Room-Temperature Aqueous Suzuki-Miyaura Cross-Coupling Reactions Catalyzed via a Recyclable Palladium@Halloysite Nanocomposite

Article abstract of DOI:10.1021/acs.orglett.9b00042

A reliable method for encapsulation of palladium nanoparticles (6-8 nm particles) in halloysite (Pd@Hal) has been developed. The Pd@Hal was found to be a highly efficient room-temperature catalyst for Suzuki-Miyaura cross-coupling reactions that gave high yields of a diverse array of coupling products in 5:2 n-PrOH/H₂O within 1 h. The catalytic system was remarkably effective with a broad substrate scope. In addition, the catalyst was easily recovered and recycled without a significant loss of catalytic activity.

Full text of DOI:10.1021/acs.orglett.9b00042

Letter
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
pubs.acs.org/OrgLett
Room-Temperature Aqueous Suzuki−Miyaura Cross-Coupling
Reactions Catalyzed via a Recyclable Palladium@Halloysite
Nanocomposite
Jumanah Hamdi, Alexis A. Blanco, Brooke Diehl, John B. Wiley, and Mark L. Trudell*
Department of Chemistry and Advanced Materials Research Institute, University of New Orleans, New Orleans, Louisiana 70148,
United States
*
S Supporting Information
ABSTRACT: A reliable method for encapsulation of
palladium nanoparticles (6−8 nm particles) in halloysite
(
Pd@Hal) has been developed. The Pd@Hal was found to be
a highly efficient room-temperature catalyst for Suzuki−
Miyaura cross-coupling reactions that gave high yields of a
diverse array of coupling products in 5:2 n-PrOH/H O within
2
1
h. The catalytic system was remarkably effective with a
broad substrate scope. In addition, the catalyst was easily
recovered and recycled without a significant loss of catalytic
activity.
alladium-catalyzed cross-coupling reactions are often
the stoichiometry Hal-(10 Å) [Al Si O (OH) ·2H O] and
2 2 5 4 2
8
P
pivotal steps in syntheses of agrochemicals, pharmaceut-
dehydrated Hal-(7 Å) [Al Si O (OH) ].
2 2 5 4
1
icals, and other fine chemicals. As originally developed, these
Several Pd−halloysite heterogeneous systems have been
9
reactions predominantly employ soluble Pd complexes with a
variety of organic and inorganic co-additives. Such complex
homogeneous reaction systems present a number of challenges
for scale-up and industrial use, inhibit product purification (Pd
reported recently, based upon both Pd/ligand−halloysite and
PdNP−Hal systems. In both systems, the palladium species
were supported on the exterior of the scrolled framework of
the halloysite. Although these systems afforded good yields of
cross-coupled products, the catalysts suffered from similar
issues typically associated with other heterogeneous systems
(lower reactivity requiring increased reaction temperatures,
leaching, and catalyst deactivation over multiple uses). Recent
reports have described the preparation of encapsulated gold,
silver, and ruthenium nanoparticle−halloysite nanocompo-
2
removal), and have limited catalyst recyclability. Efforts to
convert homogeneous Pd/ligand systems into similarly ligated
Pd/ligand heterogeneous systems using insoluble supporting
3
materials have had limited success. Recent studies aimed at
the development of robust and recyclable Pd heterogeneous
systems with catalytic activities comparable to those of
homogeneous systems have focused on the potential use of
10,11
sites.
On the basis of these studies, it became of interest to
4
explore whether encapsulated PdNP in halloysite could offer
greater stability and improved nanoparticle reactivity. To the
best of our knowledge, PdNP had not successfully been
exclusively encapsulated in halloysite; thus, our initial focus
was to develop a method for the synthesis of an encapsulated
Pd nanoparticles (Pd ), Pd -supported nanocomposite
materials,
NP
NP
5
,6
7
and Pd single-atom composite materials.
However, many of these systems suffer from issues of low
reactivity, thermal instability, metal leaching, metal agglomer-
ation, and higher reaction temperatures. Therefore, there is a
need for new heterogeneous Pd systems that offer high
catalytic activity under ambient conditions, use benign
chemical additives, are reactive in green solvent systems, can
be easily recycled, and are cost-effective.
Pd −Hal nanocomposite material (Pd@Hal) and then
NP
investigate this material as a catalyst for cross-coupling
reactions. Herein, we describe a convenient and reliable
synthesis of Pd@Hal and its remarkable catalytic activity for
the Suzuki−Miyaura reaction.
