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Microwave-Assisted Synthesis–Catalytic
Applications in Aqueous Media

Article in Coordination Chemistry Reviews · January 2015


Impact Factor: 12.24 · DOI: 10.1016/j.ccr.2015.01.011

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Coordination Chemistry Reviews 291 (2015) 68–94

Contents lists available at ScienceDirect

Coordination Chemistry Reviews


journal homepage: www.elsevier.com/locate/ccr

Review

Microwave-assisted synthesis – Catalytic applications in aqueous


media
Anuj K. Rathi a , Manoj B. Gawande a , Radek Zboril a , Rajender S. Varma b,∗
a
Regional Centre of Advanced Technologies and Materials, Faculty of Science, Department of Physical Chemistry, Palacky University, Slechtitelu 11,
783 71, Olomouc, Czech Republic
b
Sustainable Technology Division, National Risk Management Research Laboratory, US Environmental Protection Agency, 26 West Martin Luther King
Drive, MS 443, Cincinnati, OH, 45268, USA

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2. Scope of review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3. Microwave-assisted catalytic organic transformations in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.1. Cross-coupling reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.1.1. Suzuki–Miyaura reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.1.2. Sonogashira reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.1.3. Mizoroki–Heck reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.2. Synthesis of heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.2.1. Nitrogen containing heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.2.2. Sulphur containing heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.2.3. Oxygen containing heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.3. Carbon heteroatom linkage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.4. Synthesis of amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.5. C H activations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.6. Synthesis of urea derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.7. Miscellaneous reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.8. MW-assisted synthesis of coordination polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4. Conclusions and future scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Disclaimer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

a r t i c l e i n f o a b s t r a c t

Article history: The development of sustainable methods directed towards the synthesis of molecules is due to the height-
Received 22 September 2014 ened awareness and recognition of alternative eco-friendly and economical protocols that have minimum
Accepted 22 January 2015 impact on environment. Among others, microwave (MW)-assisted methodology has matured and can
Available online 30 January 2015
be used safely to substitute for conventional laboratory heating techniques; a number of chemical trans-
formations have been achieved thereby improving many existing protocols with superior results when

Abbreviations: APTS, 3-aminopropyltrimethoxysilane; ADF-STEM, annular dark field scanning transmission electron microscopy; BINAP, 2,2 -bis(diphenylphosphino)-
1,1 -binaphthyl; Bmim, 1-butyl-3-methylimidazolium; CF, continuous flow; C C, carbon–carbon; CH3 CN, acetonitrile; Cu2 O, copper oxide; DCM, dichloromethane; DBU, 1,8-
diazabicyclo[5.4.0]undec-7-ene; DVB, divinylbenzene; DMF, N,N-dimethylformamide; DBSA, p-dodecylbenezenesulfonic acid; EtOH, ethanol; iPr2 NH, diisopropylamine; ESI-
MS, electrospray ionisation mass spectrometry; Fig, Figure; FT-IR, Fourier transform infrared spectroscopy; GC–MS, Gas chromatography–mass spectrometry; H2 , hydrogen;
HCV, anti-hepatitis C virus; LiAlH4 , lithium aluminium hydride; MAOS, microwave-assisted organic synthesis; MCR, multi-component reactions; MW, microwave; MOM,
methoxymethyl ether; MO, methyl orange; NPs, nanoparticles; NaOH, sodium hydroxide; p-TsOH, p-toluene sulfonic acid; PEG, poly(ethylene glycol); PTC, phase-transfer
catalysis; TFA, trifluoro acetic acid; TBAB, tetrabutylammonium bromide; TEM, transmission electron microscope; TPP, triphenylphosphine; TBAHS, tetrabutylammonium
hydrogen sulfate; XRD, X-ray diffraction.
∗ Corresponding author.
E-mail address: varma.rajender@epa.gov (R.S. Varma).

http://dx.doi.org/10.1016/j.ccr.2015.01.011
0010-8545/Published by Elsevier B.V.
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 69

Keywords: compared to reactions performed under conventional heating conditions. The focus of this review is to
Microwave-assisted synthesis summarize recent MW-assisted catalytic reactions performed in aqueous media for the development
Aqueous chemistry of environmentally benign protocols. We review the catalytic MW-assisted methods employed for the
Metal-catalyzed reactions synthesis of a variety of heterocycles, cross-coupling reactions, C H activation reactions, synthesis of
Cross-coupling reactions
peptides, ureas, and carboxyl-containing coordination polymers and a host of miscellaneous reactions.
C C bond-forming reactions
Heterocyclic synthesis
In addition, some recent newer developments such as continuous flow capillary MW microreactors and
other related flow applications are included. This sustainable approach represents the fusion of friendly
reaction medium (water) and microwave activation in conjunction with a variety of catalysts.
Published by Elsevier B.V.

1. Introduction conventional heating is a relatively slow and inefficient method for


transferring energy into the reacting system (Fig. 1) [20].
Microwave-assisted organic synthesis (MAOS) has been rec- Newer innovations, namely MW-assisted continuous flow syn-
ognized as one of the most powerful and sustainable tools in thesis [4], have enabled fast and efficient synthesis of multigram
synthetic chemistry and has attracted much attention due to its quantities of heterocyclic compounds for eventual generation of
specific features including efficient atomic utilization, improved diverse chemical libraries [21].
temperature regulation, reaction homogeneity, and possible mod- The choice of solvents, reagents, and catalysts are chosen to
ifications of activation parameters [1,2]. Undeniably, many reports find alternative economic, greener, and more sustainable solu-
have demonstrated that a wide range of metal-catalyzed reactions tions, via the design and vigilant use of catalysts, which reduce
and cross-coupling reactions benefit immensely from MW heat- the chemical waste harmful to human health and the environ-
ing, exhibiting faster reaction kinetics [3–7]. The debate [8–12] ment (Fig. 2); fugitive emissions from organic solvents are the main
on ‘specific MW effects’ and ‘non-thermal MW effects’ continues cause of pollution problems during the synthesis of organic com-
while they are being investigated for specific chemical reactions pounds [22]. In this regard the suitable selection of the solvent and
[8]. Kappe and co-workers have re-examined Dudley’s work on catalyst appears to be the most critical decision. Replacement of
Friedel–Crafts benzylation of [D10 ] p-xylene using the 2-benzyloxy- toxic solvents by an environmentally benign alternative, such as
1-methylpyridinium salt [10,11] and concluded the MW effect does water, is an attractive option [23,24]. Though, water is the best
not occur [8]. Although non-existence of non-thermal MW effects choice, organic solvents still prevail because majority of the organic
has been agreed up on by Dudley and Stiegman [9], they contend raw materials/reactants and the reagents have poor solubility or
that ‘specific MW effects’ are clearly seen in their system; a detailed are completely insoluble in water; numerous highly reactive sub-
summary of these arguments have been reported by Ritter [12]. strates/reagents and catalysts often decompose or are deactivated
A review of the literature reveals MAOS [13] has advantage by water [25]. The solubility issue of reactants in aqueous media
over conventional heating because of its shorter reaction times and have been addressed in recent years. Jin et al. [26] have reported
formation of cleaner products. MW technology is not only appli- the use of a combined Brønsted acid-surfactant-combined catalyst,
cable for creation or transformation of a simple molecule, but is p-dodecylbenezenesulfonic acid (DBSA), which serves as a catalyst
also relevant to the assembly of desired bioactive molecules [14]; and a surfactant that enhances the solubility of organic compounds
increasingly it is becoming a fundamental tool of choice for opti- in water via the formation of colloidal dispersions. In terms of alter-
mizing key steps in the synthesis of target compounds in the field native activation methods, MW protocols are often compared with
of drug discovery [6,15–17]. In this context, several well-designed ultrasound (US)-expedited approach as has been recently reviewed
synthetic approaches for an array of N-, O- and S-containing seven- by Jhung and co-workers for the synthesis of metal organic frame-
to nine-membered heterocyclic ring systems have been developed works (MOFs) [27].
[18]. The main advantage of dielectric heating over conventional The fusion of water as a solvent and MAOS has evolved in to a
means is that microwaves couple directly with dipole or ionic rapid and greener alternative method when compared to conven-
molecules present in the reaction mixture and energy transfer tional heating [28,8] because of the sluggishness of conventional
occurs in less than a nanosecond (10−9 s) culminating in rapid rise methods of organic synthesis to meet the demand for expeditious
of temperature [19]. In contrast, conventional heating reactants are generation of compounds. Recent reviews [7,14] and books [29]
slowly activated by permeating heat through the walls of the vessel identify water as an alternative solvent, which is attractive from
that eventually reach the solvent and reactants which explains why both an economic and environmental point of view [30]. Organic

Fig. 1. Different heating mechanisms for conventional and MW heating.


Adapted from Ref. [20].
70 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

Fig. 2. Green and sustainable approach towards MW-assisted organic synthesis.

synthesis is conventionally carried out by conductive heating with generation of fine chemicals [33]. The short reaction time and
an external heat source, such as classical oil bath, which is compara- expanded reaction scope offered by MAOS are well suited to the
tively slow and inefficient method for transferring energy, dictated increased demand of faster synthesis in industry [17,34–36]. Since
by the thermal conductivity of the various materials involved, the first report in 1986 [37,38], MW-assisted chemistry has fulfilled
resulting in the temperature of the reaction vessel being higher the promise of a fast synthesis technique and the use of MW ovens
than that of the reaction mixture [6]. MW irradiation, instead, have become an indispensable tool in modern organic synthesis
produces efficient in-core volumetric heating by direct coupling [4,39–44] (Fig. 3).
of MW energy with the molecules (solvents, reagents, catalysts) From early experiments in ovens designed for household use
present in the reaction mixture [4]. The basic underlying principle [37,38] to the use of multimodal or monomodal equipment
behind the heating in a MW oven thus resides in the interaction of designed for chemical synthesis, this technology has been imple-
the polar entities of the reaction material with the electromagnetic mented worldwide and continues to be refined [45]. However,
waves. The phenomena of generating heat by electromagnetic irra- its use has been restricted in terms of scale due to the size
diation are either by collision or conduction, and sometimes both limitations of the cavity and reactor. Although, many large lab-
[31,32]. The efficiency of MW flash-heating has resulted in dramatic oratory MW systems are available that deploy various strategies
reductions in reaction times from days and hours to minutes and to achieve kilogram scale preparations including the use of paral-
are potentially important in process chemistry for the expedient lel vessels, stopped-flow, and continuous-flow systems, they have

Fig. 3. Applications of MAOS.


