Volume 21 Number 3 7 February 2019 Pages 363–714

Green
Chemistry
Cutting-edge research for a greener sustainable future
[Link]/greenchem

ISSN 1463-9262

CRITICAL REVIEW
Roya Sedghi, Rajender S. Varma et al.
Recent advances in the Suzuki–Miyaura cross-coupling
reaction using efficient catalysts in eco-friendly media
 Green Chemistry
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Recent advances in the Suzuki–Miyaura

Cite this: Green Chem., 2019, 21, 381
cross-coupling reaction using efficient
catalysts in eco-friendly media
a
Seyyed Emad Hooshmand, Bahareh Heidari,b Roya Sedghi*b and
Rajender S. Varma *c

The ever-increasing interest in the Suzuki–Miyaura cross-coupling reaction (SMR) and its applications,
with more than 40 years of history, has increased exponentially in the last decade, which speaks volumes
about its efficiency and effectiveness. This widely used powerful method provides a practical synthetic
route for the direct formation of carbon–carbon bonds, which has found considerable academic and
industrial use for the production of polymers, fine chemicals and materials, in addition to total synthesis
and pharmaceuticals. Green chemistry predicates the use of environmentally-benign media in organic
transformations and in recent years, catalytic systems have been introduced in diverse and neoteric green
Received 9th September 2018, media for SMR. In view of the widespread popularity, there is the need for a comprehensive understanding
Accepted 5th November 2018
of the various greener strategies introduced for this important reaction encompassing diverse catalytic
DOI: 10.1039/c8gc02860e systems based on palladium, nickel, gold, ferrites, copper, silver, and cobalt. The present review embodies
[Link]/greenchem literature from 2008 onward that covers the SMR using efficient catalysts in various green media.

a
Department of Organic Chemistry and Oil, Faculty of Chemistry and Petroleum Sciences,
1 Introduction
Shahid Beheshti University, 1983969411 Tehran, Iran 1.1 Green chemistry: a necessity
b
Department of Polymer and Materials Chemistry, Faculty of Chemistry and
Petroleum Sciences, Shahid Beheshti University, 1983969411 Tehran, Iran. The new sustainability-focused development plan outlined by
E-mail: r_sedghi@[Link] the United Nations in 2015 is entitled “Transforming Our
c
Regional Centre of Advanced Technologies and Materials, Department of Physical World: The 2030 Agenda for Sustainable Development” and is
Chemistry, Faculty of Science, Palacky University, Šlechtitelů 27, 783 71 Olomouc,
comprised of 17 sustainable development goals that address a
Czech Republic. E-mail: [Link]@[Link]

Seyyed Emad Hooshmand was Bahareh Heidari was born

born in Iran, in 1988 and in Qorveh/Kurdistan, Iran, in
received his [Link]. in Chemistry 1989. She received her [Link]. in
from Bu-Ali Sina University, Chemistry from Razi University,
Hamedan, in 2011, and his Kermanshah in 2011, and her
[Link]. in Organic Chemistry from [Link]. in Organic Chemistry from
Kharazmi University, in 2013. Shahid Beheshti University,
He started his Ph.D. studies at Tehran under the supervision of
Shahid Beheshti University, Dr Mohammad Reza Nabid, in
Tehran, in 2014, and was 2013. She is currently working
awarded the Shahid Shahriari towards her Ph.D. in Organic
research fellowship in 2017. His Chemistry under the supervision
Seyyed Emad Hooshmand current research interests are Bahareh Heidari of Prof. Majid M. Heravi with Dr
focused on green chemistry, Roya Sedghi as an advisor. Her
metal-catalyzed cross-coupling reactions and multi-component research interest involve the synthesis of polymeric nano-
reactions based on dithiocarbamates and isocyanides. He is the composites as catalyst, colorimetric sensors and molecularly
author of over 25 scientific articles, including, reviews, and a book imprinted polymers.
chapter.

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broad range of topics, mainly recognizing the need for green as water and ethanol (EtOH) as well as neoteric media like
and sustainable chemistry and engineering.1 Achieving the biomass-derived solvents, ionic liquids, deep eutectic solvents,
objectives of this plan is vital for the future of the planet and and supercritical carbon dioxide, etc., has encouraged us to
its biological species, which include humans, plants, and review this field.
animals. A significant challenge and barrier to attaining this
goal is the selection of appropriate media and solvents for use 1.2 The Suzuki–Miyaura cross-coupling reaction (SMR)
in industrial, hospital and research centers; the study and Transition-metal-mediated cross-couplings, namely, Suzuki–
development of eco-friendly media have been under active Miyaura, Hiyama, Stille, Heck, Negishi, Kumada, and
Published on 05 November 2018. Downloaded by Institute of Chemistry, CAS on 6/8/2019 [Link] AM.

scrutiny in diverse scientific and commercial fields. The term Sonogashira reactions, are powerful tools for C–C bond
green chemistry has been defined by IUPAC as follows: “the formation.4–11 The C–C coupling reactions have become truly
invention, design and application of chemical products and fundamental routes in natural product synthesis, materials
processes to reduce or to eliminate the use and generation of science, biological-, medicinal-, and supramolecular chemistry,
hazardous substances”.2 Importantly, an ideal green medium and also in catalysis, coordination chemistry and polymer
should be safe for both human beings and the environment synthesis.12–14 The Suzuki–Miyaura reaction has been heavily
and its use and production should adhere to the sustainability exploited in this decade, especially reactions that provide rapid
theme. From a synthetic chemist’s viewpoint, this emphasis entry to biaryl frameworks via sp2–sp2 linkages.15,16 This reac-
on environmental and health issues is leading to a paradigm tion is widely used due to attractive properties such as the
shift in the design of greener approaches for the preparation mild reaction conditions, the commercial availability of an
of all molecules without applying any toxic solvents and dama- array of precursors, the functional-group compatibility, the
ging substances; some of the traditional solvents used earlier high stabilities towards air and moisture, and the deployment
by researchers in academia and the industrial community have of nontoxic and easily synthesized boronic acids. A recent
been blacklisted by international regulations; for example, survey of the literature reveals many examples of palladium
chlorinated hydrocarbon solvents, benzene and some of its (Pd), nickel (Ni) and gold (Au) complexes as efficient catalysts
derivatives have been severely curtailed.3 Consequently, scien- for the cross-coupling reactions;17,18 the award of the Nobel
tists and researchers have been ceaselessly trying to find Prize in Chemistry for 2010 to Ei-ichi Negishi, Akira Suzuki
appropriate sustainable replacements for expensive, toxic and and Richard Heck is testimony to their valuable contribution
environmentally damaging organic solvents. In this context, to this research field.19 Several reviews on the SMR have
many efforts have been expanded during the last decade for appeared in the literature,20–23 with the initial one being
accomplishing SMR in environmentally benign media. These written by Suzuki and Miyaura in 1995. Today, numerous
remarkable developments to conduct this noteworthy and papers have emerged on the SMR in a truly explosive growth
widely deployed cross-coupling reaction in green solvents such pattern comprising diverse fields; the frequency of publi-

Roya Sedghi was born in 1980 in Prof. Rajender Varma (H-index

Tehran and received her [Link]. 102; ‘Highly Cited Researchers’
degree from the Tehran Azad 2016, 2018; Publons awardee
University of Iran in 2002 before 2018) did his PhD from Delhi
being accepted for [Link]. at University, 1976. After post-
Shahid Beheshti University. She doctoral research at Robert
completed her Ph.D. under the Robinson Laboratories, Liverpool,
supervision of Professor H. Abdi England, he was a faculty at
Oskoiee and is presently working Baylor College of Medicine and
at Shahid Beheshti University as Sam Houston State University
an assistant professor. She has prior to joining the US
authored 50 publications and Environmental Protection Agency
Roya Sedghi her research is mainly focused Rajender S. Varma in 1999 with appointment at the
on the application of nano- Regional Centre of Advanced
composites in various chemistry disciplines such as catalysis and Technologies and Materials, Palacky University at Olomouc, Czech
drug delivery. In 2017, she is awarded research project in green Republic from 2014. He has over 45 years of research experience
chemistry for Life supported by UNESCO, PhosAgro and IUPAC. in the management of multi-disciplinary technical programs.
Lately, he is engaged in greener assembly of nanomaterials and
the sustainable applications of magnetically retrievable nano-
catalysts. He is board member of several international journals,
published over 480 papers, and has been awarded 16 US Patents
with 35 000 citations.

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ations have been extended to the aqueous and heterogeneous

switching of organic transformations by amphiphilic block
copolymer-supported transition metal complexes or metal
NPs.32 The Suzuki–Miyaura reaction (SMR) has been carried
out in water via assorted catalysts, accommodating not only
hydrophilic substrates but also hydrophobic substituents in
aqueous medium, affording high to excellent yields. The
driving force for the hydrophobic guest molecules to diffuse
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onto the sphere is mainly ascribed to the hydrophobic–hydro-

phobic interactions in water. These ensuing good yields might
be due to a combination of the hydrophobic effect of water
Fig. 1 The frequency of SMR publications, obtained from a search of and the nature of the support,33 and stabilization of leached
the title, abstract, or keywords contained in Scopus from 1995 to 2017. palladium reactive species34 in water.

