DESIGN OF HETEROGENOUS CATALYSIS IN ORGANIC SYNTHESIS

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Mhadhbi et al., J. Mar. Chim. Heterocycl., 2020, Volume 19, Issue 3, Page 99-118

Journal Marocain de Chimie Hétérocyclique Moroccan Journal of Heterocyclic Chemistry

ISSN : 2605-5996

J. Mar. Chim. Heterocycl., 2020, Volume 19, Issue 3, Page 99-118

DESIGN OF HETEROGENOUS CATALYSIS IN ORGANIC

SYNTHESIS

Oumaima Mhadhbi & Néji Besbes

Group of Green and Applied Organic Chemistry, Laboratory of Composite Materials and

Clay Minerals, National Center for Research in Materials Science, Technopole of Borj

Cedria, 8027, Soliman, Tunisia.

E-mail : [email protected] ; [email protected]

Oumaima Mhadhbi is cuurently a PhD Student at the Faculty of Sciences

of Tunis. After styding Physics and Chemistry and obtaining a master degree

in organic chemistry she joined the group of Prof. Besbes in 2019 for PhD

position. 1 publication, 4 communications (2 oral and 2 posters).

Néji Besbes born June 1, 1957 in Monastir - Tunisia. Professor at the

National Center for Research in Materials Science, Specialty: Synthesis,

Reactivity and Chemical Kinetics of Heterocycles by Catalysts in

Homogeneous and Heterogeneous Media, Application of Theoretical Studies

in Organic Synthesis. Professor at the National Center for Research in

Materials Science, Founder and President of STCHA. President 2

Congresses, Co-President 3 Congresses. Supervision 9 Masters, 8

Doctorates, 3 Univeristy Habilitations. Authors 30 Books, 71 Articles, 35

Proceedings, 42 Conferences, 42 Orals, 75 Posters. Jury Member 7

University Authorizations, 43 Doctorates, 12 Masters.

Abstract

Heterogeneous catalysts is a key tool for the development of efficient, economically

interesting and ecologically compatible synthesis processes. Indeed, heterogeneous catalysts

have appeared as a green alternative including natural aluminosilicates such as clay mineral

and zeolite to conventional homogeneous catalysts, because they are easily separated by

simple filtration and can be recovered and reused. In this review, we critically discuss the

mailto:[email protected]

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structural features of these various types of solid catalysts and their applications in organic

synthesis.

Keywords : Clay mineral, Heterogenous catalysis, Homogenous catalysis, Green chemistry,

Zeolite.

Introduction

Heterogeneous catalysis plays a key role in the production of more than 80% of chemicals,

ahead of homogeneous catalysts (17%) and biocatalysts (3%) [1]. Currently, are widely used

in industrial applications due to the easy separation especially in petrochemicals

(hydrogenation and dehydrogenation reactions), in petroleum refining (catalytic reforming,

cracking and isomerization), in the mineral industry (synthesis of ammonia and production of

hydrogen) and again in polymer chemistry (polymerization of ethylene, synthesis of

methanol, dehydration) [2,3]. Heterogeneous catalysis is also finding new applications in

emerging areas such as fuel cells [4,5], green chemistry [6], nanotechnology [7] and

biorefining/biotechnology [8].

In heterogeneous catalysis, the reaction medium has two different phases, the catalyst of

which can store liquid ions, even solids from enzymatic catalysis. This type of reaction is

essentially governed by the specific surface known as the "active surface" of the catalyst,

using chemical surface concepts such as adsorption and desorption, but also porosity. A

catalyst is more effective the larger its active surface.

However, the catalytic cycle has five consecutive stages which can influence the overall rate

of chemical transformation [9,10] :

1- Diffusion of the reagents towards the active surface of the catalyst,

2- Adsorption of reagents on the catalyst surface,

3- Chemical transformation of the adsorbed species,

4- Desorption of the products from the surface of the catalyst,

5- Diffusion of the products formed outside the pores of the catalyst and evacuation of the

reaction zone.

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Figure 1. Description of the catalytic act in heterogeneous catalysis.

Traditional acids and bases have several disadvantageous properties, they are often dangerous,

flammable, corrosive or toxic, the treatment of the reaction mixture is often tedious,

producing large quantities of waste water, and the catalyst often decomposes during the

treatment. These compounds or even their preparation are often harmful to the environment.