A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 71

Fig. 4. Continuous flow, capillary MW microreactors. (A) Schematic of the single capillary reactor system. (B) Schematic of the parallel, capillary multireactor system. (C)
Photograph of the parallel, capillary multireactor system (PEEK – polyetheretherketone).
Reprinted with permission from Ref. [56]. Copyright 2005 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

intrinsic limitations [46]. The current lingering problems have been its size, dielectric properties of the reaction materials, and tem-
addressed by the combination of flow reactors with embedded perature. A variable-frequency MW reactor has been introduced
MW technology as it enables synthetic endeavours in a labour-free [69] with a cylindrical cavity that undergoes a frequency shift
and scalable manner [47,48]. Recently, continuous flow microwave depending on the dielectric properties of the materials and temper-
reactors (CF-MW) pump reagents through a small heated coil [49], ature, which was compensated by using an automatic detection and
while some others use alternative multimode batch operation frequency feedback loop. The advantages of this reactor is it auto-
[50,51]. The principal design of flow cell features modification that matically detects the suitable resonance frequency and shifts to
makes optimum use of the cavity and monitors the temperature of generate the optimum MW irradiation conditions and a semicon-
the flow cell directly using the instrument’s in-built IR sensor [45]. ductor power generator forms a more intense and sharp heating
The combination of flow-chemistry and MW synthesis was ini- zone along the tubular reactor as compare to a magnetron gen-
tially described by Strauss in 1990s [52,53], but lately several erator (Fig. 5). Generally, polar solvents such as water, ethylene
flow-based MW reactors have been introduced, especially by Ley glycol, and ethanol with high dielectric loss are frequently cho-
and Haswell [54,55]. Flow chemistry entails driving liquids through sen because they absorb MW energy efficiently and convert it
a reactor, which is often just a capillary or tubing, and had con-
siderable impact on the design of macro-scale, microscale, and
meso-scale units. Similarly, Organ et al. [56] have developed a CF-
MW parallel-capillary microreactor wherein the assembly consists
of a stainless steel mixing chamber with three inlets that merge
to a single outlet which, in turn, is connected to capillary tubes
of various internal diameters (200–1150 mm) and, ultimately, to
collection vessels; the reagents flow in sequence into a multicapil-
lary reactor device and the transformations are accelerated by MW
irradiation to produce the products (Fig. 4).
This instrument has been successfully utilized for the prepara-
tion of a small library of cross-coupled products via the sequential
injection of stock solutions by flow capillary MW irradiation
(Scheme 1).
Recently, several chemical transformations with CF-MW syn-
thesis on a gm or kg scale have been reported using a variety of
setups [57–66] that deploy either single-mode or multimode MW
equipment; the key advantage lies in the enhanced process con-
trols when compared to batch synthesis in a microfluidic reactor
[67].
Recently, Nishioka and co-workers [68] have reported a flow
type single-mode MW reactor system with an elevated-pressure
option, where MW power is measured by a temperature feed-
Fig. 5. Flow type MW reactor. (a) Schematic of tubular reactor and MW heating unit.
back module and resonance frequency auto tracking function. The
(b) Distribution of electric field in the cavity.
design and control of a single-mode for a MW reactor is compli-
Reprinted with permission from Ref. [69]. Copyright 2014 American Chemical Soci-
cated because the resonance frequency of the cavity depends on ety.
72 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

Br R
HO OH
B
Pd(PPh3 )4
+
KOH, DMF: H2 O
R
5 examples
R = CHO, OMe, Me, NO2 72-100% conversion

F
O2 N H
NH2 Hunig's base
R N
+ R
DMF
NO 2

R = ArCH 2CH 2 NH 2 , ArCH2 NH 2 etc. 5 examples


55-100% conversion

Scheme 1. Cross-coupling reaction by using flow capillary MW irradiation [56].

rapidly to thermal energy [70,71]. MW-assisted reactions in aque- carbon–carbon bond-forming reactions has improved the
ous medium (“in-water” and “on-water”) [72] and under solvent- “state-of-the-art” of organic synthesis [101,102] with versa-
and catalysts-free conditions [73] have been described recently. It tile applications exemplified by various cross-coupling reactions
has not gone unnoticed that the preparation of nanomaterials and [103–106] such as Suzuki [107], Heck [108,109], Stille [110–113],
nanostructures, whose growth is highly sensitive to reaction con- Negishi [114–116], Hiyama [117], Kumada [118,119] and
ditions, could also benefit from the efficient and controlled heating Sonogashira [120] cross-coupling reactions.
provided by MW irradiation [74–76]. The synthesis and use of nano-
materials and magnetically recyclable catalysts in organic synthesis
3.1.1. Suzuki–Miyaura reaction
under benign reaction conditions are becoming increasingly pop-
Suzuki–Miyaura reaction is one of the most useful carbon-
ular [7,77–79] and reports have appeared on the preparation of
carbon bond-forming coupling reactions which involve organic
nanomaterial’s and magnetic nanocatalysts via MW protocols and
electrophiles and organoboron compounds [106,121,122] and
their applications in organic transformation using MW irradiation
occupies an important place in synthesis of natural products,
[33,74,80–82].
pharmaceutical intermediates [123,124], pesticides, and cova-
lent organic frameworks [125]. This reaction has been conducted
2. Scope of review in aqueous medium [126] and ionic liquids [127], the lat-
ter being important due to their low vapour pressure, high
The aim of this review is to summarize recent MW technol- dielectric constant, and high thermal stability, and its suitabil-
ogy developments as they pertain to sustainable organic chemistry ity for high temperature reactions in MW systems. Schmidt
in aqueous media by using various catalysts. Consequently, MAOS et al. [128] have reported the synthesis of 2,2 -biphenols by
in aqueous medium with recently developed catalyst has become MW-accelerated aqueous Suzuki–Miyaura coupling reaction using
an important arena because water is a safe, abundant, non-toxic, Anton-Paar-monowave-300 reactor (850 W with temperature con-
non-flammable, and readily available solvent thus adhering to the trolled via IR-sensor) between unprotected o-halophenols and
prominent Green Chemistry Principles [14,75,83–88]. Reactions o-boronophenols in presence of commercially available Pd/C as
conducted in hazardous organic solvents increase a chemist’s expo- precatalyst; either one or both coupling partners have OH-group
sure during the pre- and post-workup of conventional chemical protected as a methyl ether [129,130] or as a methoxymethyl ether
reactions [89,90]. Recent advances in flow-based MW strategy are (MOM) [131]. The successful application of Pd/C as a catalyst for
highlighted which offer greater control over reaction conditions, Suzuki–Miyaura reactions of various halophenols in aqueous media
such as catalyst and heating time and selectivity and scalability of has been documented [132,133] wherein various o-iodophenols
product when compared to batch processes. with o-boronophenol give high yields of the corresponding prod-
ucts (Scheme 2), the notable exception being the bromo derivative
3. Microwave-assisted catalytic organic transformations in that afforded moderate yield.
water García et al. [134] reported phosphine-free Pd hybrid nanocat-
alysts (2.0–2.5 nm) based on carbon-supported Pd nanoparticles
3.1. Cross-coupling reactions (NPs) obtained by decomposition of an organometallic palladium
precursor, [Pd2 (dba)3 ], under H2 atmosphere in presence of carbon
The last three decades have witnessed the remarkable success materials; aqueous Suzuki–Miyaura cross-coupling reaction occurs
of metal-catalyzed cross-coupling reactions in organic chemistry with different withdrawing and electron donor substituent under
[91]. Various homogenous catalytic systems, with the availability both conventional and MW heating (Scheme 3). Interestingly, the
of ligands and building blocks, have created useful tools towards reaction rate as well as the conversion markedly increased by using
the carbon–carbon coupling reactions [76,92–96]. Currently, the a mixture of PEG and water as solvent under MW conditions at
most popular methods employ transition-metal catalysts such 150 ◦ C. The synthesized nanocatalysts are stable, ran successfully
as Pd, Fe, Cu, Ni and Zn, [97] with Pd being the most popular five times without loss of activity, and no significant metal leaching
candidate [98–100]. The development of Pd-catalyzed was observed after 5 min of reaction time.
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 73

OH HO
Br I
OH Pd/C (2 mol%), water,
+ B
OH KOH, 150 °C, 0.5h, MW
OH OH
OH
78% yield

R2 Br OH HO
OH Pd/C (2 mol%), water,
+ R2
OH B
OH additive, 150 °C, 0.5h, MW
R1 OH
R1 = H, OMe R1
R 2 = H, Me, CHO, Cl, CN , CO2Me, NHAc etc.
12 examples
Additive = K 2 CO 3, KOH, KF, TBA F 22-88% yield

Scheme 2. MW-induced Suzuki–Miyaura coupling of o-halophenols with o-boronophenol [128].

OH
B Catalyst
X OH
+ K 2 CO3 , H 2O:PEG, MW
R1 150 oC, 5- 10 min
R1
X = Cl, Br 4 examples
R 1 = H, CHO, OMe 2-95% conversion

Scheme 3. Catalytic activity of the carbon-supported Pd nanocatalysts in the reaction between arylhalides and phenylboronic acid under MW heating in a PEG/H2 O mixture
[134].