2.1 Palladium NPs

cations from 1995 to 2017 is illustrated in Fig. 1, showing an Jin et al. devised the hierarchical MFI zeolite support 1 for the
upward trend of about 4369 articles published in addition to immobilization of Pd(OAc)2 in two steps (Scheme 1),35 which
over 3506 patents. was successfully used for the SMR to afford the coupled com-
pounds under mild conditions (Scheme 2). This catalyst, with
a narrow distribution of mesopore diameters of around
2 Water 3.3 nm, was hydrothermally synthesized using a mesopore-
directing agent and possessed the specific BET surface area of
Water, a plentiful resource with an admirable specificity, is an 502 m2 g−1 and pore volume of 0.46 cm3 g−1. Interestingly,
abundant, safe and green medium and has been applied to an substrates bearing both electron-donating and electron-with-
array of organic reactions in the last two decades.24 Water drawing groups, 4, 5, were well tolerated and the catalyst can
plays a dual role as medium and as a co-catalyst in quite a few be readily recovered and recycled several times in fast reactions
of these convergent synthetic routes due to its high surface with high turnover numbers. The superior catalytic activity,
tension and hydrophobic nature, which underscore the ten- higher stability and reusability (1.5 ppm Pd metal leaching
dency of nonpolar molecules or their surfaces to aggregate in into the reaction mixture during the first run) of the catalyst
water; Breslow’s hydrophobic effect in-water emphasizes that could be attributed to the strong binding of Pd(OAc)2 to MFI-
for decreasing the exposed organic surface area, the substrates supported ionic liquid (IL) support, 2.
must be aggregated.25 On the other hand, there are some Karimi et al. reported the design, preparation and charac-
salient properties of water including a large cohesive energy terization of a water-dispersible Pd catalyst on a Fe3O4@SiO2
density derived from some characteristics of water molecules anchored hydrophilic triethylene glycol (TEG)-imidazolium IL
such as the small size and high polarity, along with the three- (Mag-IL-Pd, 7) for the SMR (Scheme 3);36 the core–shell struc-
dimensional (3D) hydrogen bond networks of water. Often,
water plays an important role in the rate acceleration of reac-
tions by establishing extensive hydrogen bonding with the
functional groups of reactants and activating them in the
process.26 In recent years, the use of water as a greener sustain-
able reaction medium has been under focus for diminishing
environmental pollution,27–30 and has been applied in the
SMR coupled with different support systems for a wide variety Scheme 2 The SMR of aryl bromides 4 with arylboronic acid 5 using
of nanoparticles (NPs) as catalysts.20,21,31 Substantial consider- MFI-supported Pd(OAc)2–IL 3.

Scheme 1 Preparative steps for MFI-supported Pd(OAc)2–IL 3 as the SMR catalyst.

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magnetic NPs led to a hydrophilic nanocatalyst that provided

an excellent dispersion of the catalyst in water. Furthermore,
supported IL not only stabilizes the Pd NPs during the reaction
but also provides an IL-based nano-environment on the
surface of magnetic Pd to increase their interaction with aryl
halides, thus improving the overall reaction efficiency.
N-heterocyclic carbenes (NHCs) have aroused considerable
attention in recent years as possible alternative ligands for
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metal-catalyzed cross-coupling reactions,37 exemplified by

N-substituted main-chain NHC-Pd polymers 11a–c (Scheme 4)
Scheme 3 The SMR of aryl halides 4 and boronic acids 5 by Mag-IL-Pd as reusable catalytic systems for the SMR of chloroarenes
catalyst 7. (Scheme 5).38 The catalyst 11c, bearing the more lipophilic
n-dodecyl group, was found to be more reactive (91% yield,
with extremely low Pd loading (0.0005 mol%)) for reactions of
ture had a narrow size distribution, with the thickness of the both deactivated and hindered aryl chlorides 4 with various
iron oxide core and the silica shell being ∼10 and 5–7 nm, arylboronic acids 5, exclusively in aqueous media. The results
respectively. The products were acquired in good to superior demonstrate that the electronic effects do not significantly
yields with high turnover numbers (TONs) (185-4000) using a affect the isolated yields for electron-deficient and electron-
very low Pd loading (0.025–0.5 mol% of catalyst), which could rich aryl chlorides. The lifetime and recycling of the catalyst
be recycled 10 times without significant loss of activity and no were investigated; the obtained data showed that catalyst 11a
apparent decrease in Pd content; nearly the same as the fresh could be consistently applied in 6 consecutive coupling reac-
catalyst (0.084 mmol Pd g−1). The TEG tags of functionalized tions of 4-chlorobenzaldehyde with phenylboronic acid to
afford the product in an average yield of 92%. The same coup-
ling model reaction in the presence of 11c (0.05 mol%) could
be successfully recycled in seven reaction runs. While the
obtained data clearly show that virtually no significant de-
activation occurred during these runs, it was necessary to
increase the reaction times after the 4th run to ensure proper
conversion.
In another variation of the methodology, Liu et al.
described a polyethylene glycol (PEG)-functionalized imidazo-
lium salts-based Pd-catalyst for the cross-coupling of aryl bro-
mides 4 and arylboronic acids 5 in the presence of 0.5 mol%
Pd(OAc)2 at 100 °C (Scheme 7),39 wherein several water-soluble
imidazolium salts bearing PEG moieties directly linked to an
N-atom of imidazole could serve as NHC precursors 16a–c
Scheme 4 Synthesis of main-chain NHC-Pd polymers 11a–c as SMR
catalysts. (Scheme 6). For comparison purposes, a kinetic study of the

Scheme 5 The SMR of various aryl chlorides 4 with arylboronic acid 5 Scheme 7 The SMR between aryl bromides 4 and aryl boronic acids 5
by N-substituted main-chain NHC-Pd polymer catalyst 11c. in water.

Scheme 6 The synthetic path to PEG-functionalized imidazolium salts, 16a–c.

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SMR was performed in the presence of Pd(OAc)2 and triethyl-

amine (Et3N) at 80 °C in aqueous media; 16c displayed a rela-
tively higher catalytic activity in a shorter induction period
than catalysts 16a and 16b. These results show that increasing
the “steric-bulk” of the ligand attached to the metal center is
crucial for attaining the Pd-catalyzed SMR; Et3N is the ideal Scheme 9 The aqueous SMR within the Pd@PNIPAM nanoreactor 18
as catalyst.
choice among the other bases such as morpholine,
CH3CH2ONa, piperidine, 1,2-diaminocyclohexane, DMEDA
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(N,N′-dimethylethanediamine) and TMEDA (N,N,N′,N′-tetra-

methylethanediamine). The superior performance of Et3N is
presumably due to its inherent tendency to re-coordinate with
the active NHC-Pd groups, thus elongating the lifetime in
solution.40
Zhang et al. reported the SMR within the core–corona Scheme 10 Preparation of Pd np/A–G 21.
nanoreactor of poly(N-isopropylacrylamide)-grafted Pd NPs
(Pd@PNIPAM) 18 with average size of ∼3 nm, which were syn-
thesized by covalently grafting the thiol-terminated PNIPAM lowed by soaking hydrogel beads in a Na2PdCl4 solution. The
brushes to Pd NPs, in water (Scheme 8).41 The Pd NPs as core reduction of Pd NPs occurs during the dehydratation step
and poly(N-isopropylacrylamide) brushes as the corona pro- (Scheme 10). The virgin catalyst system is comprised of Pd
vided the nanoenvironment to the guest molecules for the spheroidal NPs whose average size is 3.4 ± 1.4 nm, and the
SMR. Both hydrophilic and hydrophobic reactants can be material recovered after eight runs showed the NPs to be about
enriched in the nanoenvironment of 18 (Scheme 9). The hydro- 3.6 ± 1.7 nm in diameter. The Pd catalyst 21 was applied in the
philic substrates can be entrapped in the nanoreactor of SMR of 22 with potassium aryltrifluoroborates 23 (1 : 1 molar
PNIPAM brushes due to the strong hydrogen bonding at room ratio) with 0.01–0.002 mol% loading under aerobic, base-, and
temperature and therefore the SMR within the nanoreactor is phosphine-free conditions (Scheme 11); the use of other sol-
carried out in water. For hydrophobic reactants, the substrates vents in the SMR was explored and no coupling product was
can diffuse into the nanoenvironment of 18 and the SMR is discerned in MeOH or EtOH, and MeCN or DMF afforded pro-
carried out efficiently above the phase-transition temperature ducts only in lower yields. The catalyst could be reused several
of the nanoenvironment of the PNIPAM brushes. Furthermore, times without significant loss of activity, with the cumulated
the catalyst can be reused due to the reversible phase tran- TON over eight runs being 68 400.
sition of the PNIPAM brushes. At room temperature, the The immobilization of Pd NPs directly onto various sup-
PNIPAM brushes are soluble in water and the 18 nanoreactor ports such as carbon,43 zeolites,44 silica,45 and polymers,46
exists as a colloid; when reactants such as benzeneboronic and their application in cross-coupling reactions in green
acid, 4-bromophenol and K2CO3 are added and the tempera- media has been emphasized lately due to the ever-intensifying
ture is increased above the phase-transition temperature, the demand for cleaner and sustainable chemistry; the choice of
PNIPAM brushes become insoluble and collapse onto the Pd supports is shifting from petrochemical-based feedstocks to
NPs, rendering 18 as a fine flocculent suspension. After com-
pletion of the SMR, the organic compounds are extracted into
the organic solvent phase and the catalyst 18 NPs, which exist
as a fine flocculent suspension, remain in the aqueous phase;
the suspended catalyst is then carefully collected and reused
in next run of the SMR.
The SMR of arenediazonium salts, 22 can be catalyzed
using alginate/gellan-stabilized Pd NPs (Pdnp/A–G) 21 under Scheme 11 The aqueous SMR of arenediazonium tetrafluoroborates,
aerobic conditions;42 Pd NPs are stabilized by dropping an 22 with potassium aryltrifluoroborates, 23 using Pdnp/A–G 21 as the
alginate/gellan (50 : 50) solution into a CaCl2 solution 19, fol- catalyst.

Scheme 8 Schematic representation of guest molecules entrapped within the nanoreactor of Pd@PNIPAM 18.