Consequently, in recent decades, the development of heterogeneous catalytic methods has

become one of the main synthesis objectives. Heterogeneous catalysts can eliminate the

problems resulting from the use of homogeneous catalyst; they can be filtered from the

reaction mixture, thus simplifying the treatment procedure, reducing energy costs and

reducing the operating time and the amount of waste water. These are generally non-

corrosive, non-toxic and often reusable or simply recyclable materials, and in some cases,

they can induce considerable regional stereoselectivity [11-14]. Consequently, various

heterogeneous catalysts such as zeolites [15-17], clay minerals [18-20], mesoporous materials

[21,22], activated carbon [23,24], metal oxides and phosphates [25,26], exchange resins

[27,28], ionic liquids [29,30], and metal-organic frameworks (MOFs) [31,32] have shown

excellent catalytic activity in organic synthesis.

1. Clay minerals

Clay and clay minerals, either as they are or after modification, are known as materials of the

twenty-first century because they are abundant, inexpensive and environmentally friendly.

Clay is a raw material used for a long time in the various activities of human life. The word

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clay comes from the Latin Argilla. This word is derived from the Greek argillos, the root of

which, argos, means "of dazzling whiteness". The term "clay" is generally used to designate

the various sedimentary rocks. These rocks have a high mineral content. A clay was born

from the weathering of sedimentary rocks. Depending on their composition and concentration

of minerals, different clays have different structures and properties [33].

1.1. Clay formation

Clays are born from the ground in constant movement. They appear according to three main

training processes [33].

The 1st process : relates to the simple decomposition of rocks by erosion. The

phenomena characterizing soil erosion are numerous: Rain, wind, frost and waves.

The second process : is called neoformation or anthigenesis. This correspond to the

formation of the mineral. The substances transported by the soil water will combine to

form a mineral structure.

The 3rd process : corresponds to the transformation of minerals. The latter evolve by

degradation (loss of soil balance) or worsening (accumulation of sediment in a river)

of clay minerals.

1.2. Crystallochemistry of clays

Clays are hydrated alumina silicates of a sheet structure called "phyllosilicates" which are

negatively charged and responsible for its physicochemical properties such as swelling,

plasticity and adsorption properties [34]. The crystallochemical structure of clays results

essentially from the assembly of two basic sheets. Each sheet is made up of a combination of

tetrahedral and octahedral planar layers [35-37].

A tetrahedral layer (coordination 4) : each tetrahedron TO4 is composed of a central

atom T coordinated with four oxygen atoms. The cations likely to occupy the tetrahedron

centers are : Si4 +

, Al3 +

and Fe3+

.

An octahedral layer (coordination 6) : each octahedron consists of a cation M

surrounded by 6 ligands (O, OH). The octahedral layer is thinner than the tetrahedral layer.

The octahedral cations are often Al3+

, Fe3+

, Mg2+

and Fe2+

. When two out of three cavities

of the octahedral layer are occupied by a trivalent metal ion, the structure is called

dioctahedral. When all of the octahedral cavities are occupied by bivalent metal ions, the

structure is said to be trioctahedral.

Furthermore, the replacement of certain constitutive cations of the crystal lattice by others of

lower valence (replacement of an Si4+

ion by an Al3+

ion in the tetrahedral layer or of an Al3+

ion by Mg2+

in the octahedral layer) creates what is called isomorphic substitutions. This

creates a charge deficit at the level of the sheets which thus acquire a negative charge.

Compensating cations are then placed in the interfoliar space to fill this load deficit.

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Figure 2. Clay mineral structure.

1.3. Classification of clay minerals

Clay minerals are classified into four groups, depending on the thickness and structure of the

sheet [38,39] :

7 Å clay mineral : In this class, the sheet consists of a tetrahedral layer and an

octahedral layer. It is named T / O or type 1/1, its thickness is around 7Å. The types of clay

minerals belonging to this family are kaolinite and the neighboring families: dickite, nacrite

and halloysite which are differentiated by the crystal structure. The interfoliar space of this

class is empty. The sheets are linked directly to each other by hydroxyl type bonds.

10 Å clay mineral : These minerals have an octahedral layer framed by two

tetrahedral layers. This sheet is named T / O / T or type 2/1. Depending on the content of the

interfoliar space, the basal distance varies from 9.4 to 15 Å. In this class, we find by way of

example smectites and neighboring families: micas, vermiculites and illites.