The kaolinite-related clay, halloysite (Hal), has been
identified as a solid support for numerous chemical
applications. Halloysite is a dioctahedral 1:1 clay mineral and
occurs in nature as a hydrate consisting of rolled
To achieve encapsulation with halloysite nanoscrolls, our
approach was to initially preform monodispersed Pd of the
NP
2,13
1
appropriate size by reduction of palladium(II).
As
8
summarized in Table 1, treatment of palladium acetate with
sodium ascorbate afforded PdNP of the appropriate size for
encapsulation in halloysite.
aluminosilicate sheets. The morphology of Hal particles is
highly diverse, but the most common shapes are elongated,
curled particles that form nanotubes or nanoscrolls. Hal
nanoscrolls are generally 0.2−2 μm in length, having an inner
9
diameter of 10−40 nm and an outer diameter of 40−70 nm.
Received: January 4, 2019
Hal nanoscrolls are classified into two morphologies, having
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b00042
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Table 1. Two-Step Optimized Encapsulation of PdNP in Hal
a
b
c
entry
Pd(OAc) (mmol)
Pd/Hal
reducing agent (mmol)
capping agent (mmol)
description (E, A)
2
1
2
3
4
5
6
7
8
9
0.060
0.060
0.13
0.13
0.26
0.26
0.26
0.60
0.60
0.60
1:16
1:16
1:8
1:8
1:8
1:8
1:8
1:1
1:1
1:1
sodium ascorbate (10)
sodium ascorbate (7.0)
sodium ascorbate (7.0)
sodium ascorbate (7.0)
sodium ascorbate (7.0)
ascorbic acid (7.0)
ascorbic acid (4.0)
sodium ascorbate (100)
sodium ascorbate (7.0)
ascorbic acid (0.60)
ascorbic acid (0.60)
ascorbic acid (0.60)
ascorbic acid (1.4)
ascorbic acid (2.7)
ascorbic acid (2.7)
citric acid (2.7)
trisodium citrate (6.0)
trisodium citrate (1.2)
trisodium citrate (0.60)
E, A
E, A
E, A
E, A
E only
A only
A only
E only
E only
E only
1
0
sodium ascorbate (10)
a
b
c
Results are based on three trials for each set of reaction conditions. Pd(OAc) :halloysite molar ratio. Encapsulation inside the scroll (E).
2
Agglomeration of nanoparticles outside of the scroll (A).
An aqueous suspension of the synthetic PdNP when
combined with halloysite furnished the desired encapsulated
Pd@Hal nanocomposite. The degree to which the PdNP were
encapsulated versus agglomerated outside of the nanoscroll
was determined from TEM images. Initial attempts to form a
Pd@Hal nanocomposite material focused on a 1:16 Pd:Hal
molar ratio (entry 1, 10 wt %/wt) with sodium ascorbate
employed as the reducing agent for nanoparticle formation,
and citric acid was used as the capping agent to reduce the
level of nanoparticle agglomeration and control the size of the
particles. This initial attempt resulted in good encapsulation of
the PdNP in halloysite; however, there was significant
agglomeration of the PdNP outside of the scrolls, resulting in
incomplete encapsulation of PdNP.
Decreasing the amount of the reducing agent did not
improve encapsulation (Table 1, entry 2), and the use of
ascorbic acid proved to be deleterious to PdNP encapsulation
due to the formation of large nanoparticles that were incapable
of entering the scroll (Table 1, entries 6 and 7). The use of a
1
:8 Pd:Hal molar ratio gave results (Table 1, entry 3) similar
to those for the 1:16 ratio. It was not until the amount of
capping agent was increased that improved encapsulation was
observed. An optimum encapsulation was achieved with a 4.5-
fold increase in the relative amount of citric acid (Table 1,
entry 5). TEM images (Figure 1a) of the sample show that the
bulk of PdNP was encapsulated, with no agglomeration on the
halloysite surface or agglomerates outside of the scrolls. The
size of encapsulated PdNP averaged between 6 and 8 nm. This
approach (Table 1, entry 5) resulted in 98% Pd loading [based
on Pd(OAc) ] to furnish a Pd@Hal nanocomposite that was
2
4
% Pd content (weight percent) as determined by ICP-AES
analysis.