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Scheme 12 The SMR of aryl halides 4 and arylboronic acids 5 by

Scheme 14 The SMR of various aryl bromides and chlorides, 4, cata-
0.05 mol% Pd/BC catalyst in water.
lyzed by 8 wt%Pd@MIL-101Cr-NH2.
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environmentally safe materials. Bacterial cellulose (BC) is an ideal green core environment for Pd-catalyzed cross-coupling
example of such a support due to its eco-friendly properties, reactions.53 The Lipshutz group recently showed that the high
possessing a large surface area and stable heterogeneous inter- solubility of oxygen in an organic medium, including micelles,
face for developing semi-heterogeneous catalysts.47–49 In this can be beneficially applied to perform the aerobic oxidation of
context, Sun et al. introduced bio-supported Pd NPs (Pd/BC) as water-insoluble arylalkynes to β-ketosulfones under mild con-
a phosphine-free catalyst for the SMR (Scheme 12)50 via one- ditions. In 2017, Beverina et al. showed that such micelles
pot synthesis by simply mixing Pd(NO3)2 (or PdCl2) and the provide an appropriate medium for the SMR in an oxygenated
reducing reagent with BC nanofibres in a hydrothermal reac- environment at room temperature;54 Kolliphor EL can be used
tion; the ensuing Pd NPs are comprised of small polydisperse for the synthesis of popular molecular semiconductors rele-
islands with dimension of about 20 nm on BC nanofibers. vant to the classes of diketopyrrolopyrroles,55,56 diarylanthra-
Higher yields of the products were attained in water in the cenes,57 isoindigos,58 diarylbenzothiadiazoles,59 and
presence of 0.05 mol% recyclable Pd/BC catalyst, with yields perylenediimides. 60–63
The scope of the reaction is indicated
over 86% after five cycles; the Pd concentration was found to by the coupling of aryl and heteroaryl bromides with boronic
be 5.29% before reaction and 5.26% after five reaction cycles. acids and esters. A wide variety of Suzuki–Miyaura coupling
Pitchumani et al. reported the preparation and function of products, 6a–c, produced in high yield by this new catalyst is
an ionic Pd(II) complex stabilized using water-soluble pyridi- shown in Scheme 15; all reactions can be conducted directly in
nium-modified β-cyclodextrin (Pyr:β-CD) (supramolecular a standard oxygenated environmental condition in deionized
ligand) as an efficient catalyst for the SMR;51 this homo- water and the reaction medium can be reused.
geneous catalyst is very soluble in water as compared to native The Varma research group described a versatile iron-cell-
β-CD and could be reused more than six times without signifi- ulose-derived Fe3O4@CPd catalyst, 27, which has been pre-
cant loss of catalytic activity. The substrate scope, under the pared by the in situ production of nanoferrites and the incor-
optimized conditions, was explored for a range of diverse poration of carbon from renewable cellulose via calcination
4-substituted aryl bromides, 4, containing both electron-with- (Scheme 16).64 The particle size of 27 is in the range of
drawing and electron-donating groups, which all furnished 20–50 nm, the weight percentage of Pd was determined to be
products 6 in good yields in a short time, with the exception of 4.81% by ICP-AES analysis, and the surface analysis of 27
nitro-group substitution (0.5 mol% Pd(OAc)2 at 80 °C in 2 mL showed a BET surface area of 175.71 m2 g−1. The arylation of
H2O) (Scheme 13). aryl halides 4 could be easily carried out by boronic acid 5
Zou et al. developed the Pd@MIL-101Cr-NH2 catalyst via the
immobilization of Pd NPs on an amino-functionalized metal–
organic framework (MOF);52 four catalysts with different load-
ings of Pd NPs were introduced (denoted as 4-, 8-, 12-, and
16 wt% Pd@MIL-101Cr-NH2). The catalytic activity of these cat-
alysts was evaluated for the SMR, with the best catalytic per-
formance being achieved with the MOF that contained 8 wt%
Pd NPs (Scheme 14). Furthermore, the catalyst can be reused
at least 10 times without alteration of its catalytic activity.
In recent years, oxygen-equilibrated aqueous solutions of
Kolliphor EL, a well-known surfactant, have been noted to
form nanomicelles with oxygen-free cores that provided an Scheme 15 Micellar couplings in water and air by [1,1’-bis(di-tertbutyl-
phosphino) ferrocene]dichloropalladium(II) (Pd(dtbpf )-Cl2).

Scheme 13 The SMR of various aryl halides 4 with phenylboronic acid Scheme 16 Preparation of carbon-coated magnetic Fe3O4@CPd 27
5 catalyzed using the pyridinium-modified CD/Pd(OAc)2 complex. catalyst.

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Scheme 17 Arylation of aryl halides 4 using 27 as catalyst.

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Scheme 18 The preparation of water-soluble fullerene-supported PdCl2 nanocatalyst 30.

under microwave (MW) irradiation conditions within 30 min 2.2 Gold/palladium NPs
(Scheme 17) and accommodates both the electron withdrawing Jutand et al. described the homogeneous origin of Au–Pd
and electron donating substituents. core–shell NPs in aqueous SMR through Pd leaching.68 The
Huo et al. introduced a fullerene-supported PdCl2 [C60- presence of the Au core allowed the careful evaluation of
TEGS/PdCl2] 30 as a water-soluble nanocatalyst via the coordi- the surface status of the Pd NPs after a catalytic reaction
nation of water-soluble fullerene NPs 29 with PdCl2; the using surface-enhanced Raman spectroscopy (SERS); Au@Pd
average particle sizes of 29 and 30 were 42.5 nm and 61.5 nm, NPs turned out to be efficient catalysts for the SMR, where
respectively (Scheme 18).65 Both the electron-donating and even a sluggish reagent69 reacted readily in water at
electron-withdrawing groups of aryl halides 4 were coupled room temperature with an average yield of 95% in roughly 4 h
with phenylboronic acid 5, and the ensuing biphenyl com- (Scheme 20).
pounds 6 could be obtained in excellent yields using
0.01 mol% of the catalyst at room temperature (Scheme 19); 2.3 Fe-ppm Pd NPs
4-chloroacetophenone was coupled using 0.5 mol% catalyst to
Most of today’s applications of transition metal-catalyzed
afford 65% yield and the catalyst could be reused five times
cross-coupling chemistry rely on the expensive Pd. However,
without significant loss in its catalytic activity. The stable Pd
Lipshutz et al. in 2015 demonstrated that NPs from in-
catalyst 30 leached only a small amount of Pd in a long-term
expensive iron(III) chloride (FeCl3), which naturally contains
static state and ICP-AES analysis showed that there was only
ppm levels of Pd,70 can be used directly for the SMR. Using
10 wt% loss after five recycling runs.
several control reactions, it was clearly shown that successful
A heterogeneous biopolymer complex, wool-based Pd cata-
couplings require the presence of both FeCl3 and Pd within
lyst, has been reported for the SMR in water.66 Wool is an in-
these nanocomposites. All reactions were carried out using
expensive natural biopolymer comprising amino acids cross-
2-dicyclohexylphosphino-2,6-dimethoxybiphenyl (SPhos) as a
linked via S–S bonds, the main component being keratin. This
ligand in various ratios. The reduction of 5 mol% of pure
biodegradable biopolymer, bearing numerous amino acids
FeCl3 with 10 mol% of MeMgCl in the presence of 5 mol%
units with functional groups such as –NH–CO–, –NH2 and –S–
SPhos and 320 ppm Pd(OAc)2 generated a superior nano-
S– etc.,67 serves as a green support for facile reactions and the
catalyst that mediated the formation of the desired coupled
broad scope of these reactions with respect to both coupling
product 6 in 95% isolated yield (Scheme 21). Doping pure
partners has been explored.
FeCl3 with 500 ppm of other metals, such as Ni(acac)2, NiCl2,
MnCl2, CoCl3, Cu(OAc)2 or CuBr2 produced catalysts that gen-
erated variable levels of product; in all cases, the yields were
≤38%.

Scheme 19 The SMR of arylboronic acid 5 with aryl halides 4 using

catalyst 30. Scheme 20 The SMR via Au–Pd core–shell NPs.

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firm anchoring of the glutathione on the ferrite support via

the thiol group is responsible for achieving the high reusability
of the catalyst.

2.7 Gold NPs

Scheme 21 Couplings between aryl halides and aryl or alkenyl boron
Although the chosen catalyst for the SMR is invariably Pd NPs,
derivatives.
Au(I) complexes can also be applied as efficient alternatives.74
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Au NPs have gained significant prominence in catalytic

applications75–77 as exemplified by the facile synthesis of
2.4 Cu-ppm Pd NPs
highly poly(2-aminothiophenol) (PAPT)-stabilized Au NPs78
The same research group reported copper-catalyzed Suzuki– applied for the SMR. The proposed mechanism of Au NPs use
Miyaura reactions under remarkably mild conditions, wherein in SMR may follow a homogeneous route, as the leaching of
ppm levels of Pd(OAc)2 worked synergistically with Cu catalyst Au was observed in the first half-hour of the coupling reaction
to generate biaryls in the absence of organic solvent;71 the (5.5% of the initial catalyst charge).79 Importantly, the precise
investment of significant energy in the form of typically harsh control over the size of Au NPs and the amount of PATP stabil-
reaction temperatures could thus be eliminated. A new P(O),N- izer are crucial for improving the catalytic activities of Au NPs;
ligand generated in situ from a readily available precursor has an increase in size from 1.0 to 2.0 and 5.0 nm decreased the
been uncovered that allows couplings to occur with in- yield from 87% to 76% and 10%, respectively. On the other
expensive Cu(OAc)2. The entire aqueous system containing hand, when the size of Au NPs was maintained at 1.0 nm but
nanomicelles as the reaction vessels, base, copper and palla- with considerably more stabilizer added, only a trace amount
dium can be recycled, further attesting to the eco-friendly of product was formed. It is known that the smaller size of Au
nature of this technology. NPs will lead to higher catalytic activity, while the effect of
polymer amount on the Au activity may be attributed to the
2.5 Nickel NPs
fact that the PAPT polymer may act as a catalyst inhibitor.
Nickel nanoparticles, formed in situ and used in combination With only 0.05 mol% of Au catalyst loading, high yields of pro-
with micellar catalysis, catalyze the SMR under mild aqueous ducts from substituted aryl chlorides 4 and arylboronic acids 5
reaction conditions;72 the proper choice of ligand on the were attained (Scheme 23) and the recovered Au catalyst, by
metal, complementing the hydrophobic characteristics of simple filtration, retained its activity without significant loss
aqueous nanomicelles achieves the objective. This newer tech- over six cycles, with yield loss being within 3% for six cycles.
nological development also showcases broader substrate The preparation of Au NPs and graphene oxide (GO)-incor-
scope, essentially stoichiometric levels of reaction partners, porated strontium ion cross-linked alginate/carboxymethyl-
considerable flexibility in the choice of both leaving group and cellulose (Sr/Alg/CMC/GO/Au) composites was accomplished
source of boron, very mild reaction conditions and notably, using dissipative convective procedures that were followed by
the option for recycling of the aqueous medium containing the freeze-drying method (Scheme 24). In the case of the Sr/
both the surfactant and the catalyst. Alg/CMC composite, capillary formation in the range of
50–80 µm with interconnected pores having a diameter of
2.6 Ferrite NPs
about 5–20 µm was observed. Incorporation of Au-NPs into the
The potential application of the glutathione-based organo- alginate/CMC composites resulted in organized capillaries of
catalyst, having uniform-sized particles with cube-like mor- 25–50 µm with interconnected pores around 5–30 µm.
phology with an average size range of 10–15 nm, was intro- Moreover, the Sr/Alg/CMC/GO/Au composite gel revealed capil-
duced in the homocoupling of aryl boronic acids 5 under the laries and pores with diameter around 10–15 µm and 5–20 µm,
microwave (MW)-assisted aqueous synthesis of symmetric respectively; its application for the SMR required only
biaryls 6 by Varma and co-workers (Scheme 22).73 A wide range 0.005 mol% catalyst (Scheme 25).80 Higher yields were
of substituents, regardless of their electron-withdrawing or obtained in the case of substituted aryl iodides, while substi-
donating nature, was accommodated and the catalyst was tuted aryl chlorides gave a lower yield. The composites dis-
found to be reusable after 4 cycles; easy recovery from the reac- played 6 cycles of recyclability and 98% isolated yield, the turn-
tion mixture was facilitated using an external magnet. The

Scheme 22 Aqueous homocoupling of substituted arylboronic acids 5 Scheme 23 The SMR of aryl halides 4 and arylboronic acids 5 by Au
by the glutathione-based catalyst under MW irradiation. catalyst in water.