Castro et al. [135] reported MW-assisted Suzuki–Miyaura reac- thermal or MW heating using a CEM Discover Labmate 300 W
tion in the solvent mixture containing the 4-picoline-derived ionic oven. The best results were obtained with aqueous potassium
liquid (C4 MPyBF4 ) and water (Scheme 4). hydroxide in presence of tetra-n-butylammonium bromide (TBAB),
Aqueous medium had the beneficial effect in C4 MPyBF4 /H2 O while organic base-like triethylamine gave slightly lower yields
system due to enhanced fluidity of the reaction media allow- and the use of N,N-dimethylformamide (DMF), dioxane or toluene,
ing energy and mass transfers between organic (substrates) and instead of water, resulted in poor yields; optimized MW conditions
aqueous-ionic (catalytic) systems in the Suzuki reaction. showed superiority over conventional heating for various sub-
Fluorous, oxime-based palladacycles have emerged as signifi- strates (Table 1). This system was also effective for Heck–Mizoroki
cant catalysts for carbon–carbon bond-forming reactions as they C C cross-coupling of arylthiazole and styrene derivatives with
are thermally stable complexes and are easily obtainable from good yields (88–90%) (Schemes 6 and 7).
inexpensive materials [136]. Generally, transition metal catalysis is Similarly, Hanhan et al. [143] have reported the synthesis of
accomplished in organic or perfluorocarbon solvents [137] and only a series of air-stable and water-soluble Pd(II)-pyridyl-imine com-
few exceptions of fluorous Pd-based catalysis being known in aque- plexes (Fig. 6) for the aqueous Suzuki cross-coupling reaction under
ous media [126,138,139]. Lam and co-workers [140] have reported MW irradiation conditions; catalytic activity increased with addi-
the synthesis of a recyclable, fluorous, oxime-based palladacycle tional CH3 groups and highest activity (98%) was observed by
(0.05 mol% Pd) and illustrated its application in Suzuki–Miyaura,
Sonoghashira, and Stille reactions in water under MW irradiation
conditions with high yields (Scheme 5). Table 1
The rationale behind the selection of thermally robust oxime- Suzuki cross-coupling reaction of thiazole with conventional or and MW heating
[142].
derived palladacycle is due to their many attractive features
including insensitivity to air and moisture, and their use as a Entry Boronic acid Conventional MW heating
precatalyst with an ability to slowly release Pd(0) which sup- Time (h) Yield (%) Time (min) Yield (%)
presses the growth of large Pd metal particles [141]. The important
1 Ph 10 97 20 95
advantage is the reactions are not contaminated with hard to
2 4-ClC6 H4 10 97 20 95
remove phosphine oxide. Similarly, Dawood et al. [142] have devel- 3 3,4-(OCH2 O)C6 H3 12 89 25 85
oped the benzimidazole oxime-based palladium (II) complex for 4 3-Thienyl 10 93 25 90
Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions for 5 4-Tolyl 9 97 20 95
6 4-MeOC6 H4 17 89 20 92
deactivated arylthiazole bromides and chlorides in water under
74 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

B(OH)2
X Pd(OAc) 3 (3%mol)
R1
R1 C 4 MPyBF4/water
Et 3N, 150 oC, 5 min.
MW
X = I, Br 8 examples
R 1 = 4-OMe, 4-NO2 , 2&3-Me, 4-OAc 53-95% yield

Scheme 4. MW-assisted Suzuki reaction using C4 MPyBF4 /water system [135].

X
B(OH)2
Palladacycle (0.05 mol % Pd)
+ K 2CO3 , H 2O, TBAB R1
R1 140 °C, MW, 2-6 h

R 1 = OMe, CF3 , CN etc 4 examples


X= Br, Cl, I 82-98% yield

X
Palladacycle (0.05 mol % Pd)
+ Pyrrolidine, H 2 O, 140 °C, MW R1
R1 2-12 h

R 1 = NO2 , H, Cl 4 examples
X= Br, I 86-96% yield

X
Sn Palladacycle (0.05 mol % Pd)
O
+ TBAB, H 2O, 100 °C, MW R1
R1 2-10 h

O 4 examples
81-94% yield
R1 = CHO, heterocyclic
X= Br, I

Scheme 5. Applications of palladacycle under MW in water [140].

Cl
Cl
Pd
N N OH
Br
N Ar
N
R + ArB(OH)2
TBAB, KOH, H 2O N
MW, 20-25 min R
S
S
15 examples
Ar = Ph, 4-ClC 6H 4 , 3,4- (OCH2 O)C6 H3, 85-95% yield
3-thienyl, 4-tolyl, 4-MeOC 6 H4
R = NHMe, NH Ph, CH3

Scheme 6. MW-assisted Suzuki cross-coupling of thiazole with various arylboronic acids [142].
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 75

Cl
Cl
Pd
Br N N OH
R
N

N
+ R
TBAB, KOH, H2 O
S
MW, 30 min
S N
R= Ph, CO 2Bu

2 examples
88-90% yield
Scheme 7. MW-assisted Heck–Mizoroki C C cross-coupling reactions [142].

X B(OH) 2
Catalyst (0.1 mol% )
+
K 2CO3 , H 2O, MW
R1 R2 5 min R1 R2

19 examples
8-98% yield for NBu4 + based complex
X = Br, Cl 8-96% yield for Bmim based complex
R1 = H, Me, OMe, COOMe, 4-OH, 4-COOH etc.
R2 = H, 4-Me, 4-Cl, 4-F

Scheme 8. MW-assisted Suzuki coupling of various aryl halides with arylboronic acid [143].

using NBu4 + ionic groups without TBAB (Scheme 8) and 1-butyl- [148] reported the synthesis of 6-arylpurines via Suzuki–Miyaura
3-methylimidazolium [Bmim] with TBAB as an additive under cross-coupling reactions of 6-chloropurines and sodium tetraarylb-
MW irradiation (850 W) in 5 min. The high activities of both com- orate within a short reaction time (30 min) using single-mode
plexes can be explained by the favourable effect of bulky groups microwave (MAS-I, Sineo MW oven) with continuous irradiation
and due to the ability of NBu4 + group to act as counter-ion for power 400 W, in neat water (Scheme 9).
SO3 − . MW heating was more efficient and 24-fold faster than The optimized reaction condition has been tried for a number
conventional heating although these complexes were suitable for of 6-chloropurine derivatives with varied substituents, including
only bromo substrate; chloro compounds afforded only reduced a sugar carbon substituent at N9; desired 6-phenylpurine deriva-
conversion. tives were obtained in good to excellent isolated yields (54–98%).
Purine and their derivatives with various substituents (such as However, acetylated nucleosides, when subjected to the reaction
C , N , O , S ) at C-6 are employed in various important building in water, C N glycosidic bond cleaved products were obtained.
block of DNA and have broad application in biological and pharma- The protocol avoids the use of toxic solvents, such as acetoni-
ceutical chemistry [144,145] including anti-hepatitis C virus (HCV), trile, toluene, tetrahydrofuran, and 1,4-dioxane and seems to be an
cytostatic, and anti-mycobacterial activities [146,147]. Qu et al. environmentally acceptable procedure for the synthesis of these
important 6-arylpurines.
Len and co-workers [149] described an efficient methodology
R'' R' using AntonPaar Monowave 300, for the ligandless Suzuki–Miyaura
cross-coupling of 5-iodo-2 -deoxyuridine in water using low load-
ing of Na2 PdCl4 (0.05–0.1 mol%) as a PdII source; very few methods
N N SO 3R are known for the introduction of an aromatic moiety on the het-
erocyclic part of nucleosides using MW irradiation [148,150–155].
Pd
Cl R' The catalyst loading 0.1 mol% of Na2 PdCl4 was effective in compar-
Cl
ison to lower loading of Na2 PdCl4 (0.05 mol%); sterically hindered
R= Na, NBu4 , Bmim substrates delivered modest yields while the aromatic heterocyclic
R'= H, CH 3 , CH(CH 3) 2 derivatives and the styrenyl compound gave high yields. Only 2-
R''= H, CH3 , acetylphenylboronic acid and 2-formylphenylboronic acid showed
less conversion due to the formation of dehalogenated byproduct
Fig. 6. Structure of Pd complexes. (Scheme 10).
76 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

Cl
N Pd(PPh3 )2 Cl2 N N
N
Ar4 BNa
+ Na2CO3, H2O, MW, 30 min
N N X N N X
100 °C
R R
18 examples
X = H, NH2 54-98% yield
R = Bn, 2-ClC6H4, Ph, Me, Et, AcO O
CH2CH2CH3, CH2CH2CH2CH3, , etc
Ar = Aryl AcO
OAc

Scheme 9. MW-assisted reaction of Ar4 BNa with various 6-chloropurines [148].

3.1.2. Sonogashira reaction was found to be essential; smaller amounts of TBAB resulted in poor
Sonogashira cross-coupling reaction is an important method for yields (Scheme 12).
C C bond formation, often conducted in polar, high-boiling sol-
vents such as DMF, N-methyl-2-pyrrolidone (NMP), and dimethyl 3.1.3. Mizoroki–Heck reaction
sulfoxide (DMSO), with a palladium catalyst and phosphine ligands Heck reactions between aryl halides and alkenes continue
in the presence of a copper as a co-catalyst [156–166]. to attract attention in the synthesis of pharmaceutical products
Wan and co-workers [167] developed an efficient protocol for [171,172], polymers, dendrimers, and various conjugated architec-
the copper-catalyzed Sonogashira coupling of aryl iodides with ter- tures of interest in materials science [173–179]. In contrast to other
minal acetylenes in nontoxic, recyclable water–polyethylene glycol C C bond forming reactions that involve a polar addition, the Heck
(CuI/PPh3 /PEG–water) in the presence of a base, K2 CO3 ; the proto- reaction tolerates many sensitive functionalities such as unpro-
col worked well for both electron-rich and electron-deficient aryl tected amino, hydroxy, aldehyde, ketone, carboxy, ester, cyano, and
iodides under MW heating conditions using CEM Discover system nitro groups [180]. The possibility of carrying out Mizoroki–Heck
within 20–50 min with good to excellent yields while the con- cross-coupling reaction in water could be of great value for the
ventional heating required 24 h for completion of the reactions development of industrial processes [171,181–185]. Kirschning
(Scheme 11). and co-workers [186] have used Discover LabmateTM MW oven
The reaction between 4-iodotoluene and phenyl acetylene (300 W) for MW-accelerated Mizoroki–Heck reactions in water
under MW irradiation was chosen as a model reaction to optimize using 2-pyridinealdoxime-based Pd(II)-complex as a heteroge-
the reaction conditions using various organic co-solvents admixed neous precatalyst. The catalytic activity of the Pd(II) precatalyst has
with water and the best yield (96%) was obtained in mixture of been optimized in the reaction of 4-bromoacetophenone with tert-
water: PEG-600 (3:1). butyl acrylate; 100% conversion in water and DMF in the presence of
TBAB is one of the most common phase-transfer (PT) catalysts, NaOH/iPr2 NH and TBAB has been achieved wherein water enabled
being employed in numerous C C, C N, C O, C S, and C P bond the enhanced reusability of the catalyst relative to DMF. The
forming reactions performed under liquid–liquid and liquid–solid cross-coupling reaction of aryl and heteroaryl bromides has
phase-transfer catalysis (PTC) conditions, as well as in halogenation been highly regio- and stereoselective and provided only the
and oxidation reactions. The presence of Bu4 NBr has proven indis- thermodynamically more stable E-isomer of ␤-substituted tert-
pensable in a number of carbon–carbon bond forming reactions butyl acrylates. The reaction with less reactive styrene, however,
such as the alkylation of allyl sulfones [168,169]. resulted in the formation of two isomeric products (12:1
Van der Eycken and co-workers [170] reported transition- ratio); major products were the E-isomers of 1,2-disubstituted
metal-free Sonoghashira type-coupling reaction of aryl halide in alkenes while the minor by-products were clearly not Z-isomers
water with phenylacetylene as the coupling partner in the pres- but 1,1-disubstituted alkenes (Scheme 13). The preparation of
ence of TBAB using single mode microwaves (150 W). The use of benzo[b]furans from alkynes and ortho-halophenols have also been
one equivalent of TBAB and an excess of base Na2 CO3 (4.0 equiv.) reported using this methodology.