14 Å clay mineral : These minerals are T / O / T / O or type 2/1/1 which have an

octahedral layer framed by two tetrahedral layers. The interfoliar space is occupied by a layer

of octahedra (layer of brucite, Mg (OH), with substitution Mg-Al). Take, for example,

chlorites.

Figure 3. 7 Å clay mineral. Figure 4. 10 Å clay mineral.

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Figure 5. 14 Å clay mineral.

Interstratified clay minerals: One of the most interesting discoveries in recent

years on the mineralogy of clay concerns that of interstratified clay minerals. These

minerals result from the alternating stacking of two or more sheets of different natures.

Depending on whether this alternation is regular or not, we speak of regular or irregular

interstrate. The thickness of the sheet is variable.

Figure 6. Crystal structure of interstratified clay.

1.4. Clay groups

• Kaolinite : Al2 Si2 O5 (OH) 4

The kaolinite sheet is always neutral and dioctahedral. The composition of this clay is (Si2)

(Al2) O5 (OH)4 per half-mesh. Morphologically, kaolinite is in the form of hexagonal particles

made up of stacks of sheets. The low exchange capacity of kaolinites is due to amphoteric

surface sites [40].

• Illite : (K H3O) (Al Mg Fe)2 (Si Al)4 O10 (OH)2 (H2O)

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The illite belongs to the 2/1 family. The sheets have a negative overall charge, higher than

that of smectites. This charge is compensated by potassium ions K+. The presence of

potassium, an anhydrous cation, in the interfoliar space ensures a rigidity of the bond between

the sheets which prevents the swelling of these minerals in the presence of water. These

potassium ions are difficult to exchange which is the cause of low CEC [40].

• Chlorites : (Mg Al Fe)6 [(Si Al)4 O10] (OH)8

Chlorites belong to the 2/1/1 family. They may be present in small quantities in the soil. The

negative charge is compensated by a layer of octahedra based on magnesium hydroxide

(brucite Mg(OH)6) or aluminum hydroxide (gibbsite Al2 (OH)6) in the interfoliar space [40].

• Smectites : (OH)4 Si8 (Al10 / 3 Mg2 / 3) O20 nH2O

Smectite is the most studied clay in research and industry. Smectites are also phyllosilicates

of type 2: 1 or TOT whose elementary sheet is formed by an alternation of octahedral layers,

mainly made up of aluminum cations (Al3+

) interposed between two tetrahedral layers, mainly

made up of silicon cations (Si4+

). The minerals that belong to this family are montmorillonite,

saponite, beidellite and hectorite. Furthermore, this type of mineral is characterized by a very

high cation exchange capacity due to tetrahedral isomorphic (Si4+ → Al

3+, Fe

3+) and / or

octahedral (Al3+

→ Mg2+

, Fe2+

, or Mg2+

, or Li+) substitutions of compensating cations (Na

+,

Ca2+

) are placed in the inter foliar space to fill the load deficit. The electrostatic attraction

between the sheets is weak which allows this type of clay to incorporate the water molecules

in their interfoliar space. Smectites are therefore swelling clays [40-42].

Figure 7. Smectite structure.

1.5. Physicochemical properties of clays:

a) Specific surface:

Clays are widely used as adsorbents due to their large specific surface which is due to the

small size of clay minerals. This specific surface includes the sum of two surfaces, one

external between the particles and the other internal corresponding to the interfoliar space. It

is expressed in m2 per gram of clay. The minerals of the smectite family are characterized by

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a very large specific surface compared to that of other types of clays due to their swelling

properties. The specific surface can reach 800 m2 / g.