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num ions and extra hydroxyl groups on their outer surface,

provide the ability for immobilization of metal ions.96 The par-
ticle sizes of the resultant Fe3O4@Boehmite-NH2-CoII NPs 40,
in irregular geometric shape, were about 13–54 nm. Under
the optimized reaction conditions, a variety of structurally
divergent aryl halides 4 reacted with phenylboronic acid 5 to
produce the desired coupling products 6 (Scheme 27) and the
superior catalytic activity of the new nanocatalyst was not
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significantly decreased even after seven recycle runs. The hot

filtration test demonstrated that a negligible amount of active
species (less than 0.31 mol% by ICP-OES analysis) was leached
out during the catalytic reaction.

3 Ethanol
The selection of an appropriate solvent or solvent mixture as
the reaction medium is of paramount importance besides
task-specific reaction catalysts and energy requirements. The
Scheme 24 Schematic representation of the Sr2+ crosslinked alginate/ influence of solvent on chemical reactivity has been studied
CMC composite hydrogels synthesis process. Reproduced with per- for more than a century, beginning with the work of Berthelot
mission from ref. 80. Copyright (2017) Elsevier. and Pe′an de Saint Gilles in Paris, France in 1862 on the esteri-
fication of acetic acid with ethanol (EtOH);97 EtOH is a green
and ideal renewable solvent for numerous organic reactions.

3.1 Palladium NPs

Several scientific groups have developed catalytic systems that
operate in EtOH solvent for cross-coupling reactions. Wu et al.
Scheme 25 The SMR of aryl halides 4 with phenylboronic acids 5 cata- devised a novel reusable alkoxy Pd complex based on the
lyzed by Sr/Alg/CMC/GO/Au composites. N, O-ligand 43 (Scheme 28) that demonstrated superior catalytic
activity in EtOH for the SMR without using any phosphine
ligand (Scheme 29);98 complex 43 showed high catalytic activity
over frequency (TOF) value being 4900 h−1; ICP-MS analysis for an array of aryl bromides to give excellent yields and no sig-
did not show any leaching of Sr2+-ions. nificant loss of catalytic activity was discerned after six cycles.
The Nahra research group introduced the [NHC·H][Pd(η3-R-
2.8 Cobalt allyl)Cl2] complexes 44 as facile, environmentally-friendly and
In recent years, considerable attention has been focused on effective catalysts for electron-withdrawing and electron-donat-
Pd-free reactions as the awareness sets in that transition metal ing aryl bromides and chlorides as well as heteroatom-contain-
catalysts such as Ni,81 Cu,82 Fe83 and Co,84,85 may serve as sub- ing and sterically hindered aryl halides 499 (Scheme 30).
stitutes for air-sensitive and expensive precious metals such as Wang et al. produced (Ni,Mg)3Si2O5(OH)4 solid-solution
Pd. Although Co-catalyzed reactions have been relatively nanotubes (NTs) of tunable compositions via hydrothermal
rare,86,87 they have attracted attention in organic synthesis synthesis by varying the molar ratio of Mg2+ to Ni2+, which
owing to their superior reactivity for various C–C bond were then loaded with Pd (∼0.045 wt%); the ensuing catalyst
forming reactions in view of nontoxicity, low cost, accessibility demonstrated superior activity for the SMR between iodoben-
and their interesting mode of action;88,89 both homogeneous zene or 4-iodotoluene and phenylboronic acid (Scheme 31).100
and heterogeneous Co-based catalysts in combination with Among the various ratios of Mg2+ : Ni2+ investigated
various ligands have improved the cross-coupling (Mg2+ : Ni2+ = 0 : 2.0, 0.5 : 1.5, 1.0 : 1.0, and 1.5 : 0.5), hydrother-
reactions.90–94 Akhlaghinia et al. introduced a green magnetic mally stable (Ni,Mg)3Si2O5(OH)4 solid-solution silicate NTs
catalyst based on Fe3O4@Boehmite NPs 35 of very small size; with Mg2+ : Ni2+ ratio = 1.0 : 1.0, provided an ideal tubular-
the immobilization of Co(II) was accomplished via the reaction structured support for catalysts with low Pd loading, excellent
of Fe3O4@Boehmite-NH2 39 with ethanolic solution of recycling performance for 10 cycles, with yields of ∼99%, and
CoCl2·6H2O (Scheme 26) and the ensuing catalyst used for an extremely low Pd release level of ∼0.02 ppm was also
SMR.95 Boehmite NPs 32, a component of the aluminum ore, observed; Pd was 0.0449 wt% before the 1st cycle and
bauxite, with octahedral double sheets centered with alumi- 0.0447 wt% after the 10th cycle.

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Scheme 26 The preparative steps for Fe3O4@ Boehmite-NH2-Co(II) NPs 40.

3.2 Copper/palladium
A Suzuki-type C–H arylation of azoles was accomplished using
Pd(OAc)2, Cu(OAc)2 and CuCl101 and the beneficial effect of
CuCl was described in the Pd(OAc)2 catalyzed SMR with
2-heterocyclic boronates.102 Liebeskind et al. introduced a Pd
Scheme 27 The SMR of diverse aryl halides with phenylboronic acid
catalyzed, Cu-mediated route for the reaction of aryl- and
catalyzed using 40.
alkenyl halides and arylboronic acids with Cu(I) thiophene-2-

Scheme 28 The synthetic steps for assembly of the Pd complex based on N, O-ligand 43. Conditions: (i) n-BuLi, THF; (ii) Ph2CvO; (iii) 2 N HCl; (iv)
Pd(OAc)2, toluene, room temperature, 3 days.

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larger size range, accompanied by some aggregation of NPs. At

this Pd/Mn+ ratio, the particle size was close to 7 ± 2 nm irre-
spective of the gelling metal Mn+, except Cu2+ for which a
special narrow size distribution was obtained. The ensuing bi-
metallic hybrid catalysts are of special interest because they
Scheme 29 Modified SMR of aryl bromides 4 with boronic acid 5 by
catalyst 43 in EtOH solvent.
incorporate the textural properties of alginate, the excellent
catalytic activity of Pd NPs and the presence of a second metal
species that influences the catalytic activity as highlighted in
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the superior performances of Pd NPs supported on copper-

alginate aerogels for the SMR. This heterogeneous catalyst,
which could be reused for several cycles without significant
loss of activity or metal leaching, showed excellent catalytic
activities as illustrated by a TOF value of 10 s−1 and a TON
value close to 106.

4 Water/ethanol mixture
4.1 Palladium NPs
Scheme 30 Scope of the SMR using catalyst 44 in EtOH solvent. Over the last few years, GO105,106 and chemically-derived gra-
phene (CDG)107 have been introduced as extremely versatile
carbon materials; GO and its CDG derivatives have been used
as supports for Pd clusters and NPs as superior catalysts for
the SMR in aqueous EtOH. In contrast to the conventional Pd/
C catalyst, GO and graphene-based catalysts afforded much
higher activities with TOF exceeding 39 000 h−1 and very low
Scheme 31 The SMR between 4-iodotoluene 4 and phenylboronic
acid 5. Pd leaching, the highest activity being achieved with Pd2+-GO
and the H2-reduced derivative Pd0-CDG-H2, followed by Pd0-
CDGEXP and Pd/C (Scheme 33).
carboxylate as a mediator in the absence of a base.103 Alginate- Recently, Fu et al. disclosed a facile photodeposition strat-
based nanocatalysts have been used for the C–C bond for- egy to produce a green catalyst, Pd/g-C3N4 nanocomposite with
mation via a procedure that might be applied for gelling many lower Pd contents (Pd0.10/g-C3N4), for the SMR (Scheme 34)
metals Mn+ (Ca, Ba, Mn, Zn, Ni, Ce, Cu, and Co), allowing the where the Pd NPs are uniformly dispersed on the g-C3N4
straightforward preparation of a panel of alginate/Mn+/Pd NPs surface;108 excellent catalytic activity was observed at room
gels (Scheme 32).104 The main influence of the gelling metal
nature on the surface areas of alginate/Mn+/Pd NPs aerogels
has been disclosed. Although Mn2+, Zn2+, Ni2+ and Co2+ did
not induce considerable change, the use of Ca2+, Ba2+, Cu2+
and Ce3+ increased the surface areas when compared with the
solids obtained without gelling metal Mn+. The optimum Pd/
Mn+ ratio was found to be 97/03, which resulted in the for- Scheme 33 The SMR of various aryl Bromides 4 using 0.25 mol%
mation of monodisperse Pd NPs; higher ratios produced a Pd(II)–GO.

Scheme 32 Schematic diagram of Pd NPs supported on copper-alginate aerogels. Reproduced with permission from ref. 104. Copyright (2012)
American Chemical Society.