O O
I Ar
NH NH
OH Na 2PdCl4
N O N O
O + B O
Ar OH KOH, H2O, 100 °C, MW
8 min- 1h
HO HO
HO HO

Ar = Ph, 2-MeC6H4, heteroaryl etc. 14 examples


0-85% yield

Scheme 10. MW-assisted ligandless Suzuki–Miyaura coupling with 5-iodo-2 -deoxyuridine in water [149].
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 77

I R1
CuI, PPh3 , K 2CO3
+ R1 Water-PEG (3:1), MW
R 120 °C, 20- 50 min
R
R = 4-Me, 4-OMe, 2-Me, 4-NO2, 4-CN, 15 examples
4-CH3 CO, H 69-96% yield
R1 = Ph, C 5H 11

Scheme 11. Cross-coupling reaction of aryl iodides with alkynes under MW irradiation [167].

R1
X TBAB , Na2 CO3
+ R1
H2 O, MW, 175 °C
R 10-25 min R

R =Aryl, heteroaryl, 1-naphthyl 17 examples


R1 = Ph 0-86% yield
X = Br, I, Cl

Scheme 12. MW-promoted Sonogashira-type coupling of aryl halides and phenylacetylene in water [170].

Singh et al. [187] described an efficient and cost effective proto- 3.2. Synthesis of heterocycles
col for aqueous phosphine-free Heck reactions using Pd(l-proline)2
complex as the catalyst in the presence of TBAB and NaOAc under Heterocyclic compounds comprise the largest class of organic
controlled MW irradiation conditions (single mode CEM Discover, molecules and are of enormous importance biologically and
200 W) (Scheme 14). The method provides an environmentally industrially. The majority of pharmaceuticals and biologically
benign procedure without phosphorus ligands and excellent yields active agrochemicals are sulfur and nitrogen-containing hetero-
of products in short reaction times. cyclic compounds [188] along with other heteroatoms such as

N
N PdCl2
O
+ CO2 tBu CO 2tBu
Ar-X Ar
base, H 2 O, TBA B, MW
150 °C, 5-20 min 6 examples
Ar = Aryl, heteroaryl 96-100% yield
X = Br, I

N
N PdCl 2
O
+ Ph Ph
Ar-X Ar + Ar Ph
base, H2 O, TBAB , MW
160 °C, 5-20 min
Ar = Aryl, heteroaryl
X = Br, I 6 examples
91-97% yield
N
N PdCl2
O
Ar-X + Ph Ar Ph
base, H 2O, TBAB, MW
160 °C, 5-20 min 6 examples
Ar = Aryl, heteroaryl 41-100% yield
X = Br, I

Scheme 13. MW-assisted Mizoroki–Heck reaction of heterocyclic bromides with tert-butyl acrylate [186].
78 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

R2 Pd(L-proline) 2, TBAB H R2
R 1-X + NaOAc (10 mol%), H 2O
R3 R3 R1
MW, 80–140 °C, 10–50 min
R 1 = Aryl, benzyl 27 examples
X = Cl, Br, I 77-94% yield

R 2 = COOMe, COOEt, CN, COOn-Bu, Ph


R 3 = H, Ph
R 2– R 3 = -(CH2 )4 -

Scheme 14. MW-assisted Heck reaction of aryl/benzyl halides with various alkenes [187].

oxygen [189], phosphorus [190], selenium [191], and many natu- NH 2


rally occurring such as procaine, codeine, reserpine, and morphine O Si
OH Cu (I)
are heterocyclic compounds [192–194]. O
MNP O NH 2
3.2.1. Nitrogen containing heterocycles Si
O
Nitrogen heterocyclic compounds such as pyridine, diazine, OH
pyrimidine, pyrazine, etc. are abundant in nature and are important MNPs-CuBr
because their structural subunits exist in many natural products
such as vitamins, hormones, antibiotics [195–197], and alkaloids, Fig. 7. Structure of magnetic nanoparticles (MNPs)-CuBr.
as well as pharmaceuticals, herbicides, dyes, and many more com-
pounds [198–201]. Consequently, they have attracted considerable
attention in the realm of synthetic organic chemistry [202,203]. synthesis from benzyl/alkyl halides, functional alkynes and sodium
The pyridine nucleus comprises important heteroaromatic class azides in water via a combination of one-pot multi-component
of compounds with a wide range of activities [204,205]. Nico- reaction in the presence of magnetic nanoparticles (MNPs)–CuBr
tinic acid derivatives and its isomers have been investigated for supported catalysts under MW irradiation (480 W) (Scheme 16).
the prevention or delay of the onset of type 1 diabetes mel- The bare MNPs were prepared by the conventional
litus. They have anti-bacterial, anti-oxidant, anti-inflammatory, co-precipitation method and subsequently reacted with 3-
and anti-carcinogenic activities, and have putative activity against aminopropyltrimethoxysilane (APTS) or [3-(2-aminoethylamino)
osteoarthritis and granuloma annulare [204]. Sriram and co- propyl]trimethoxysilane (AAPTS) to yield well characterized
workers [206] reported the synthesis of novel isoniazid (INH) amino-modified MNPs (Fig. 7). The synthesized catalyst was tested
analogues via MW-assisted one pot reaction of various benzalde- for a variety of substrates wherein the regiospecific formation of
hydes and dimedone in water with catalytic amount of DBSA 1,4-disubstituted 1,2,3-triazoles in good to excellent yields, and
(Scheme 15); they demonstrated the versatility of the reaction with no formation of the undesired 1,5-isomers occurred; most of the
29 examples providing 65–96% yields. functional groups such as OH, O , COOR, and N(CO) were
1,2,3-Triazoles are of considerable interest because of their tolerated under this one-pot CuAAC reaction conditions.
useful applications as pharmaceutical agents, agrochemicals, Similarly, Zarei et al. [215] have used Milestone microsynth
dyes, corrosion inhibitors, photostabilizers, photographic materi- oven, at power level 400 W, for a one-pot, MW-assisted, aqueous
als [207–209] and as anti-HIV agents [210]. Several methods are click synthesis of 1,4-disubstituted 1,2,3-triazoles via in situ gen-
known for their synthesis but the most common pathway exploits eration of aryl azides from aryldiazonium silica sulfates followed
thermally induced Huisgen cycloaddition reaction between azides by coupling with a terminal alkyne in the presence of copper cat-
and alkynes [211]. A recent example entails Cu(I)-catalyzed alyst without using any additional ligand (Scheme 17). Generally,
azide–alkyne 1,3-dipolar cycloaddition (CuAAC) [212,213]. The aryldiazonium salts are handled below 0 ◦ C to avoid their decom-
practicality and eco-friendliness of the CuAAC reaction has been position, but new aryldiazonium salts supported on the surface
improved by Xiong and co-workers [214] where they reported a of silica-sulfuric acid could be stored at room temperature under

O Ar O

O
DBSA
CONHNH2 N
O
2 Water, MW HN O
N 10-16 min
Ar H O

N
Ar = Ph, 2-MeOC 6 H4 , 3-MeOC6 H4 etc.
29 examples
65-96% yield

Scheme 15. MW-assisted synthesis of isoniazid (INH) analogues in water using DBSA catalyst [206].
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 79

MNP-CuBr N N
R 1X + NaN 3 + R2 R2
H 2O/PEG, MW,80 °C N
15-28 min R1
R 1 = Bn, n-But
12 examples
R 2 = Aryl, heteroaryl
89-96% yield
X = Cl, Br

Scheme 16. Copper (I) catalyzed 1,4-disubstituted 1,2,3-triazoles under MW irradiation in water [214].

R
+ - NaN3 CuSO 4, Na ascorbate, H2 O Ar
ArN2 OSO3 -SiO2 ArN 3 N N
N
H2 O, rt MW, 65 °C, 15 min
R
Ar = Aryl, heteroaryl 20 examples
70-91% yield
R = Ph, 4-MeC6 H 4, butyl

Scheme 17. MW-assisted one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles [215].