Figure 8. Internal and external surface of clay particles (smectite).

b) Cation exchange capacity (CEC) :

Cation exchange capacity (CEC) is a measure of the ability of a clay to exchange

compensating cations. Indeed, it measures the number of monovalent cations that it is possible

to replace the compensating cations (Li+, Na

+, Ca

2+, K

+ or Mg

2+) in order to compensate for

the electrical charge of 100 g of calcined clay at pH 7. Conventionally, it is expressed in

milliequivalents per 100 g of dry clay (meq / 100 g). Thus the cation exchange capacity is

mainly due to isomorphic substitutions at the level of the tetrahedral and octahedral layers of

the sheet. These substitutions give the sheet a negative charge which will be compensated by

cations placed in the interfoliar spaces. Generally, smectites have the most important CECs

among other clays. This capacity is typically in the range of 70 to 160 meq / 100 g. It allows,

given the large surface area of montmorillonite, to efficiently fix heavy metal cations, organic

cations and some hydrocarbons [43-45].

c) Swelling property:

The property of swelling in the presence of water varies greatly from one clay family to

another. All clays have a capacity for retaining more or less important water molecules, but

only a few are capable of incorporating appreciable quantities of water molecules in their

interfoliar spaces. Generally, smectites and vermiculites are among the clays which are

characterized by a strong capacity of water adsorption between the sheets of their structure.

This causes a variation in their volumes which results in a spacing between the sheets and

thus causes them to swell. These clays are called swelling clays or "swelling clays" [47-49].

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Figure 9. Representation of clay swelling mechanism.

d) Acid-base properties of the reaction sites :

The acid-base character of clays is generally assigned to the surface silanol or aluminol

groups with X-OH borders (with X = Al or Si) and compared to that of mineral oxides (Figure

10) [50]. We can distinguish two types of acid-basicity:

• Acido-basicity in the sense of Bronsted : when the surface sites of X-OH silanols or

aluminols (X = Al or Si) have amphoteric properties. They are then likely to capture or

release a hydrogen ion according to the following two reactions:

X-OH + H+

X-OH+

2

X-OH X-O- + H

+

Acido-basicity in the sense of Lewis : the atom X (Si or Al) of group X-OH acts as a Lewis

acid electron acceptor and can thus be linked to the base OH- electron donor or to a other

donor L according to the following balance:

X-OH + L-

X-L + OH-

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Figure 10. Bronsted and Lewis acidic sites on the surface of clay.

1.6. Field of application of clays

Thanks to their physicochemical characteristics (adsorption and absorption of molecules,

composition, particle size), clays have very useful applications in various fields:

Pesticide retention : most pesticides exert a toxic action on water, sediment and soil. These

pesticides are retained by clays thanks to their high adsorption capacity [51,52].

Adsorption of heavy metals : Clays have a large adsorption capacity thanks to their specific

surface. In addition, the presence of associated minerals such as iron, aluminum and

calcium oxides can increase adsorption, especially for heavy metals including arsenic [53-

55].

Catalyst : clay can act as a catalyst in the petrochemical industry.For this property, clays

allow the heterogeneous catalysis of petroleum to transform it into petrol. This step is prior

to refining the oil [56].

Use as an anti-infectious, intestinal purifier and destroyer of bacteria [57].

1.7. Valorization of clays by modification

Clays in their natural states have fairly poor properties (surface area, exchange adsorption

capacity, swelling, etc.) and their use in industry does not arouse much interest. Several

methods have been proposed in order to improve these properties by modifications. The

susceptibility of clay modification lies in the fact that their interlamellar cations can easily be

replaced by other cations or other molecules.

1.7.1. Acid activation of clays

Activation is a classic process that involves improving the adsorption properties of clay by

subjecting it to a chemical treatment (acid attack), with a solution of mineral acid (HCl,

H2SO4). Acid treatment causes several changes in the structure of the clay. These include:

pore volume, surface acidity, cation exchange capacity and even the texture of these

materials. In general, acid activation is often accompanied by the departure of Al3+

and Fe3+

from the octahedral layer. And often generates acid Bronsted (H+) sites which are important

for the organic modification of clay, this leads to the substantial increase in surface area

(exchange of alkaline and alkaline earth cations by more acidic cations Al3+

, Mg2+

and H+),

therefore the cation exchange capacity decreases. On the other hand, the Si framework is not

affected by activation, its rate increases in the material. The quantity of compounds released is

proportional to the concentration of the activating agent, the departure of all these constituents

causes the start of formation of amorphous silica [58-60].

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Figure 11. Representation of the effect of acid activation on clay.

1.7.2. Pillared clays

Because of their great catalytic performances and especially their thermal stabilities, many

scientific research laboratories have been interested in pillared clays. Generally, pillaring of

clays essentially lies in the intercalation between sheets of large single or mixed metallic

polycations by cation exchange of compensating ions in order to obtain microporous

materials, with rigid structure and with a large interfoliar spacing. The most commonly used

polycations are zirconium and aluminum [61].