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Scheme 34 The SMR of aryl halides 4 on the catalytic conversion to

biaryls 6.
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temperature with quantitative conversion and a high yield of

97% for biphenyls. The high catalytic activity in the SMR
was accredited to the specific nanostructured characteristics of
Pd/g-C3N4; i.e., the concerted effects of g-C3N4 in conjunction
with ultrafine Pd particles. The exact amounts of Pd in
Pd/g-C3N4 were detected via ICP-AES and the contents of Pd in
Pd0.05/g-C3N4 and Pd0.10/g-C3N4, were measured to be 4.4 wt%
and 8.8 wt%, respectively.
Scheme 36 Schematic of the fabrication process for the 3D IL-rGO/Pd
In another methodology, Astruc et al. reported the use of
hydrogel. Reproduced with permission from ref. 110. Copyright (2018)
Pd NPs (1.4 nm) that were stabilized by dendritic nanoreactors Elsevier.
containing 1,2,3-triazole ligands bearing TEG termini and its
application for the SMR of aryl bromides 4 at sub-ppm levels
(Scheme 35);109 the hydrodynamic diameters of the TEG den-
drimers determined by DOSY NMR and DLS were 5.5 ± 0.2 nm
and 9 nm, respectively. The structure of TEG termini of the
dendrimer tethers are responsible for this excellent degree of
intra dendritic Pd NP stabilization since they interact inter
dendritically to form large assemblies; the TONs are very Scheme 37 The SMR of a variety of aryl halides with phenylboronic
impressive at 80 °C, sometimes even larger than 106 with only acids catalyzed by the 3D IL-rGO/Pd hydrogel.
0.3 ppm of Pd for bromides.
It has been shown that 3D amine-terminated IL covalently
functionalized graphene (3D IL-rGO)/Pd composite aerogels
Silyl ketones have recently emerged as visible-light photo-
(Scheme 36) can be used as efficient and stable catalysts for
initiators in polymer science,111 which, upon irradiation,
the SMR under mild conditions (Scheme 37).110 The catalyst
undergo homolytic Norrish type I C–C or C–Si bond cleavage
was synthesized via a green reduction-inducing self-assembly
and the ensuing radical fragments initiate the polymerization
process; the cations of NH2-IL introduced to the surface of gra-
process. This strategy was exploited by Studer et al. for the
phene sheets prevented the restacking of graphene sheets and
preparation of Pd NPs starting with Pd(OAc)2 under visible
developed the specific surface area, which improved the per-
light-emitting diode (LED) irradiation.112 Depending on the
formance of the catalyst. The negatively charged Pd precursor,
photoinitiator used, the diameter of the Pd NPs could be
adsorbed on the positively charged imidazolium ring moiety
adjusted to 1.9 or 5.2 nm and stabilized with polyvinylpyrroli-
of NH2-IL, created Pd NPs with small sizes uniformly distribu-
done (PVP); these recyclable catalysts accomplished the SMR at
ted on the graphene sheets, which increased the active surface
low loading (0.5 mol%) to produce excellent yields of substi-
area of catalysts and enhanced their catalytic activity
tuted biphenyls (Scheme 38), with Pd leaching content being
(Scheme 36). The cross-coupling of aryl halides with phenyl-
0.1 ppm after 0.5 h.
boronic acid was investigated under 5 wt% loading amount of
The nanostructured Pd NPs, immobilized on the surface of
Pd in mixed solvents, EtOH/H2O. Non-substituted aryl halides,
modified magnetic GO by poly 2-acrylamido-2-methyl-1-pro-
iodobenzene and bromobenzene afforded good yields up to
pansulfonic acid (GO/Fe3O4/PAMPS/Pd), were introduced as an
90%, with electron-withdrawing groups delivering higher
efficient nanocatalyst for the SMR in a mixture of H2O and
yields than electron-donating groups, while the yield of chloro-
benzene was still very low even after a prolonged reaction time.

Scheme 38 The SMR under irradiation with a visible light-emitting

Scheme 35 The SMR between bromoarenes 4 and phenylboronic acid 5. diode (LED).

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Scheme 39 The SMR of various aryl halides 4 with aryl boronic acids 5
Scheme 41 The SMR by Pd–Ag@CQD 45.
catalyzed by the GO/Fe3O4/PAMPS/Pd nanocomposite.
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0.871 ppm Pd and 0.520 ppm Ag in the reaction mixture,

EtOH by Sedghi and co-workers (Scheme 39);113 superior cata-
amounting to a loss of 0.058% Pd and 0.034% Ag from the
lytic activity was observed for the cross-coupling of alkyl
total amount of the catalyst. The highest TON and TOF were
iodides, aryl bromides as well as aryl chlorides as the challen-
found to be 752.3 and 12.53 min−1, respectively, for the cross-
ging substrates. The Fe3O4 NPs are quasi-spherical, with
coupling reaction. In another report, Yamashita et al. had the
average diameters of 16 nm and the Pd-NPs having a mean
same bimetallic Pd/Ag nanocatalyst on SBA-15 mesoporous
size of 5 nm were dispersed in close contact with the surface
silica as a plasmonic catalyst in the SMR with high catalytic
of the GO sheet; the Pd content was estimated to be
efficiency.116
1.1150 mmol g−1. The results revealed that PAMPS is a
Ultrasound and microwave irradiation represent alternative
superior ligand with advantages such as performance in green
energy input systems to conventional heating and classical
solvent, ease of separation, shorter reaction times, recyclabil-
methods, and have received noticeable attention in the past
ity, much-reduced Pd leaching and high isolated yields.
decades for a variety of chemical processes;117–119 these
methods often fulfill green chemistry objectives via faster heat-
4.2 Palladium/silver NPs and mass-transfer, culminating in better yields and selectivity,
Carbon quantum dots (CQDs) make an interesting choice for short reaction times, and energy savings.120 Cavitation is
supporting metals because of their high surface area, chemical caused by the formation of gas or vapor bubbles and clouds of
stability and inertness.114 This was exemplified by the synergis- bubbles in a liquid that can be amplified by acoustic or hydro-
tically active bimetallic Pd–Ag hybrid NPs supported on CQDs dynamic effects, and their collapse generates higher localized
(Pd-Ag@CQD) 45, which were formed by an expeditious UV- temperature and pressure.121 Gogate et al. disclosed the useful-
light-driven (365 nm) one-step wet chemical protocol via the ness of ultrasound for the SMR of 4-bromoanisole with phenyl-
in situ reduction of Pd(II) and Ag(I) ions (Scheme 40);115 CQDs boronic acid, catalyzed by 5 wt% Pd/C in a mixture of ethanol
served as both stabilizing agent and reducing agent. The Pd– and distilled water under ambient conditions.122 Ultrasound
Ag nanohybrid particles nucleated on the CQDs, thereby reduced the reaction time from 70 min to only 35 min, with
forming a stable and supportive nanohybrid structure and stat- catalyst loading of 1.5 mol%, a frequency of 22 kHz and power
istical analysis demonstrated that the size distribution was dissipation of 40 W.
between 2 and 6 nm, with the largest dimension being in the
range of 3–5 nm. The presence of electron-donating substitu- 4.3 Nickel
ents on aryl halides as well as the aryl boronic acid resulted in Although Pd catalysis has dominated the field and was respon-
less time for the completion of the reaction, whereas those sible for the coveted 2010 Nobel Prize in Chemistry, there has
with electron-withdrawing substituents took a bit longer, pre- been much attention toward the identification of complemen-
sumably due to the presence of polar electron-donating groups tary Ni-catalyzed processes,123–125 which tend to be low-cost
on the surface of the nanohybrid CQD catalyst (Scheme 41). operations as compared to Pd catalysis,123,124 besides the
The catalyst was found to be reusable up to the third run, opportunity to discover new reactivity.126 Patel et al. produced
without any loss of the catalytic activity. The leaching studies Keggin-type mono Ni(II)-substituted phosphomolybdate and
with Pd and Ag in the reaction medium showed the leakage of used it as a catalyst for the SMR with 0.1 mol% catalyst
loading;127 various reaction parameters were investigated, with
the highlight being the realization of >97% yield under mild
reaction conditions (Scheme 42).

Scheme 42 Coupling of diverse halobenzenes 4 with phenylboronic

Scheme 40 Synthesis of the Pd–Ag@CQD 45 nanohybrid. acid 5.

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4.4 Fe2O3 NPs

Astruc et al. unveiled the usefulness of α-Fe2O3 nanoclusters of
1.8 nm in size that were homogeneously deposited on the edge of
the GO sheets (α-Fe2O3 nanocluster/GO) as an efficient catalyst in
parts-per-million for the SMR;128 the reaction was conducted over-
night at 80 °C in the presence of 150 ppm mol%. Bromobenzene Scheme 45 Substrate scope for the SMR using Pd(OAc)2 in WERSA.
derivatives containing electron-donating and electron-withdrawing
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groups, 4, in the para positions were suitable coupling partners,

forming 6 with good yields (Scheme 43); the catalyst could be The deployment of 1 mol% Pd(OAc)2 in WERSA appeared to be
recycled at least four times with good yields. the ideal catalyst loading at room temperature, where most of
the reactions generated the corresponding coupling products,
6, in moderate to high conversion yields, irrespective of the
5 Aqueous extracts presence of electron withdrawing groups or electron donating
groups in the substrates 4 and 5.
5.1 Water extract of rice straw ash (WERSA)
The chemical analysis of rice straw ash has shown that it
Rice straw or its derived residues have been attractive feed- primarily consists of oxides like SiO2, Al2O3, Fe2O3, TiO2, CaO,
stocks for energy manufacture due to its accessibility around MgO, K2O, Na2O, P2O5, etc.130 It is believed that alkali oxides
the globe, and therefore its use in organic synthesis would be of potassium, sodium, calcium and magnesium react with
of tremendous interest from the environmental perspective as water to generate the corresponding metal hydroxides and
an inexpensive and eco-friendly renewable natural material. these alkali metal hydroxides act as internal bases to facilitate
Saikia et al. introduced the neat aqueous extract of rice straw the SMR. The recovered catalyst system was directly used for
ash (WERSA) as a novel green catalyst for the SMR at room several reaction cycles; the yields were, however, slightly lower
temperature (Schemes 44 and 45)129 as the reactions pro- in the 5th and 6th cycles.
ceeded smoothly in the Pd(OAc)2–WERSA system without the
use of any base/ligand/promoter/additive or organic media. 5.2 Water extract of banana (WEB)
Saikia et al. reported an efficient and expedient greener system
for the Pd(OAc)2-catalyzed ligand-free SMR in neat water
extract of banana (WEB) under ambient aerial conditions in
the absence of base/ligand/promoter/organic co-solvents
(Schemes 46 and 47);131 0.5 mol% of catalyst provided the
cross-coupled product in high yield (99%) within a short reac-
Scheme 43 The SMR catalyzed by α-Fe2O3 nanocluster/GO. tion time (5–90 min). Furthermore, it was possible to reuse the
catalytic medium after the extraction of products but the yields
produced in consecutive steps were low (60% yield in the 1st
recycle) possibly due to the dissolution of Pd(0) or Pd(II)
species in the extraction solvent.

