
[83] G.W. Kabalka, B. Venkataiah, Tetrahedron Lett. 43 (2002) 3703–3705.
[84] C.S. Freitas, A.M. Barcellos, V.G. Ricordi, J.M. Pena, G. Perin, R.G. Jacob, E.J.
Lenardao, D. Alves, Green Chem. 13 (2011) 2931–2938.
[35] G. He, S. Chen, Q. Wang, H. Huang, Q. Zhang, D. Zhang, R. Zhang, H. Zhu, Org.
Biomol. Chem. 12 (2014) 5945–5953.
[36] K. Semba, T. Fujihara, J. Terao, Y. Tsuji, Chem. Eur. J. 18 (2012) 4179–4184.
[85] R. Srinivasan, A.G. Coyne, C. Abell, Chem. Eur. J. 20 (2014) 11680–11684.