anhydrous conditions; heterogeneous reaction occurs without any OH NO2


ligand within 15 min. H2 SO4 , H 2O HO
The reaction condition was optimized via in situ generation of OH +
phenyl azides followed by addition of aqueous solution of sodium 220 °C, MW
40 min N
ascorbate and catalytic amount of CuSO4 (12 mol%) to generate the OH
Cu(I) catalyst in situ followed by reaction with phenylacetylene 77% yield
under MW irradiation. Best results were obtained for expedi-
tious assembly of 1,4-disubstituted 1,2,3-triazoles in good yields Scheme 18. Modified Skraup reaction under MW irradiation [230].
(70–91%) when the reaction was conducted at 65 ◦ C in water.
Additionally, in situ generation of aryl azides is more convenient temperature less than 200 ◦ C which deprives the formation of the
in the absence of any organic solvent and expensive material than target heterocycle.
the reported protocols [216–222]. 2,3-Dihydropyrido[2,3-d]-pyrimidin-4(1H)-ones are another
Quinoline and related fused heterocyclic derivatives are impor- important class of fused heterocycles which possess a wide
tant target structures [223] for new drug development. The range of biological properties and have been assigned as priv-
structural quinoline core has been constructed by various methods ileged structures in drug development [231–234]. Yang et al.
such as Skraup reaction [224], Doebner–Miller reaction [225], and [235] developed an efficient and good yielding aqueous MW
Friedlander reaction [226], among others. Although Skraup reaction method by using Biotage MW reactor for the synthesis of a series
entails a simple experimental procedure, it requires harsh acidic of 2,3-dihydropyrido[2,3-d]pyrimidin-4(1H)-ones via condensa-
reaction conditions, higher temperature (∼200 ◦ C), and a tedious tion of 2-amino-nicotinonitriles with carbonyl compounds in the
isolation of product. In fact, most of classical protocols for the syn- presence of non-nucleophilic, strong tertiary amine base, 1,8-
thesis of 6-hydroxyquinoline did not build the quinoline core, but diazabicyclo[5.4.0]undec-7-ene (DBU). Interestingly, the reaction
started from 6-substituted quinoline having either a chlorine atom time has been reduced to 5 min by use of a small amount of DBU
[227], methoxy group [228] or benzyl group [229]. in water and avoiding the use of other organic solvents such as
Recently, Len and co-workers [230] reported a modification of cyclohexanone, THF, methanol, CH3 CN, CH2 Cl2 , and dioxane. This
Skraup reaction by using mono-mode cavity Monowave MW reac- strategy provided good to excellent yields for all tested cyclic,
tor for the synthesis of 6-hydroxyquinoline starting from glycerol branched or linear ketones and aromatic aldehyde with varied sub-
and nitrobenzene (Scheme 18). The use of nitrobenzene as start- stituents ranging from electron-donating to electron-withdrawing
ing material provided the 77% yield of 6-hydroxyquinoline under groups (Scheme 19). The methodology was suitable for substituted
MW irradiations at 220 ◦ C in water while 4-hydroxyaniline and 2-amino-nicotinonitriles bearing electron-donating or electron-
4-nitrophenol gave poorer yields, 27%, 55%, respectively. Lower- withdrawing groups in C-5 and C-6 position with high yields. Lower
ing the temperature from 220 ◦ C to 150 ◦ C decreased the yield yields are obtained with all substituted position of 2-amino nicoti-
because the formation of acrolein from glycerol was not efficient at nonitriles due to stearic factors (Scheme 20); recyclability of the

O
CN O DBU , H 2O NH
+ R2
N NH2 R1 R2 MW, 3-5 min
N N R1
H

15 examples
R1 , R 2 = Cyclic, branched or linear ketones 82-97% yield
and aromatic aldehyde

Scheme 19. MW-assisted synthesis of pyridopyrimidinone derivatives [235].


80 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

R1 O
R1
O R2
R2 CN DBU, H 2O NH
+
MW, 3-10 min R3 N N
R3 N NH 2 H

8 examples
R 1 = H, 4-FC 6H 5 , 4-ClC 6H 5 63-97% yield
R 2 & R 3 = H, NH 2, Br, CN, cyclic

Scheme 20. MW-assisted synthesis of spiro-cyclohexane-pyridopyrimidinone derivatives [235].

catalyst up to 5 times with no substantial reduction in activity is precursors for the synthesis of antihistaminic, anti-inflammatory
another advantage. compounds [262–265], anticancer compounds [266] and antimi-
Indenoquinoline derivatives, associated with various biological crobial compound [267]. Although numerous methods have been
properties such as anti-inflammatory activity [236], act as anti- developed for assembly of these polycyclic contexts, they are gen-
tumor agents [237,238], acetylcholinesterase inhibitors [239], and erally lengthy or require deployment of stoichiometric amounts of
antimalarials [240] have garnered attention from organic chemists organometallic reagents, which largely limits their synthetic use-
[241]. Tu et al. [242] developed a MW-assisted, three component fulness [260,268–290].
condensation of aldehydes, 1,3-indanedione and enaminones using Xu et al. [291] reported the chemoselective- and regioselec-
p-toluene sulfonic acid (p-TsOH) as a catalyst in high-temperature tive aqueous MW synthesis (Biotage MW system) of tetracyclic
water with excellent yields in MW oven (Scheme 21). indole derivatives containing a seven-membered ring by a gold-
The use of p-TsOH in the aqueous synthesis of polysubstituted catalyzed Michael addition/intramolecular annulation cascade
indeno[1,2-b]quinolines was found to be superior to other acid cat- (Scheme 22); water is rarely used in transition metal catalysis
alysts such as l-proline, silica sulphuric acid, HCl, H2 SO4 , H3 PO4 , because many catalysts are highly sensitive towards moisture
and KHSO4 ; 1 equivalent p-TsOH gave better results in terms [292].
of excellent yields and MW irradiation helped reduce the reac- It has been observed that 10 mol% Au catalyst is the most effec-
tion time in comparison to conventional heating methods. It was tive for this transformation in the presence of 20 mol% trifluoro
noticed that MW irradiation reduced the reaction time to 2–7 min acetic acid (TFA) as an additive and delivers good to excellent yields,
from 2 h with enhancement in yields when compared to traditional whereas protic acids, such as PhCOOH, ClCH2 COOH and CH3 COOH
heating conditions. and other Lewis acids, such as AgSbF6 , AgOTf and Yb(OTf)3 could
Indole ring system, a privileged set of structures used in medic- not catalyze this cascade cyclization. Surprisingly, the use of water
inal chemistry, are found in many natural products [243] and had an effect on the rate and selectivity of reaction due to the ease
represent important class of therapeutic agents such as anticancer of free OH groups of interfacial water molecules to form H bonds
[244], antioxidant [245], antirheumatoidal [246], and anti-HIV with the H bonds accepting groups [293] while in presence of other
[247,248]. Consequently, researchers have focused on their solvents such as toluene, THF and DMF, the yields of the desired
synthesis [249,250] and various routes have been established for product were decreased; even 1:1 ratio of toluene and water mix-
their assembly via cyclization reaction. Generally, the cyclization ture was not effective, most likely due to the reduction in chemical
is accomplished using strong bases [251,252] or acid, or transi- interactions between reactants and catalysts.
tion metals [253,254] under harsh conditions, with few examples Azaindoles and their derivatives play an imperative role in
describing the use of MW in this type of cyclization [255,256]. various bioactive physicochemical and pharmacological proper-
Polycyclic derivatives of indole are important scaffolds and they ties [294–296]. The synthesis and functionalization, including
are found in a large number of natural products and bioactive the cyclization reactions of 2-alkynylanilines and alkynylpyrid-
molecules [257–261]. Tricyclic and tetracyclic derivatives of indole, inamines, represent a major pathway to 2-substituted and
possessing a seven-membered ring, have been used as direct 2,3-disubstituted indoles [249,250,297] and their aza-analogues

CHO
R

R
O O O
R 2 R2 p-TsOH, H 2O
MW 250 W, 2-7 min
R2
N
O R2
HN O R1
1
R
23 examples
R = 4-ClC 6H 4 , 4-NO 2C 6H 4, 4-CH 3OC6 H4, heteroaryl etc. 86-94% yields
R1 = Cyclopropyl, CH2COOH, CH3 , H, 4-CH3 C6 H4 , C 6H 5
R2 = CH 3 , H,

Scheme 21. Synthesis of poly-substituted indeno[1,2-b]quinolines using p-TsOH as catalyst in aqueous media under MW irradiation [242].
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 81

R3
NO 2 NO 2

Au catalyst, TFA
R1 + R3
N H2 O, MW, 120 °C R1 NH
H 20 min
R2
R2 CH3 28 examples
C 53-95% yield
-
R1 , R3 =
Aryl + N
SbF6 Au
R2 = Aryl, alkyl tBu
P
tBu

Au catalyst

Scheme 22. Gold-mediated one-pot domino MW synthesis protocol [291].

H 2 O, base R1 R
R1 N
MW, 200 °C
NH2 H
45-90 min
19 examples
5-98% yield
R = H, aryl, alkyl etc.
R1 = Aryl, heteroaryl

Scheme 23. MW-assisted synthesis of indole derivatives in water [303].

[298–300]. With the aim of developing cleaner and more benign Benzothiazole derivatives exhibit diverse chemical reactiv-
processes, the use of MW heating has found important applications ities and a broad spectrum of biological activities including
[4,255,301] especially for reactions that are conducted in water anti-tumour [306], anti-microbial [307], anti-malarial [308], and
and under superheated conditions [14,302]. As an example, Adri- anti-HIV activities [309,310]. Venugopala et al. [311] have
ano Carpita et al. [303] described an efficient methodology for the standardized a one-pot aqueous synthesis of 2,6-substituted
preparation of substituted indoles and azaindoles via MW-assisted benzo[d]thiazole and 2,4-substituted benzo[d]thiazole via three
cycloisomerization in water at 200 W (Scheme 23). component condensation reaction of substituted arylaldehyde,
The rate of cyclization has been enhanced by the use of catalytic 2-amino-6-chlorobenzo[d]thiazole and 6-hydroxyquinoline or 2-
amounts of inorganic salts such as KCl and NaHCO3 or by addition of naphthol under MW irradiation (320 W) (Scheme 24). The use
pyrrolidine. Assessment of the results showed that MW condition of sodium chloride (10%, w/v) increased the ionic strength and
delivered good yields of products with shorter reaction times when afforded higher yields (85–93%), but other ionic salts such as LiCl,
compared with conventional heating. NaBr, NaF, NaNO3 , Na2 SO4 , LiNO3 and Li2 SO4 have not been very
effective for this transformation.
3.2.2. Sulphur containing heterocycles
Sulfur-containing heterocycles represent an important group 3.2.3. Oxygen containing heterocycles
that are promising as physiologically active substances, dyes, and Oxygen heterocycles constitute an important class of hetero-
oil additives [304,305]. cyclic compounds in view of their wide spread occurrence and a

R2

O R1 S N
OH N
H 10% w/v NaCl in water NH
R1 + + NH2
X S 90 °C, MW, 8-10 min
R2 OH

X= H, N
X
R 1 = H, 4-OH,, 4-OCH 3, 4-NO2 , 4-CN, OH etc.
R 2 = 6-Cl, 6-Br, 4-CH3
16 examples
85-93% yield

Scheme 24. MW-assisted synthesis of 2,6- and 2,4-substituted-benzo[d]thiazole analogues [311].