6 Poly(ethylene glycol)
Today, poly(ethylene glycol) (PEG) oligomers are efficient, eco-
friendly and low-volatility liquids and are organic compounds

Scheme 44 Preparation of WERSA and its catalytic activity in the SMR.

Reproduced with permission from ref. 129. Copyright (2015) Royal Scheme 46 Various stages of WEB preparation. Reproduced with per-
Society of Chemistry. mission from ref. 131. Copyright (2015) Royal Society of Chemistry.

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Scheme 47 Pd(OAc)2 and WEB-catalyzed SMR of aryl halides 4 with aryl boronic acids 5.
Published on 05 November 2018. Downloaded by Institute of Chemistry, CAS on 6/8/2019 [Link] AM.

with a broad spectrum of chemical, industrial and medical model substrates and higher yields of the product in shorter
applications,132 although explored and produced indepen- reaction time periods were obtained in PEG and K2CO3 as a
dently in 1859 by Wurtz and Laurence.133 PEGs are readily mis- base at 60 °C. Another heterogeneous catalyst, in the form of a
cible with water and polar organic solvents, but immiscible reusable heterogenized Pd nanocatalyst, was prepared on
with non-polar organic solvents, aliphatic hydrocarbons and mesoporous MCM-41 support145 and applied for the synthesis
supercritical CO2.134 In recent years, relatively inexpensive of biphenyls 6 via the carbon–carbon cross-coupling reaction
PEGs have been widely used as greener media in several of sodium tetraphenylborate (NaBPh4) 46 with aryl halides 4 in
organic reactions as they are nearly harmless, being routinely PEG-400 under phosphine-free conditions (Scheme 49). This
used in drug formulations. Additionally, PEGs have a very low catalyst displayed excellent catalytic activity and air- or moist-
vapor pressure, high catalytic capacity, high thermal stabi- ure-stability for the SMR with good to excellent yields and high
lity135 and stability in both acidic and basic media, which turnover frequency. The surface analysis showed that the BET
make them suitable media for oxidation/reduction transform- surface area of the MCM-41 and Pd-TEDETA-MCM-41 is 1372.3
ations. Furthermore, PEGs have been used as efficient addi- and 908.6 m2g−1, respectively. The immobilization of organic
tives in aqueous-phase cross-coupling transformations to layers and Pd-complex onto the mesoporous wall were con-
improve the interaction between water-soluble catalysts and firmed by investigation of the large BET pore volume for
organic reactants.136,137 Varma and co-workers reported the MCM-41 and Pd-TEDETA-MCM- 41, which was found to be
first study of PEG as a preferred solvent for the Pd-catalyzed 1.521 and 1.471 cm3 g−1, respectively. The catalyst could be
SMR,138 which was adapted by other research groups using Pd recovered and reused several times; the amount of Pd in Pd-
salts such as PdCl2139 and Pd(OAc)2 140 or Pd NPs.141 de Souza TEDETA-MCM-41 was determined before and after the reaction
and co-workers deployed Pd2(dba)3 as a catalyst in PEG-300 and was found to be 0.0029 mol g−1 and 0.0028 mol g−1,
(the attached numbers in all cases refer to the average mole- respectively (1.52% leaching).
cular weight of PEG) for carbon–carbon bond formation under The plasmonic characterization and catalytic efficiency of
ligand-free conditions (Scheme 48);142 the salient advantages Pd particles anchored to the surface of the TiO2 were investi-
being milder reaction conditions, shorter reaction times, ease gated for the SMR by Hosseini-Sarvari and co-workers;146 the
of handling and excellent yield (up to 98%) of products 6 with photodeposition procedure under sunlight was used for the
high turnover number of ∼9700; the reaction system enables synthesis of nano Pd/TiO2 and this semiconductor with band
recycling of the catalyst, similar to ionic liquids, and it could gap ≥3 eV generated C–C bond formation. Notably, the Pd NPs
be reused several times with no decrease in activity. size was responsible for improving the localized surface
The Cho research group demonstrated that a catalytic plasmon resonance (Scheme 50). This novel photocatalyst
amount of Ni(0) powder and K2CO3 in PEG-400 at 110 °C are
equally as effective for the SMR;143 biaryls were obtained from
reactions of iodoarenes and arylboronic acids in high yields
and bromoarenes could also be coupled with arylboronic acids
under similar reaction conditions with further addition of
iodine. Naghipour et al. reported the use of a heterogeneous
Fe3O4@chitosan-Schiff base Pd nanocatalyst as a robust and
magnetically-recoverable catalyst for the SMR.144 Various sol-
vents such as water, DMF, DMSO and PEG were investigated in Scheme 49 The SMR of aryl halides 4 with NaBPh4 46 in PEG 400.
the SMR of 4-nitrobromobenzene with phenylboronic acid as

Scheme 48 The SMR catalyzed by Pd2(dba)3 in PEG-300. Scheme 50 The SMR under visible light irradiation.

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Walden in 1914. The discovery of this new class of media did

not have the expected impact until 1982 when dialkylimidazo-
lium chloroaluminate melts were introduced by Wilkes and co-
workers. A decade later, the new generation of air-stable
1-ethyl-3-methylimidazolium-based ILs was reported, thus
allowing the successful use of ILs147 with unique task-specific
features. The notable physicochemical properties of ILs, such
as non-flammability, non-volatility, polarity and stability
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(thermal, chemical and electrochemical) can be substantially

modified by changing the cationic and/or the anionic com-
ponents,148 which can give rise to ILs with specific properties
via numerous combinations of cations and anions. In view of
these attributes, ILs have been used in diverse applications,
for instance, batteries, fuel cells, sensors, thermal fluids, plas-
ticizers, lubricants, extractants and as a reaction media in syn-
thesis, analysis, catalysis, and separation as well as medicine
and pharmaceuticals.149 Not surprisingly, ILs have been used
Scheme 51 The suggested mechanism for enhanced catalytic activity in SMR-based transformations in recent years as efficient and
under visible light irradiation. Reproduced with permission from ref. 146. sustainable media. The Welton research group reported the
Copyright (2018) Elsevier.
first study of ionic liquids as a solvent for Pd-catalyzed C–C
cross-coupling reactions150 followed by several others. For
example, in 2015, Singh et al. devised an efficient recyclable
could accomplish the heterogeneous cross-coupling reaction at clay carbapalladacycle nanocomposite for the SMR in tetra-
room temperature in the H2O-PEG mixture by efficiently acti- methyl butyl ammonium bis (trifluoromethanesulfonyl) imide
vating substrates via the generation of photo-generated elec- [TMBA]NTf2 IL (Scheme 52);151 chloro-, bromo- and iodo-sub-
tron–hole pairs under visible light irradiation conditions. A stituted aryl halides 4 generated the desired products 6 in
rational mechanism has been proposed to explain the tentative good to excellent yield and selectivity.
reaction pathway that may occur under visible light irradiation Several Pd-based catalytic systems for the SMR were
(Scheme 51). introduced in different ionic liquids, namely, 1-butyl-1-methyl-
pyrrolidinium bis(trifluoro methylsulfonyl)imide [bmpy]
[NTf2]–water,152 1-aminoethyl-3-methyl imidazolium bromide
[Aemim]Br,153 1-butyl-1,4-diazabicyclo[2.2.2]octane dicyana-
7 Ionic liquids mide [C4-DABCO][dca],154 and trihexyltetradecylphosphonium
bis(trifluoromethylsulfonyl)imide ([P66614][NTf2]),155 among
Ionic liquids (IL) are increasingly being used as popular media
others, (Table 1).
in a diverse range of scientific and technical applications; the
Interestingly, the reaction can be conducted at room
first ionic liquid, ethylammonium nitrate, was described by
temperature with the appropriate yield (entry 2) and a base-
free efficient cross-coupling reaction is feasible (entry 3). The
Ni-catalyzed SMR for the formation of biaryls and terphenyls
has also been described.156 In the presence of β-diketone and
PPh3 ligands, Ni(TFA)2 performed as a robust catalyst for the
SMR of aryl halides 4 with arylboronic acids 5 in a mixture
of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)
imide [bmim][Tf2N] and water; the desired products 6 were
achieved in good yields using this catalytic system
Scheme 52 Pd-catalyzed SMR in ionic liquid. (Scheme 53).

Table 1 Comparison of various ILs reported in the literature for the SMR

Entry Solvent Catalyst Base T (°C) Time (h) Yielda (%) Ref.

1 [bmpy][NTf2]–water PdCl2 K3PO4 65 2 84–99 152

2 [Aemim]Br [[Gmim]Cl–Pd(II)] Et3N 25 1–10 65–94 153
3 [C4-DABCO][dca] PdCl2 — 110 3–6 40–99 154
4 [P66614][NTf2]–water Pd2(dba)3 Cs2CO3 160 48 19–99 155
a
Isolated yield.

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Scheme 53 Ni-catalyzed SMR in the ionic liquid.