Having identified conditions for the successful encapsulation
Figure 1. TEM images of Pd@Hal nanocomposites: (a) entry 5 of
Table 1 and (b) entry 10 of Table 1.
of Pd , we turned our attention toward increasing the loading
NP
of encapsulated Pd . In these studies, trisodium citrate was
NP
B
DOI: 10.1021/acs.orglett.9b00042
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Table 2. Optimization of the Suzuki−Miyaura Reaction
a
b
entry
2:1 (mmol)
4% Pd@Hal loading (wt %/wt)
solvent (base, 2 equiv)
1,4-dioxane (Cs CO )
T (°C), time (h)
yield (%)
,
c d
1
2
3
4
5
6
7
8
9
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.5:1.0
1.2:1.0
1.2:1.0
1.2:1.0
1.2:1.0
1.2:1.0
1.2:1.0
1.2:1.0
1.2:1.0
5.7:5.0
11.8:11.6
11.8:11.6
10
10
10
10
10
10
10
10
10
10
10
10
10
5
80, 6
80, 24
reflux, 6
reflux, 24
80, 24
reflux, 24
reflux, 8
reflux, 8
rt, 24
rt, 24
rt, 1
rt, 1
rt, 1
rt, 1
rt, 1
rt, 8
rt, 1
rt, 8
rt, 1
22
76
2
3
,
c d
1,4-dioxane (Cs CO )
2
3
c
e
,
e
1,4-dioxane (Cs CO )
CM
CM
NR
2
3
1,4-dioxane (Cs CO )
2
3
f
toluene (Cs CO )
2
3
e
toluene (Cs CO )
CM
2
3
d
toluene (Cs CO )
65
2
3
f
H O (Cs CO )
NR
CM
CM
93
2
2
3
e
e
4:1 toluene:H O
2
10
11
12
13
14
15
16
17
18
19
20
21
22
4:1 1,4-dioxane:H O (Cs CO )
2 2 3
4:1 n-PrOH:H O (Cs CO )
2
2
3
4:1 n-PrOH/H O (Cs CO )
94
99
98
75
95
87
96
99
2
2
3
5:2 n-PrOH/H O (Cs CO )
2
2
3
5:2 n-PrOH:H O (Cs CO )
2
2
3
2
2
5:2 n-PrOH:H O (Cs CO )
2
2
3
5:2 n-PrOH:H O (Cs CO )
2
2
3
10
10
10
10
5
5:2 n-PrOH:H O (K CO )
2
2
3
5:2 n-PrOH:H O (K CO )
2
2
3
5:2 n-PrOH:H O (K CO , 3 equiv)
2
2
3
g
5:2 n-PrOH:H O (Cs CO )
rt, 1
rt, 1
rt, 8
97
70
98
2
2
3
h
h
5:2 n-PrOH:H O (Cs CO )
2
2
3
5
5:2 n-PrOH:H O (Cs CO )
2
2
3
a
The 10 wt %/wt 4% Pd@Hal relative to bromotoluene (1) corresponds to 5.6 μg of Pd/mmol of 1. The 5 wt %/wt 4% Pd@Hal relative to 1
b
corresponds to 2.8 μg of Pd/mmol of 1. The 2 wt %/wt 4% Pd@Hal relative to 1 corresponds to 1.1 μg of Pd/mmol of 1. Isolated yields based on
at least three trials. Sealed vial under air. Isolated yield of the coupling product and homocoupling product also present. CM, complex mixture of
the starting material, coupling product, and homocoupling product. NR, no reaction, only starting material. On a 5 mmol scale. On a 12 mmol
scale.
c
d
e
f
g
h
employed as the capping agent because it had been reported to
control the aggregation of PdNP better than citric acid.
(aryl bromide). This corresponds to a metal loading of 5.6 μg
of Pd/mmol of 1. The base was used in excess (2 equiv)
relative to the boronic acid. As summarized in Table 2, a
survey of conditions was performed with 4-bromotoluene (1)
and 4-methoxyphenylboronic acid (2) to identify optimized
reaction conditions for cross-coupling to yield 4-methoxy-4′-
methylbiphenyl (3). Traditional solvents used in Suzuki−
Miyaura reactions (1,4-dioxane and toluene) gave low yields or
complex mixtures of coupling products and homocoupling
12,13
Given the larger amount of palladium in the reaction mixture,
it was assumed that trisodium citrate would facilitate
encapsulation over aggregation. Using a 1:1 Pd:Hal molar
ratio and trisodium citrate, higher levels of encapsulation of the
PdNP could be achieved. In addition, a large excess of sodium
ascorbate was employed to promote the formation of small
PdNP and facilitate the encapsulation into the halloysite (Table
1
, entry 8); under these conditions, excellent encapsulation was
14
byproducts (Table 2, entries 1−7). Homocoupling by-
observed but the PdNP were extremely small (1−2 nm).