82 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

O
O
O
OH [Cp*RhCl 2] 2
+ Cu(OAc)2 .H 2O, H 2O R
R H 120 °C, MW, 30 min

8 examples
R = H, Me, F, Cl, Br, I, NO2 31-85% yield

Scheme 25. Efficient synthesis of isocoumarins via MW-accelerated protocol [316].

range of biological activities [33]. They constitute versatile inter- The addition of copper acetate was essential for completion of
mediates for natural products such as sugars, vitamins, hormones, the reaction, as the acetate anion and the copper cation are critical
antibiotics and pigments [312]. for the cyclometallation step and the regeneration of the catalyst;
Isocoumarins are useful intermediates in the synthesis of a vari- Cu(BF4 )2 ·6H2 O and CuCl2 ·2H2 O were less effective.
ety of important hetero- and carbocyclic compounds, including The cationic rhodium (III) catalyst has been explored for
isocarbostyrils, isoquinolines, isochromenes, and various aromatic the oxidative coupling of acrylic acid derivative and alkyne,
compounds [313,314] besides being of interest for broad ran- providing a step-economic access to ␣-pyrones. When asym-
ging biological properties [315]. Yi and co-workers [316] reported metrical alkynes were employed, the insertion of an aryl
water as a green solvent for the efficient synthesis of isocoumarins alkyl-di-substituted alkyne occurred with remarkably high region-
and their heterocyclic analogues via MW-accelerated and Rh/Cu- selectivity with the aryl substituted carbon centre being installed
catalyzed C H/O H bond functionalization in Biotage MW oven at the 3-position. This catalytic system worked smoothly for
(Schemes 25 and 26). the oxidative annulations of the C H/N O bonds cleavage

O
O
[Cp*RhCl2 ]2 O
OH
X
+ Cu(OAc)2. H2 O, H2 O X
H 120 °C, MW, 30 min
R1
X = O, S 2 examples
R1 37-78% yield
R 1 = Ph, Me
O
O [Cp*RhCl2] 2
O
OH + Cu(OAc)2. H2 O, H2 O
120 °C, MW, 30 min
H
R1
R1
R1 = Ph, Me 2 examples
61-66% yield
O
O
[Cp*RhCl 2] 2 O
H
O
R + Cu(OAc)2. H2 O, H2 O
120 °C, MW, 30 min
H

R = Cl, Br, I, F, NO2 ,CH 3, 8 examples


29-92% yield

O
O
[Cp*RhCl 2] 2 NH
OH
N
H + Cu(OAc)2. H2 O, H2 O
120 °C, MW, 30 min
H

51% yield

Scheme 26. MW-assisted synthesis of isocoumarins/isoquinoline and their heterocyclic analogues via Rh-catalyzed oxidative C H/O H/N O bond cleavage sequence
[316].
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 83

Pd(OAC) 2/TPPTS
R OAc Nu R Nu
MW, [EMIm]BF4 /H 2 O
1.5-10 min 12 examples
0-99%

OAc
TPPTS = P [EMIm]BF 4= N N
R =Ph, H, BF4-
SO 3Na 3

Nu = NaN 3, NaSO 2Ph, HNEt2, morpholine etc.

Scheme 27. MW-assisted Tsuji–Trost reaction in water as a recyclable medium [320].

for the synthesis of 3,4-diphenylisoquinolin-1(2H)-one and 1- Recently, Varma and co-workers synthesized a magnetically
methyl-3,4-diphenylisoquinoline from N-hydroxybenzamide and separable glutathione-linked catalyst via post-synthetic function-
acetophenonoxime, respectively using water as a solvent. alization method (Scheme 29) and successfully utilized it in various
aqueous reactions such as Paal-Knorr reaction, aza-Michael addi-
3.3. Carbon heteroatom linkage tion, and the synthesis of pyrazoles under MW irradiation with
excellent yields [322]. Furthermore, the catalyst could be used for
The chemo-, regio-, and stereoselective organic synthesis for the aqueous homocoupling of arylboronic acids under MW heating
constructing the C C, C N and C O bonds has benefitted from conditions resulting in higher conversions within 45–60 min (CEM
the Tsuji–Trost reaction, a consistent and widely used method discover reactor, 300 W) (Scheme 30) [323]. After optimization, the
[317]. MAOS has been accepted as a standard method for these substrate scope was extended to a variety of arylboronic acids that
types of reactions in terms of reducing the reaction time by several delivered good to excellent yields of products using 0.1 M aqueous
orders of magnitude and increasing yields of product compared to NaOH solution within 45 min at 120 ◦ C.
conventional methods [27,318,319]. Liang and co-workers [320] Accommodating atom-economic concept and minimum work-
introduced a MW-assisted allylic substitution with various carbon up effort, the tandem-, cascade-, or domino-reactions have a
and heteronucleophiles catalyzed by palladium(0)-TPPTS in water significant impact on the synthesis of fine chemicals and pharma-
and ionic liquid ([EMIm]BF4 ) medium at 400 W (Scheme 27). ceutical intermediates. A number of tandem reactions [324,325]
The reaction of cinnamyl acetate with sodium azide employing homogeneous bimetallic complexes as catalysts have
has been conducted in ionic liquid, ([EMIm]BF4 ), in the been reported in the literature. However, apart from complicated
presence of a catalytic amount of Pd(OAc)2 and 3,3 ,3 - catalyst compatibility with residual materials in solution, these
phosphanetriyltris(benzenesulfonic acid) trisodium salt (TPPTS), homogeneous bimetallic catalysts are often difficult to recycle.
but the reaction did not proceed. By contrast, the use of the mixture Liu et al. [326] developed a mesoporous silica-supported
of [EMIm]BF4 /H2 O (1:1) instead of [EMIm]BF4 alone was helpful bifunctional Ti-Ru-SBA-15 catalyst using organometallic com-
for the formation of desired product in good yield; water plays plexes RuCl2 (PPh3 )3 and Ti(OiPr)4 onto PPh2 -SBA-15, which has
seemingly an important role due to good solubility of Pd(OAc)2 been utilized for the aqueous tandem allylation-isomerization
and TPPTS. reaction of benzaldehyde under MW irradiation (Sineo MW reac-
Cadierno et al. [321] reported an aqueous green method for the tor, 700 W). The catalyst could be recycled five times without loss
Meyer–Schuster isomerization of propargylic aryl carbinols into of selectivity and activity (Scheme 31).
␣,␤-unsaturated carbonyl compounds using catalytic amounts of Mesoporous materials have been ideal supports for the immo-
InCl3 under MW irradiation (CEM discover synthesizer, 300 W) bilization of catalysts and have displayed some unique salient
(Scheme 28). features [327–329] as these mesoporous silica-supported catalysts
The most significant finding has been the isomerization of sec- possess a high surface area and ordered mesopore channels, which
ondary terminal alkynols and the generation of enals in all cases are beneficial for the enhancement of loading amounts and disper-
as the thermodynamically remarkable stereoselectivity provided sion of catalytically active sites.
more stable E isomer. This method was not limited to the aque- Ullmann-type C N coupling reaction is an important approach
ous isomerization process of propargylic aryl carbinols bearing a to assemble nitrogen-containing heterocycles, which are widely
terminal C C bond, but also efficiently generated the correspond- employed as building blocks for the synthesis of pharmaceutical
ing enones. and natural products [330,331]. However, the use of copper-
catalyzed reaction often requires high temperature (generally
140 ◦ C or higher), longer reaction times, and strong bases [332]
HO H O in organic solvents such as DMF [333,334], DMSO [335,336], NMP
InCl3 (1 mol%) [337,338], and CH3 CN [339,340], but water has been recently
R2 R3
R1 R3 employed as a solvent [341–343]. Li et al. [344] described effi-
R1 MW, H 2O,160 oC
R2 cient aqueous C N bond forming reactions catalyzed by copper (I)
5-360 min
16 examples iodide with calix[4]arene supported amino acid ionic liquid cat-
81-95% yield alyst which can be used as both the ligand and the surfactant in
R1 & R 2 = Aryl, heteroaryl
the Ullmann C N coupling reaction (Scheme 32). Calix[4]arene
R3 = H, Me, Ph
[Emim][Pro] (Fig. 8) has been synthesized [345] via benzylation
Scheme 28. MW-assisted Meyer–Schuster isomerization of terminal propargylic
of p-t-butyl-25,27-bis-o-(2-bromo-ethoxy) calix[4]arene followed
aryl carbinols/internal alkynols [321]. by treatment with 10 equiv. of 1-methyl-1H-imidazole and finally
84 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

O
HO O
NH2
HO
O
OH HN
O O OH
O NH
HN
O N O
S S NH2
NH H O
O Fe 3O4
+ HS Sonication
NH
Fe 3O4 O OH
RT, H 2 O
S
NH2
O
OH HN
O NH OH
Glutathione (reduced) H 2N O
O
O
OH

Scheme 29. Synthesis of magnetically separable glutathione-based catalyst [322].

OH R
B Nano-Fe3 O4 -Glutathione
OH
0.1M NaOH, H2 O, MW
R 45-60 min
R
R = Cl, OH, Me, OMe, MeCO, CF3 , heteroaryl 12 examples
59-94% conversion

Scheme 30. MW-assisted aqueous homocoupling of substituted arylboronic acids using nano-magnetite glutathione as catalyst [323].

an anion exchange reaction with 201 × 7 styrene-divinylbenzene 3.4. Synthesis of amides


(DVB) which was neutralized with l-proline. The catalyst was
successfully utilized for the coupling of a variety of nitrogen Peptides play an important role in medicinal chemistry lead-
heterocycles under MW conditions (CEM monomode reactor) ing to the discovery of a number of drugs [346–348]. The amide
within 10 min with good to excellent yields, while conventional group is an important functional group with well-known chemistry
heating required 48 h for this transformation. and comprises an integral part of numerous bioactive molecules

OH OH O
O Catalyst
Sn(CH 2CH=CH 2) 4
H
MW, H 2O, 100 oC
10 min
2 3 4
1
99% conversion
96% selectivity

Scheme 31. MW-assisted tandem allylation-isomerization reaction of benzaldehyde [326].

R1
X R2 10 mol ligand, CuI (10 mol%)
R1 + HN
R3
K2 CO 3, H2 O, MW, 100-140 °C R2
N
10 min
R3
R1 = CHO, Me, NH 2, COOEt, NO2 , Heteroaryl
16 examples
R2 & R3 = imidazole, indole, benzotriazole, pyrazole etc. 73-98% yield

Scheme 32. MW-assisted C N coupling reaction [344].


A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 85

O
O O R
H H 2N TBTU, HOBt, DIEA H
N O
Fmoc/Boc
N
OH + R
O
MW, H2 O, 60 °C Fmoc/Boc N
H
R1 30 min R1 O
n n= 1-4

28 examples
R1 = Fmoc/Boc protected amino acid 57-90% yield
R= metyl ester of amino acid
Scheme 33. MW-assisted amidation reaction [358].