Scheme 55 Pd-catalyzed SMR in choline chloride and glycerol system.
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8 Deep eutectic solvents 100 °C using 0.1–1 mol% of PdCl2 as the catalyst, cationic
Deep eutectic solvents (DES), introduced initially by Abbott phosphine ligands and K2CO3 as the base (Scheme 55). Among
et al., are important alternatives to room temperature ionic the various eutectic mixture systems examined, ideal results
liquids (RTIL), due to their interesting properties and benefits were obtained with choline chloride and ethylene glycol, fol-
such as low cost, ease of synthetic accessibility, benign and lowed closely by choline chloride and glycerol. Glycerol is
safe nature along with renewability and biodegradability.157 In greener than ethylene glycol, and with the minimal difference
general, DES are prepared via the complexation of quaternary in the obtained yield, the choline chloride and glycerol system
ammonium salts as hydrogen-bond acceptors with a hydrogen has become the chosen medium for this reaction.166 After
bond donor such as urea, carboxylic acids, amino acids, completion of the reactions, DES and catalyst can be recovered
sugars, and glycerol or M2+ ions such as Zn2+.158 The charge and reused five times.
delocalization occurs via hydrogen bonding between the elec-
tronegative component, such as a halide ion, and the hydro-
gen-donor moiety, which is responsible for the decrease in the 9 Supercritical carbon dioxide
melting points of the mixture relative to the melting points of
the individual components. One of the most characteristic pro- Supercritical or liquid carbon dioxide (compressed CO2) has
perties of DESs is their high viscosity due to the presence of an attracted enormous interest as an efficient and green alterna-
extensive hydrogen-bonding network, relatively large ion sizes, tive to many hazardous organic solvents. Supercritical CO2 is
and electrostatic forces within the liquid.159 Furthermore, they an abundant, cheap, nontoxic and non-flammable reagent
possess negligible volatility, a broader liquid temperature that is readily available and inexpensive. Carbon dioxide emis-
range than conventional molecular solvents, and are generally sions due to human activities, especially in densely populated
non-flammable. DESs as green media have been used for areas, have greatly increased over the past century. With
many chemical processes160,161 such as creating alloys, extrac- increasing awareness of its role in climate change, there is an
tion, surfactant chemistry, electrochemistry, polymerization, ever increasing interest in finding applications for the cap-
gas adsorption, biomass processing, nanotechnology and tured carbon dioxide.167 At room temperature and pressure,
various organic and inorganic transformations.162–164 The first CO2 is gaseous in nature, which facilitates the recovery of the
reported use of DES in the SMR was described by König and analyte and provides solvent-free analytes. CO2, being a linear
co-workers when they synthesized biaryls with the Pd-catalyzed and small molecule, diffuses much faster than other conven-
cross-coupling of aryl halides with boronic acids in a manni- tional solvents168 and has been used to replace harmful
tol–DMU–NH4Cl mixture; phenylboronic acid 5 was coupled Freons and certain organic solvents. Supercritical CO2 (scCO2)
with aryl bromides 4 in the DES at 90 °C using 10 mol% of Pd has ideal properties for the extraction of non-polar com-
(OAc)2 as a catalyst and 1.2 equiv. of Na2CO3 as a base, result- pounds, for example hydrocarbons, while its large quadrupole
ing in the nearly quantitative conversion of the starting moment also enables it to dissolve some polar compounds
materials after 6 h (Scheme 54).165 such as aldehydes, ketones, alcohols, and esters.169 For the
The formation of various biaryls 6 using SMR in a DES first time, Holmes and co-workers reported the application of
system has been reported via the construction of C–C bonds at scCO2 as a solvent in carbon–carbon bond formation via the
Pd-catalyzed SMR,170 followed by Feng et al. who reported the
use of SBA-15-supported Pd catalyst for the SMR in scCO2.171
The use of supercritical CO2 as an eco-friendly medium not
only preserves the simplicity but also prevents the leaching of
the Pd metal from their support. Furthermore, to expand the
repertoire of the new synthetic methodology using scCO2,
Wang and co-workers explored an environmentally benign and
efficient access to C–C bonds in good to high yields, which
comprised the use of Pd2(dba)3 under [hmim]NTf2 47 and a
Scheme 54 Pd-catalyzed cross-coupling of aryl halides 4 with boronic supercritical CO2 biphasic system employing K2CO3 as a base
acids 5 in DES. (Scheme 56).

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10 Biomass-derived solvents
Nature provides us with a generous supply of molecules that
can be applied as media either directly or after purification or
processing (valorization). In addition to the aforementioned
water, pioneering investigations are currently underway
exploiting the biomass-derived solvents as green and plentiful
resources. Biomass-derived solvents, which satisfy the seventh
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Scheme 56 The SMR under the [hmim]NTf2/supercritical CO2 biphasic principle of the green chemistry protocol, are emerging as
system. favourable alternatives as feedstock and renewable resources
for solvent production. This has been a burgeoning field of
interest within the fields of green and sustainable chemistry
The combination of scCO2 and ILs may provide a unique and the following section describes several biomass-derived
synthesis strategy in which reaction and separation can occur solvents that have been used in the SMR, e.g., glycerol,
consecutively. Owing to the strong electrostatic forces between 2-methyltetrahydrofuran (2-MeTHF), ethyl lactate and
cations and anions, scCO2 dissolves well in ionic liquids, but Cyrene, etc.
ILs actually do not dissolve in supercritical CO2.172 This cata-
lytic system has several advantages such as operational simpli- 10.1 Glycerol
city, ease of isolation of products, and high yields. The cata- The etymology of the word ‘glycerol’ is from the Greek word
lytic system could be easily reused for up to six consecutive ‘glykeros’ which means ‘sweet’. Since its discovery in 1779 by
cycles without noticeable loss in activity. A plausible mecha- the Swedish chemist Carl Scheele, the polyol has been used in
nism for this reaction is shown in Scheme 57. Initially, several disciplines.173 Glycerol, also known as glycerin, or as
Pd2(dba)3 can react with ionic liquid [hmim]NTf2 to form the 1,2,3-propanetriol, is an environmentally benign, hygroscopic,
metal carbene complexes Pd (NHC) NTf2, followed by the oxi- colorless, and sweet-tasting viscous liquid that is the principal
dative addition of bromobenzene 4 to Pd (NHC) NTf2 to obtain by-product of the biodiesel industry; 100 kg of glycerol is pro-
the aryl palladium intermediate A. Phenylboronic acid 5, acti- duced for every ton of biodiesel. Glycerol finds use in various
vated by K2CO3, reacts with intermediate A, which generates fields such as the pharmaceutical, cosmetic, and food indus-
the intermediate B upon transmetallation. Finally, the reduc- tries, where it is mainly employed as a humectant, thickener,
tive elimination of intermediate B produces the desired lubricant, sweetener or anti-freeze, besides being a green
product 6, which was separated from the reaction mixture by medium for a wide range of chemical processes. This eco-
scCO2 extraction during the course of the reaction. friendly medium can dissolve a lot of organic and inorganic
substances, including transition-metal complexes, with several
advantages of high efficiency, low cost, biodegradability, non-
toxic nature (does not metabolize to toxic products, unlike
ethylene glycol) and nonflammability. In addition, its high
boiling point enables the conduction of reactions at elevated
temperatures without losses via evaporation.174 In this regard,
glycerol as an effective medium has been used in many
organic syntheses as well as various cross-coupling reac-
tions,175,176 particularly for the SMR where the glycerol was
initially deployed as an efficient medium in 2007 when
Wolfson and co-workers reported their results with several aryl
halides.177 Gómez et al. prepared Pd NPs stabilized by tris(3-
sulfophenyl)phosphine trisodium salt (TPPTS) in glycerol,
starting from Pd(II) and Pd(0) precursors and other reactants;
this nanocatalyst was used for the SMR in glycerol and t-BuOK
as a base at 100 °C with excellent yields.178 Also, Cravotto et al.
demonstrated the use of microwave (MW) radiation and ultra-
sound (US) energy and combinations thereof (MW/US), instead
of conventional heating to produce C–C bond formation in gly-
cerol; Pd salt or the corresponding amount of solid catalysts
(5% Pd/C or Pd-cross-linked chitosan) were used.179 The use of
alternative energy input systems, such as US and MW as sub-
stitutes for conventional heating and classical methods for a
variety of chemical processes, has received noticeable attention
Scheme 57 Possible mechanism for the Suzuki reaction. in the past two decades.118,120,180 US-promoted SMR in glycerol

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Scheme 58 The SMR process in glycerol under ultrasound irradiation. Scheme 60 Ni-catalyzed SMR in 2-MeTHF.
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has been reported under mild conditions (Scheme 58)181 and

four new Pd N-heterocyclic-carbene (NHC)-based complexes an environmentally benign and harmless medium, may be
were prepared with 3,4,5-trimethoxybenzyl, alkyl and sulfonate used in the pharmaceutical chemical process.186 Garg and co-
N-substituents. The catalytic activity of catalysts was investi- workers reported an efficient and inspiring concise synthesis
gated in the synthesis of various biphenyls in a short reaction of various biaryls 6 using boronic acid derivatives 5 and aryl
time at 40 °C; aryl iodides and bromides 4 reacted successfully halides 4 or phenol-derived substrates 48 via the Ni-catalyzed
with arylboronic acids, naphthalene-1-boronic acid or potass- SMR in 2-MeTHF (Scheme 60);187 1–10 mol% of commercially
ium phenyltrifluoroboronate 5 with good to excellent yields. available bis(tricyclohexylphosphine)nickel(II) dichloride
Recently, Grison et al. disclosed the usefulness of NiCl2(PCy3)2 complex was used as an efficient catalyst for this
Eichhornia crassipes, commonly known as water hyacinth, to reaction. Additionally, several bis(heterocyclic) frameworks are
prepare recyclable EcoPd.182 Based on the natural ability of easily accessible and so is the potential for these cross-coup-
Eichhornia crassipes to bioconcentrate Pd in its roots, the lings to be performed for the preparative gram scale assembly
authors reported the transformation of plant-derived Pd of bis-heterocyclic frameworks with low catalyst loadings.
metals as eco-friendly catalysts. This biobased EcoPd has been The impressive influence of the biosolvent, 2-MeTHF, in
used for the SMR of various heteroaryl rings with good yields the SMR was demonstrated by the Bora research group, where
and enabled the expeditious synthesis of a broad spectrum of arylboronic acids 5 were allowed to react with acid chlorides 49
heterocyclic biaryl and heterocyclic-heterocyclic biaryl to produce aryl ketones 51 using 0.4 mol% of oxime-pallada-
scaffolds, in the presence of a small amount of catalyst in gly- cycle 50 as a catalyst in excellent yield in open air
cerol and in the absence of ligands or any additives. Nagarkar (Scheme 61).188 Gratifyingly, the reaction under a N2 atmo-
and co-workers reported the Ni-catalyzed SMR of phenyl- sphere provides a slightly lower yield of the coupling product.
boronic acid 5 with various aryl diazonium salts 22 in glycerol This suggests that the presence of dissolved air in 2-MeTHF
with good to excellent yield without using any base accelerates the catalytic cycle by enhancing the rate of acti-
(Scheme 59);183 this greener protocol can be successfully vation of arylboronic acid to aryl ion species, vital for the cata-
repeated for up to five consecutive cycles with no considerable lytic transmetalation step. A wide variety of aromatic acid
loss in catalytic activity. chlorides have been applied in this catalytic system but ali-
phatic acyl chlorides were not reactive under otherwise identi-
10.2 2-Methyltetrahydrofuran (2-MeTHF) cal reaction conditions. The salient advantageous feature of
this approach is the application of water-immiscible 2-MeTHF
2-Methyltetrahydrofuran (2-MeTHF) is accessible from natural as the medium, which provides convenient isolation of the
resources from biomass-derived compounds such as furfural crude reaction mixture via the separation of 2-MeTHF–water
or levulinic acid and is a good alternative medium for the layers, followed by the evaporation of 2-MeTHF. Moreover,
development of green synthetic methodologies. Its chemical oxime-palladacycles are stable to heat, air and moisture, and
and physical properties, namely its low miscibility with water, are easily accessible from low-cost starting materials.
boiling point, significant stability compared to other cyclic-
based media such as THF, 1,4-dioxane and others, renders it
more attractive for processes involving olefin metathesis,184
organocatalysis, and organometallics.185 Also, 2-MeTHF being