Decreasing the amount of sodium ascorbate gave larger
nanoparticles (6−8 nm) and excellent encapsulation (Table
products were observed when the reaction was performed in
air (Table 2, entries 1−3), so to prevent the formation of the
homocoupled byproducts, the reactants and reaction mixtures
were maintained under a nitrogen atmosphere until the
1
, entries 9 and 10). Optimized conditions were established
using a 1:1 Pd:Hal molar ratio, with a 16-fold excess of sodium
ascorbate and an equal molar amount of trisodium citrate
15
reaction reached completion. It was interesting that although
water was a poor solvent for the reaction (Table 2, entry 8),
addition of water to 1,4-dioxane and toluene (Table 2, entries
(Table 1, entry 10). These conditions furnished a Pd@Hal
nanocomposite with 98% encapsulation with no observable
external scroll decoration (Figure 1b). The palladium content
of this Pd@Hal nanocomposite was found to be 25% (weight)
based upon ICP-AES analysis.
Having produced quality Pd@Hal nanocomposites, we
turned our attention toward the application of this new
material in cross-coupling reactions. Initial optimization of
Suzuki−Miyaura reaction conditions employed the 4% Pd@
Hal nanocomposite material prepared previously (Table 1,
entry 5). A catalyst loading of 10 wt %/wt Pd@Hal
nanocomposite was employed relative to the limiting reagent
9
and 10, respectively) promoted the coupling reaction at
room temperature. This prompted the use of the more polar
solvent, n-propanol, as a co-solvent with water. Much to our
surprise, a 4:1 n-propanol/water solvent mixture furnished the
desired coupling products at room temperature in 93% yield
within 1 h (Table 2, entry 11). The coupling reaction proved
to be highly efficient, requiring only a slight excess of boronic
acid (Table 2, entry 12) with no homocoupled byproduct
observed. A slight increase in the amount of water, to a 5:2 n-
propanol:water ratio, gave optimum conditions for the
C
DOI: 10.1021/acs.orglett.9b00042
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
coupling reaction and afforded coupled product 3 in nearly
quantitative yield [99% (Table 2, entry 13)].
Under these conditions, catalyst loading was evaluated. It
was determined that 5 wt %/wt loading of 4% Pd@Hal was
equally effective, affording 3 in 98% yield within 1 h (Table 2,
entry 14). This corresponds to a metal loading of 2.8 μg of Pd/
mmol of 1. Further reduction of the catalyst loading to 2 wt
to diminish. In addition, the palladium content of the Pd@Hal
catalyst was determined after five recycled reactions and ICP-
AES analysis indicated no significant loss of palladium. It was
also determined by ICP-AES analysis that some residual Pd
(6.4 ppm) was present in 3 after the first cycle of the study. It
is unclear if this low level of Pd residue is due to ionic Pd(II)
or soluble Pd(0) species released during the reaction or the
recovery/workup procedure.
%/wt required a longer reaction time to achieve the same
success but nevertheless gave 3 in 95% yield after 8 h at room
temperature (Table 2, entries 15 and 16).
To demonstrate further the utility of this catalyst system for
the Suzuki−Miyaura cross-coupling reaction, a series of aryl
halides (4) and boronic acids (5) were investigated as
substrates for cross-coupling. As summarized in Scheme 1,
Initially, Cs CO (2 equiv) was used in these studies as the
2
3
base. However, it was later found that K CO could
2
3
successfully substitute for Cs CO . Using 2 equiv of K CO
2
3
2
3
required a longer reaction time; however, 3 equiv of K CO
Scheme 1. Pd@Hal-Catalyzed Suzuki−Miyaura Cross-
2
3
a
gave a yield comparable to that of the Cs CO system (Table
Coupling Reactions
2
3
2
, entries 17−19). In addition to the mild and efficient nature
of this reaction, it was extremely satisfying to realize that the
catalytic reaction could be scaled without a loss of yield under
the ambient conditions. Using 10 wt %/wt 4% Pd@Hal, a 97%
yield of 3 (0.96 g, 5 mmol scale) was obtained after 1 h (Table
2
, entry 20). Similarly (Table 2, entry 22) using 5 wt %/wt 4%
Pd@Hal, a 99% yield of 3 (2.27 g, 11.6 mmol scale) was
obtained after 8 h.