Allam et al. [359] reported a convenient and effective direct


one-pot route to primary amides from aldehydes using Sc(OTf)3 as
catalyst under MW heating (300 W); the efficient and rapid reaction
provided excellent yields in 15–35 min in the presence of Na2 CO3
(Scheme 34).

O O O O 3.5. C H activations
Bn Bn
+
N Although regioselective functionalization of arenes via C H
+ N activation (mainly by rhodium and palladium catalysts) is well doc-
N
umented [360–365], the ruthenium-based catalysts have shown
N
excellent activity both in terms of efficiency and regioselectivity
N COO - [366,367]. However, the ruthenium catalyzed processes proceed
N COO - H at high temperature and, hence, require the use of higher boiling
H organic solvents, typically toluene or NMP.
Adrio et al. [368] have reported one-pot direct aqueous C H ary-
Fig. 8. Structure of calix[4]arene [Emim][Pro].
lation of arenes catalyzed by RuCl3 ·nH2 O–NaOAc in the presence of
Zn (Scheme 35); the reaction has been accelerated by the use of MW
irradiation and can be scaled up to a multi-gram scale with excellent
[349–354]. Amides have been often obtained by the acid or base yields. The selective high yield ortho monoarylation of 2-phenyl
catalyzed hydration of nitriles [355–357]. However, under these pyridine with arylchloride and heteroarylchloride has been accom-
harsh conditions, various by-products, such as carboxylic acids, plished in 1 h under these conditions while conventional heating
are formed by hydrolysis of the amides or nitriles and sensi- required 20 h for this transformation.
tive functional groups present in such molecules cannot survive
such conditions. Solution phase peptide synthesis has been known 3.6. Synthesis of urea derivatives
in various solvents, but the application of water as a reaction
medium has not been explored. Recently, Jain and co-workers [358] N-Monosubstituted ureas are an important class of organic
have developed MW-assisted aqueous phase peptide synthesis of compounds occurring both, as natural products [369–371] and as
a wide-variety of structurally diverse dipeptides, tripeptides and synthetic components [372]. Their synthesis is of great interest
tetrapeptides consisting of Fmoc and Boc-protected amino acids owing to their broad applications in pharmaceutical and agro-
using CEM Discover reactor at 40 W. The synthesis showed that chemical industry due to antidiabetic and herbicidal properties,
neat water can be the medium of choice for solution phase peptide respectively [373–375]. Numerous procedures are available for the
synthesis under MW irradiation using N,N,N ,N -tetramethyl-o- preparation of symmetrical and unsymmetrical di- or trisubstituted
(benzotriazol-1-yl)uronium tetrafluoroborate (TBTU) as a coupling ureas by using reaction of primary amines with toxic phosgene or
reagent and hydroxybenzotriazole HOBt as an auxiliary nucleophile its hazardous derivatives [376,377], or via the catalytic insertion of
(Scheme 33). The method has proven useful for unprotected amino CO or CO2 into amino compounds, in organic solvents at elevated
acids on the reactive side chain and the selectivity towards the pressure and temperature [369,372,378–383].
racemization-free high yield peptide synthesis where purity has Luca et al. [384] used a self-tuning single mode CEM Dis-
been maintained. cover focused synthesizer and described a high-yielding aqueous

O (10 mol%) Sc(OTf)3 O


R H + NH2 OH.HCl
MW, Na2 CO 3, H 2 O R NH2
135°C, 15-35 min
R= aryl, allyl, alkyl 18 examples
82-94% yield
Scheme 34. Sc(OTf)3 -catalyzed MW-assisted synthesis of primary amides [359].
86 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

N
Ar-Cl N N
Ru, NaOAc, Zn
+ Or
Het-X
Water, 140 °C, MW Ar(Het) + (Het)Ar Ar(Het)
1h

a b

Cl R Cl N
Ar = Cl N

R = H, p-CH3 , p-CN, p-OCH3 , p-OH,


m-N(CH3 )2 , o-NH 2, heteroaryl

Scheme 35. MW-assisted functionalization of 2-phenylpyridine with aryl chlorides and heteroaryl chlorides [368].

MW methodology for the preparation of N-monosubstituted ureas chelating ligands such as 2,2 -bis(diphenylphosphino)-1,1 -
via reaction between potassium cyanate and an array of amines binaphthyl (BINAP), 2,2 -p-tolyl-phosphino-1,1 -binaphthyl
(Scheme 36). The reaction was not limited for aliphatic, N- (Tol-BINAP), 1,1 -bis(diphenylphosphanyl) ferrocene (DPPF),
substituted hydrazines and anilines but was also suitable for amino tris(dibenzylideneacetone)dipalladium (Pd2 (dba)3 ), or phosphine-
acids as they have good solubility in water and no acid was required based ligands [397–404].
for improving the solubility. Velmathi et al. [405] demonstrated the ligand-free Pd-catalyzed
aqueous C S coupling reactions under MW heating (Scheme 37);
3.7. Miscellaneous reactions TBAB and NaF were required to catalyze this transformation, but
the strategy could not be used for chloro-substrate.
Sulfides and their derivatives are attractive building blocks The utilization of terminal alkynes in cycloaddition
in the synthesis of biologically active compounds [385–387] [215,406–411] and coupling reactions [412–418] has stimulated a
and their formation has been generally carried out by the con- significant level of interest for chemists due to the pharmaceuticals,
densation of activated alkyl halides with alkali-metal thiolates and agrochemical properties of the ensuing products [419–424].
[388–390] or via the reduction of sulfones or sulfoxides using Huang and co-workers [425] reported an efficient MW-assisted
strong reducing agents such as DIBAL-H or LiAlH4 [332,391]. A copper(I) oxide (Cu2 O) catalyzed, three-component synthesis of
growing number of synthetic methodologies deploy transition arylaminomethyl acetylenes via the coupling of aromatic boronic
metals such as Fe [392], Co [393], Ni [394], and Cu [395,396] acids, ammonia, and propargyl halides in water (Scheme 38).
for C S bond formation often promoted by the addition of Shorter reaction times and higher product yields were principal

O
H2 O, H +
X X
R NH 2 + KOCN
80 °C, MW, 1h R N NH 2
H
R = Alkyl, aryl 12 examples
X = CH 2, NH 85-88% yield

O
NH2 H2 O, H +
R + KOCN
80 °C, MW, 1h
R
N NH 2
H
R= Aryl 3 examples
75-87% yield

R O
R 80 °C, MW, 1h
HOOC NH2
+ KOCN
H2 O
HOOC N
H
NH 2

7 examples
R = Alkyl, aryl, cyclic etc. 68-90% yield

Scheme 36. Synthesis of N-monosubstituted ureas by MW irradiation [384].


A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 87

R1 R2

R1 R2 HS Pd(OAc)2 , NaF, TBAB


S
+ H 2O, MW, 150 °C, 20 min
X R3

X = I, Br, Cl
R 1 = H, COMe, OMe, NH2 , Ph R3
R 2 = H, OMe 16 examples
R 3 = H, NH2 , Me 65-89% yield

Scheme 37. MW-assisted Pd-catalyzed coupling reaction of aryl halides with aryl thiols [405].

B(OH) 2
K 2CO3 , Cu2O R1
+ + NH 3.H2 O MW, H 2O, 10 min NH
R1 X
5W

11 examples
71-87% yield
R 1 = H, OCH3 , Cl, Br, I
X= Br, Cl
Scheme 38. MW-assisted synthesis of arylaminomethyl acetylenes [425].

advantages that render this procedure a greener alternative to equivalent of NaCl (Scheme 39). The scope of this reaction has
conventional chemical synthesis. The reaction was favoured in been extended to a variety of less reactive malonate derivatives
water while other solvents such as DMSO and DMF afforded poorer (Scheme 40) wherein the addition of 1 equivalent of lithium sulfate
yields and no product was detected when 1,2-dichloroethane or increases the yields, as it combines the best chelating properties of
toluene were used as solvents. the cation and an optimum pH profile of the anion. This methodol-
Activated esters, which include substrates such as malonates, ␤- ogy realizes a useful confluence of green solvent, short conversion
ketoesters, and ␣-cyanoesters, are important precursors in organic times, and obviating the use of DMSO solvent.
synthesis [426]. The Krapcho decarboxylation has been a con- Luque and co-workers have reported Pd NPs supported on a
venient protocol for the removal of an ester moiety from an variety of mesoporous carbon materials/beads for both, the aque-
electron-deficient carbon, a task conventionally accomplished by ous oxidation and hydrogenation reactions under MW irradiation
a cyanide-mediated process. Lately, this could be achieved by wet [430]. Palladium NPs are prepared via organometallic approach
DMSO as solvent without the need for cyanide [427,428]. Mason using either triphenylphosphine (TPP) or trioctylphosphine (TOP)
et al. [429] reported a high yielding aqueous process within 5 min as stabilizing ligands [431]. The oxidation of benzyl alcohol to
under the Krückert’s conditions at 185 ◦ C without using DMSO. benzaldehyde (99% selectivity) was realized by using Pd(TOP)/MB-
Interestingly, the yield could be increased by the addition of 1.2 H2 O2 (Pd content 2.58 wt%) within 3 min under MW using CEM

O O
NaCl, H 2O,
MW, 185 °C, 5 min O O
O O
86% yield

Scheme 39. MW-assisted decarboxylation of ethyl 2-acetyl-3-oxo-6-phenylhexanoate [429].

O
O O Li2 SO4

H 2O, 30 min, 210 °C O


O O
MW R
R
7 examples
R= Ph, CH2 Ph, CH 2CH2 Ph, CH2 COPh,
34-87% yield
CH2 CH2 CO 2Et, CH 2 CH 2CN,

Scheme 40. MW-assisted decarboxylation of less reactive malonate derivatives [429].


88 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

O
OH Pd catalyst O
Water:H 2O 2, MW + OH
3 min

H Catalyst
O 1. Decarbonylation O
O 2. Hydrogenation
30- 35 min

Scheme 41. MW-assisted oxidation and hydrogenation reaction with Pd catalyst [430].