Scheme 59 Ni-catalyzed SMR of phenylboronic acid 5 with various aryl

diazonium salts 22 in glycerol. Scheme 61 Synthesis of aryl ketones 51 in 2-MeTHF.

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The mechanism proposed by the authors shows that

initially, Pd(0) is formed by the reduction of the Pd–C bond of
oxime-palladacycle 50 and then the oxidative addition of acid
chloride 49 to Pd(0) produces the acylpalladium(II) chloride
intermediate A. Under alkaline conditions, the subsequent
transmetallation of ArB(OH)2 5 to the acylpalladium inter-
mediate A occurs at the Pd–Cl bond to generate (acyl)(aryl)pal-
ladium(II) species B, which upon reductive elimination delivers
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the oxidative coupling product 51; the active Pd(0) species were
regenerated and the catalytic cycle resumed (Scheme 62).

Scheme 63 The SMR catalyzed by melamine–Pd complex 53 in pure

10.3 Ethyl lactate ethyl lactate.
Ethyl lactate, a lactic acid ethyl ester, is an important mono-
basic ester that is found naturally in small quantities in a wide
range of foods including wine, chicken, and some fruits. Its soluble polymeric catalyst that can be recovered after cross-
industrial preparation, in the form of a racemic mixture, coupling. The melamine–palladium system is inexpensive,
occurs via a reversible reaction between lactic acid and easy to handle, bench-stable and effective in catalysis in the
ethanol. It is a slightly yellowish liquid, has a pleasant odor presence of a variety of impurities. The authors, via this mela-
and is a suitable solvent for many organic reactions due to mine–palladium system, could successfully synthesize
attractive properties such as nontoxicity, high solvency power, Felbinac, a topical anti-inflammatory drug, on a gram-scale in
low vapour pressure, high boiling point (154 °C), and low a single step in nearly quantitative yield using unfiltered
surface tension. Furthermore, ethyl lactate as a sustainable Arkansas River water as the solvent.
medium has been used in the pharmaceutical and cosmetic
10.4 Cyrene
industries.189 Wan and co-workers used ethyl lactate as a
solvent in the SMR190 where the reaction occurred at 60 °C Dihydrolevoglucosenone (Cyrene) 54, obtainable from cell-
with Pd(OAc)2 as a catalyst and K2CO3 as a base in the mixture ulose in two steps, has been demonstrated to have physical
of H2O/ethyl lactate under ligand-free conditions. Later on, the properties similar to dimethylformamide (DMF) and other
Chalker research group developed another system that used dipolar aprotic solvents and, so far, has not shown any adverse
pure ethyl lactate for the SMR (Scheme 63),191 where a mela- effects. In 2018, Watson et al. reported a greener route for the
mine–Pd complex 53 was used as an effective catalyst to SMR, which employs 54 as an eco-friendly and efficient
provide direct access to biaryl 6 structures in high yields. alternative to conventional solvents such as DMF, THF, and
Furthermore, this catalyst is soluble and active in common tap 1,4-dioxane (Scheme 64);192 this benign method offers simpli-
water. Next, the melamine–palladium catalyst can also be city and excellent functional group tolerance and generality
cross-linked by reaction with formaldehyde to generate an in- with appropriate yields in both small and larger scale
synthesis.

11 Solvent-free conditions
According to the principles of green chemistry and addressing
sustainable development from both economic and environ-

Scheme 62 Probable mechanism for the cross-coupling reaction

pathway. Scheme 64 Pd-catalyzed SMR in Cyrene 54.

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global warming crisis, green and sustainable protocols have

turned out to be commonplace strategies in every aspect of
human activities both in academia and industry. In this
regard, comprehensive discussion and analyses of recent
advances in cleaner approaches will help us to gain better
insight into the holistic aspects of green metrics. This article
spotlights the most relevant advances in eco-friendly and
Scheme 65 Solvent-free synthesis of biphenyl 6 under MW and ball-
milling. environmentally-benign media for the synthesis of organic
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compounds via the SMR as a key step and a practical approach

to total synthesis and organic transformations. A wide spec-
mental perspectives, organic reactions under solvent-free con- trum of homogeneous and heterogeneous catalytic systems,
ditions have garnered much attention in the recent years in an especially nanocatalysts with metals such as palladium, nickel,
attempt to curb the production of pollutants, reduce the utiliz- gold, ferrite, copper, silver, and cobalt for the SMR have been
ation of or eliminate hazardous and expensive organic sol- summarized. Diverse classes of heterogeneous catalysts
vents, as well as operational simplicity. The solvent-free syn- based on graphene, zeolites, Fe3O4, carbon quantum dots,
thetic route is in compliance with the philosophy of green cellulose, wool, polymers, MCM-41, and chitosan, etc., have
chemistry since that can improve the E-factor (defined as the shown their usefulness in friendly vehicles ranging from
ratio of the weight of waste to the weight of product) and the water, ethanol, glycerol, PEG, and ionic liquids to newfound
process mass intensity, defined as the total mass of materials media such as DES, aqueous extracts, supercritical carbon
used to produce a specified mass of product.193 Solvent-free dioxide, and biomass-derived solvents such as ethyl lactate,
reactions have gained considerable attention as green method- Cyrene etc. Notably, in all the aforementioned efforts, the
ologies that are alternatives to the traditional procedures,194 researchers have tried to improve the important outcomes
often using supported reagents under MW irradiation con- such as yield, time, amount of catalyst, TON, TOF and gener-
ditions.195 These include grinding methods (performance of ality with a wide substrate scope. It is important to evaluate
the reaction in standard glassware using a magnetic stirring bar the number of effective catalysts used and their prowess
for mixing) and high-speed ball milling.196 in recent years, the under both homogeneous and heterogeneous catalysis,
SMR has been conducted under solventless conditions.197,198 which may differ as has been shown very recently.202 In the
Schneider et al. demonstrated a greener protocol for solvent-free near future, the emergence of the neoteric biocompatible
SMR in the presence of an inorganic solid support (KF–Al2O3) catalytic systems for SMR will prompt the utilization of cata-
and the development of alternative energy forms such as lysts supported on biomass such as sugarcane bagasse, silk,
mechanochemical treatment (grinding with mortar and pestle carrageenan, casein, pullulan, hyaluronan, glucan as well as
and ball milling) and MW irradiation (Scheme 65).199 nanocomposite materials based on the chitosan, cellulose
Tolerance toward atmospheric oxygen, desirable safety and alginate. Furthermore, the option to explore a combi-
aspects, higher yields and shorter reaction times make this nation of alternative energy output systems such as micro-
strategy a facile and attractive version of the SMR. Very recently wave, ultrasound and mechanochemical bill-mill operation or
in 2018, Baran et al. reported a magnetically recoverable sporo- solar and visible light-assisted reactions in conjunction with
pollenin-based Pd catalyst for the direct synthesis of biaryl renewable biomass-derived greener media such as Cyrene,
compounds via SMR with high turnover frequency and turn- ethyl lactate or γ-valerolactone (GVL) present exciting oppor-
over numbers;200 the recyclability of the catalyst was inspected tunities. In addition, the predominant use of earth-abundant
to ten consecutive cycles for the synthesis of biaryls with only base metals that are cheaper and safer should be examined
minor decreases in the reaction yields from 99 to 93%. In an for this protocol, which will open new avenues. Moreover, the
interesting work, Borchardt et al. described the mechanochem- newer developments in flow chemistry as a key enabling
ical Suzuki polycondensation as a greener and more effective technology along with greener media described in this review
alternative to the conventional media-based polymerization can forge an effective alliance in this cross-coupling reaction,
transformation of poly( phenylene)s.201 Under optimized con- capitalizing on the use of newer substrates other than aryl
ditions, this synthetic route can produce linear polymers with halides. Further improvements in benign by design method-
an outstanding degree of polymerization, under ligand-free ologies are expected in the coming decades and hopefully,
conditions in 30 minutes. Furthermore, the strategy was broad- this review will stimulate the design of more innovative,
ened to a hyperbranched system with high-temperature resis- efficient, biocompatible and biodegradable, non-metallic
tance in moderate to good yields in a short span of time. systems to help circumvent any limitations of this widely-
used coupling protocol.

12 Conclusions and future prospects

Conflicts of interest
After nearly three decades of enthusiastic green chemistry
activity in the face of increasing worldwide pollution and the Authors do not have any conflict of interest.

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Acknowledgements 28 A. Shaabani, R. Afshari and S. E. Hooshmand, New

J. Chem., 2017, 41, 8469–8481.
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Research Council of Shahid Beheshti University. R. S. Varma, Green Chem., 2015, 17, 1243–1248.
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