The high reactivity of Pd@Hal is believed to be due to the
synergy of the PdNP (large reaction surface area) in halloysite
(
a confined amphiphilic environment) because control
reactions showed that neither PdNP nor halloysite alone
exhibited catalytic activity in this reaction system. The catalytic
effect of halloysite-encapsulated PdNP is believed to be similar
to the micellar effects observed for a variety of metal-catalyzed
16
reactions in aqueous-based systems.
The Pd@Hal catalyst was found to be durable and
chemically robust. The catalyst could be recovered by simple
centrifugation and filtration and reused without loss of activity
or structural change to the Pd@Hal nanocomposite based
upon TEM analysis. Moreover, the Pd@Hal nanocomposite
could be stored for several months and used without loss of
activity.
a
Isolated yields based on a minimum of three trials.
As illustrated in Figure 2, recycling studies with 4% Pd@Hal
Table 1, entry 5) showed that the catalyst could be cycled
(
through nine consecutive coupling reactions with no loss of
activity and excellent isolated yields of coupling product 3 in
each trial. It was not until the ninth trial that the yield started
the Pd@Hal catalyst demonstrated high reactivity in the
presence of a variety of functional groups to afford cross-
coupling products (6) in excellent yields under very mild
conditions. In all examples, product formation began
immediately and within 1 h limiting reagent 4 was completely
consumed. Both hydrophobic and hydrophilic substrates were
equally tolerated by the reaction conditions. It is noteworthy
that the hydrophilic cross-coupling products, 4-hydroxy-4′-
methoxybiphenyl (6m, 97%) and 4-amino-4′-methoxybiphenyl
(
6n, 92%), were obtained in high yield from the corresponding
aryl bromides.
In summary, we have developed a new extremely effective
Pd@Hal nanocomposite catalyst for Suzuki−Miyaura cross-
coupling reactions. This material produces high yields of a
diverse array of coupling products within 1 h at room
temperature in a 5:2 n-PrOH/H O mixture. The Pd@Hal
2
catalytic system was remarkably effective with both hydro-
phobic and hydrophilic substrates. The Pd@Hal nano-
composite material is a cost-effective, highly efficient, and
easily recyclable material. This newly developed nano-
composite presents a significant advance in heterogeneous
catalysis, exploiting the nanoporous structure of halloysite.
Figure 2. Pd@Hal recycling studies.
D
DOI: 10.1021/acs.orglett.9b00042
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
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ASSOCIATED CONTENT
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AUTHOR INFORMATION
Corresponding Author
27682. (f) Scheuermann, G. M.; Rumi, L.; Steurer, P.; Bannwarth, W.;
■
̈
Mulhaupt, R. J. Am. Chem. Soc. 2009, 131, 8262−8270. (g) Divakar,
D.; Manikandan, D.; Kalidoss, G.; Sivakumar, T. Catal. Lett. 2008,
*
E-mail: mtrudell@uno.edu.
1
25, 277−282.
ORCID
(7) Chen, Z.; Vorobyeva, E.; Mitchell, S.; Fako, E.; Ortuno, M. A.;
Lopez, N.; Collins, S. M.; Midgley, P. A.; Richard, S.; Vile, G.; Perez-
Ramirez, J. Nat. Nanotechnol. 2018, 13, 702−707.
John B. Wiley: 0000-0002-6954-6752
Mark L. Trudell: 0000-0001-6201-0253
Notes
(
8) (a) Liu, M.; Jia, Z.; Jia, D.; Zhou, C. Prog. Polym. Sci. 2014, 39,
1498−1525. (b) Abdullayev, E.; Lvov, Y. J. Mater. Chem. B 2013, 1,
2
894−903. (c) Joussein, E.; Petit, S.; Churchman, J.; Theng, B.; Righi,
The authors declare no competing financial interest.
D.; Delvaux, B. H. Clay Miner. 2005, 40, 383−426. (d) Hendricks, S.
B. Nature 1938, 142, 38.
ACKNOWLEDGMENTS
Support from National Science Foundation Grant CHE-
412670 (A.A.B. and J.B.W.) and the Department of
■
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G.; Liotta, L. F.; Parisi, F.; Pettignano, A.; Riela, S. New J. Chem. 2018,
Chemistry at the University of New Orleans is gratefully
acknowledged.
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Appl. Mater. Interfaces 2016, 8, 4862−4869. (e) Hong, M. C.; Ahn,
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