BF4- BF4-
N+ N+
SO3 H SO3 H

I L- 1 I L- 2

CH3 SO3 -
CH3 SO3 - N+
N+ SO3 H
SO3 H
IL-4
IL-3

Fig. 9. Bronsted acidic R T-ILs investigated in C5 dehydration.

discover reactor operating at 300 W in aqueous H2 O2 while the reflux conditions in a neutral aqueous solution and delivered high
two-step decarbonylation and subsequent hydrogenation of fur- benzaldehyde selectivity.
fural was accomplished in the mixture of water: formic acid (1:1) Furfural and its derivatives have been making headlines in the
as solvent and a hydrogenation source, respectively; >90% conver- production of jet and diesel fuel range alkanes [434–436] and other
sion and 80% selectivity to THF was achieved in 30–35 min without useful platform chemicals such as furfuryl alcohol and tetrahydro-
any contamination of furfuryl alcohol by 2-MTHF and related com- furan [437], including methyl-tetrahydrofuran and liquid alkanes
pounds as by products (Scheme 41). [436,438]. Conventionally, they are obtained [439] using corro-
Chen and co-workers [432] reported MW-assisted synthesis of sive, toxic concentrated sulphuric acid and require longer reaction
carbon nanotube (CNT) supported Pt-based bimetallic nanopar- times which lead to extensive side reactions including the forma-
ticles (PtRu/CNT and PtSn/CNT) and examined their catalytic tion of humins. Juan Carlos Serrano-Ruiz et al. [440] reported an
performance in the aerobic oxidation of benzyl alcohol under efficient MW-assisted furfural production from a lignocellulosic
base-free aqueous solutions. These catalysts were synthesized by waste-derived biorefinery syrup enriched C5 oligomers via two step
alloying Pt with Ru or Sn via MW-assisted polyol reduction (MAPR) hydrolysis, followed by subsequent dehydration of C5 sugars in
method [433] using acid-functionalized CNTs, and appropriate aqueous media catalyzed by small amounts of SO3 H-functionalised
amount of metal precursor aqueous solution, drying at 100 ◦ C in ionic liquids (Fig. 9). Interestingly, furfural was obtained in 30%
a vacuum followed by sonication with EG, and finally heating in yield at 150 ◦ C within 2 h under MW irradiation which increased to
MW reactor at 160 ◦ C for 2 min. The catalytic aerobic oxidation of 45% after 4 h; increasing the temperature to 180 ◦ C did not improve
benzyl alcohol using molecular O2 was conducted at 80 ◦ C under the product yield (Scheme 42).

OH OH
HO O OH
3 H 2O
H 2O
O
O O OH
HO HO OH O
O
Hydrolysis HO O Dehydration O
HO OH
O OH

O
O

Scheme 42. Reaction scheme for the conversion of C5 oligomers into furfural [440].
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 89

O
Na2 WO4 , TBAHS
R OH R OH
H 2O 2, MW, 20 min
4 examples
60-84% yield
R = Aliphatic primary, benzyl

OH O
Na2 WO4 , TBAHS R1 R2
R1 R2
H 2O2 , MW, 10 min
5 examples
77-94% yield

R1 , R 2 = Aliphati, cyclic, aromatic

Scheme 43. MW-assisted oxidation of alcohols with hydrogen peroxide [441].

Fig. 10. Schematic illustration of MO degradation mechanism during


Bogdal et al. [441] reported MW-induced modification of Noy-
MW/catalyst/H2 O2 combined process.
ori’s procedure for the oxidation of primary alcohols to carboxylic
Reprinted with permission from Ref. [442]. Copyright 2009 American Chemical Soci-
acids and secondary alcohols to ketones using 30% aqueous H2 O2 ety [442].
and sodium tungstate with tetrabutylammonium hydrogen sul-
fate (TBAHS) as a phase-transfer catalyst (Scheme 43). The reaction
was performed in a monomode MW reactor and best results were irradiation, catalyst, and H2 O2 . The oxygen ions derived from sur-
obtained at 90 ◦ C and 100 ◦ C for primary and secondary alcohols face chemisorbed oxygen and lattice oxygen of CuO/CeO2 could
within 20 min and 10 min, respectively. effectively react with the adsorbed MO molecules on the catalyst
Xu and co-workers synthesized CuO/CeO2 catalysts by surface. The lost lattice oxygen dissolved in water and added H2 O2
coprecipitation method using mixture of Ce(NO3 )3 ·6H2 O and could partly transform into • OH on the surface of CuO/CeO2 catalyst
Cu(NO3 )2 ·3H2 O as starting material and their performance was with the assistance of MW energy, thus improving the degradation
evaluated for the degradation of methyl orange (MO) in aqueous efficiency.
medium by combining MW irradiation in the absence and pres- In the aqueous solid-phase peptide synthesis (SPPS), researchers
ence of H2 O2 [442]. MW-enhanced catalytic degradation of MO have focused on developing novel hydrophilic N-protecting groups
in the absence of H2 O2 was examined to investigate the correla- for amino acids in order to improve their water solubility as
tion between calcination temperature and catalytic activity of the the conventional protecting groups deployed such as Boc-, and
CuO/CeO2 catalysts. The roles of MW irradiation, CuO/CeO2 , and Fmoc-groups are hydrophobic [443]. Hojo et al. [444] reported the
H2 O2 in the combined degradation process were examined; MO water-based MW-assisted solid-phase synthesis using Boc-amino
degradation efficiency increases from 57.7 to 85.2% with increasing acid nanoparticles (Fig. 11) and used that for the syntheses of Leu-
H2 O2 concentration from 0 to 16 mmol/L (Fig. 10). enkephalin, Tyr-Gly-Gly-Phe-Leu-OH, and difficult sequence model
The superior MO degradation performance in this process was peptide, Val-Ala-Val-Ala-Gly-OH in high yield and purity. The tert-
ascribed to a synergistic, rather than an additive, effect of MW butyloxycarbonyl protection group was identified [445] to be the

Fig. 11. Aqueous microwave (MW)-assisted solid-phase synthesis using Boc-amino acid nanoparticles.
Adapted from Ref. [444].
90 A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94

Fig. 12. Binding modes of carboxylic acid in the frameworks of (a) HKUST-1, (b) CHB and (c) ZHB.
Reprinted with permission from Ref. [446]. Copyright 2014, The Royal Society of Chemistry.

most suitable for industrial and sustainable synthesis, because only laboratories to incorporate MW-expedited synthesis into their drug
gases are generated, without any other by-products produced dur- discovery efforts.
ing de-protection. Recently, there has been concerted effort on continuous flow
MW chemistry and its applications in sustainable organic synthesis.
Additionally, MW technology has ideal fusion with nanomateri-
3.8. MW-assisted synthesis of coordination polymers als/nanocatalysts, especially recyclable magnetic nanocatalysts, for
the synthesis of important drug intermediates and organic transfor-
Park and co-workers [446] described the high yield syn- mations, which can replace traditional catalysts, thus blurring the
thesis of a carboxyl-containing coordination polymer catalyst distinction between homogeneous and heterogeneous catalysis.
{Cu(Hip)2 (Bpy)}n (CHB) in aqueous medium using MW energy Modern MW-assisted synthesis provides unique capability to
(100 W) at 100 ◦ C within 6 min while a comparable hydrothermal cool the reaction vessel while simultaneously pumping more MW
synthesis required two days at 125 ◦ C [447]. The copper centre of energy into a chemical reaction; a greater MW power input results
CHB was expected to function synergistically with the hydrogen in substantially enhanced chemical reactions while maintaining a
bonding capable COOH and OH groups in promoting catalysis. CHB desired bulk temperature. This is particularly useful for chemical
and HKUST-1 were synthesized from a cupric nitrate precursor and reactions with large activation energies. Lately, MW technology has
isostructural tripodal ligands, with totally different structures and been employed for the dielectric heating of fluids in microfluidic
geometries (Fig. 12). The exact zinc analogue of CHB in its con- devices, synthesis of well-defined, uniformly small-sized nano-
stituents, viz., ZHB (ZnHipBpy) was non-isostructural with CHB. materials and their applications not only for catalysis, but for
Additionally, the avoidance of high-boiling organic solvents such MW-enhanced catalytic degradation of dyes.
as DMF, N,N-Diethylformamide (DEF) etc. for material synthesis, Microwave technology has also a great potential for utility in
the use of aqueous medium and shorter reaction time are the microfluidic devises, for precise use in rapid thermocycling pur-
main advantageous of the present approach. The synthesized cat- poses that will lead to new applications for selective heating in a
alyst showed excellent selectivity of 99.9% and 89.2% yield for allyl microfluidic environment. The recently designed MW flow reac-
glycidyl carbonate (AGC) in the presence of the quaternary ammo- tors could be used for scalable hazardous reactions using toxic or
nium salt co-catalyst TBAB under ambient temperature at 80 ◦ C. reactive reagents in a continuous flow mode from milligram and
The catalyst could be successfully recycled up to four times without kilogram scale.
the degradation of any covalent/coordinate linkages of the catalyst In the light of aforementioned comments, it is recognizable that
framework. fusion of metal catalysis in aqueous media and its tuning with MW
selective heating will make substantial contributions in develop-
ment of sustainable pathways.
4. Conclusions and future scope

This review focuses on greener contexts and envisages the Disclaimer


future directions on the development of robust synthetic meth-
ods under MW-assisted catalytic protocols in aqueous media. In The U.S. Environmental Protection Agency (EPA), through its
spite of known shortcomings delineated in the introduction sec- Office of Research and Development, partially funded and collabo-
tion about the depth of penetration and limitations on up scaling rated in, the research described herein. It has been subjected to the
of the MW reactions [46], MW heating equipment is an impor- Agency’s administrative review and has been approved for external
tant tool for the controlled bulk heating of reactions. The MW publication. Any opinions expressed in this paper are those of the
approach enables expeditious chemical transformations and offers author(s) and do not necessarily reflect the views of the Agency,
the possibility of high throughput library generation of medicinal therefore, no official endorsement should be inferred. Any men-
compounds [13]. The presented examples indicate that the fusion tion of trade names or commercial products does not constitute
of microwave/catalysis strategy enables an enhanced scope in the endorsement or recommendation for use.
future development of clean and sustainable organic chemistry
because of successful combination of MW absorbing metal catal-
ysis in water as a polar solvent. The salient features of the MW Acknowledgment
heating technology include rapid volumetric heating, higher chem-
ical reaction rate and selectivity, shorter reaction time, and higher The authors gratefully acknowledge the support by the project
product yields as compared to conventional heating. These are the LO1305 of the Ministry of Education, Youth and Sports of the Czech
principal reasons for many pharmaceutical companies and research Republic.
A.K. Rathi et al. / Coordination Chemistry Reviews 291 (2015) 68–94 91

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