Figure 12. Pillars of Smectite clay.

After calcination at different temperatures, the intercalated polycations transform into pillars

in the form of a cluster of rigid and resistant metal oxides. This gives these solids a high

stability, a developed microporous surface, a high acidity and also makes it possible to

separate the sheets and then create a larger interfoliar space therefore promoting adsorption.

1.7.3. Organophilic clays

Generally, the organophilic treatment is a cation exchange. The inorganic compensating

cations naturally present in the interfoliar space of the clay are replaced by organic

surfactants. These surfactants (surfactant molecules) have a hydrophilic polar head and an

apolar aliphatic chain. The most commonly used surfactants are alkylamonium ions. During

the exchange reaction, the polar head of the surfactant replaces the cation and the surfactant

then lodges in the interfoliar space, thus making the organophilic clay (Figure 13). This

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chemical treatment increases the interfoliar distance and the adsorption affinity of organic

molecules [62].

Figure 13. Schematic representation of an organophilic clay.

1.8. Application of clays in organic synthesis

Clays have been widely used as active and selective catalysts in several organic reactions

because they are reusable, non-toxic and easily separable from reaction medium. Due to the

versatile nature of K10 montmorillonite, it can be easily modified and employed for a wide

variety of organic reactions. Mariappan and his team [63] have shown that montmorillonite

K10 clay has shown a catalytic performance in the synthesis of 2-phenylquinoxaline from 1,2-

diaminobenzene and phenacyl bromide. The product is obtained with an excellent yield

(92%).

Scheme 1. Synthesis of 2-phenylquinoxaline.

Recently, Sudhakar and al., [64] have reported that montmorillonite K10 used as highly

efficient catalyst for the synthesis of phenols from arylboronic acids.

Scheme 2. Synthesis of phenol.

Acid activated clay

The literature has reported that acid-activated montmorillonites and other smectites are also

good catalysts for the esterification of lauric acid acid with methanol [65], wet Peroxide

Oxidation of Paracetamol [66], for the synthesis of dioxolanes and oxazolidines [67], for the

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rearrangement of N-acyl-2,2-dimethyl aziridine into a mixture of allylamides, amidoalcohols

and oxazolines [68], Isomerization of α-pinene [69] and dehydration of glycerol to acrolein

[70]. YuFeng [71] showed that Montmorillonite-H+ proved to be a very effective and

reusable catalyst for the endocyclization of phenylethylamine derivatives with aldehydes

under solvent-free conditions.

Scheme 3. Phenylethylamine reaction with benzaldehyde.

In the same context, Motokura and al [72] have shown that acid-activated montmorillonite

(Mont-H+) is an excellent catalyst for the allylsilylation reaction of aromatic and aliphatic

alkenes.

Scheme 4. Addition of allylsilanes with aromatic and aliphatic alkenes.

Recently, Alali and al [73] used acid-activated clay as an effective catalyst in the synthesis of

(2,2-dimethyl-1,3-dioxolan-4-yl) methanol named solketal from glycerol and acetone. The

solketal is obtained with an excellent yield (89%).

Scheme 5. Solketal synthesis.

Pillared clay

In a large number of organic reactions clays have been used as catalysts. Properties of clays

can be further improved by making pillared clays. Pillared clays are clays with high

permanent porosity obtained by separating the clay sheets by a molecular prop or pillaring

agent. These pillaring agents can be organic, organometallic, or inorganic complexes [74,75].

Pillared clay (PILC) possesses several interesting properties, such as large surface area, high

pore volume and tunable pore size (from micropore to mesopore), high thermal stability,

strong surface acidity and catalytic active substrates/metal oxide pillars. These unique

characteristics make PILC an attractive material in catalytic reactions. It can be made either as

catalyst support or directly used as catalyst [76-78]. In fact, clay pillaring with titanium have

been prepared for the oxidative desulfurization of dibenzothiophene [79], and iron pillared

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clay were used as catalyst for 2-nitrophenol reduction [80]. Alumina pillared clay based

catalytic systems have been studied for several catalytic reactions such as catalytic wet

peroxide oxidation, hydroxylation of benzene, hydroformylation of alkenes, epoxidation of

cyclooctene, oxidation of propene, hydrodrchlorination of 4-chlorophenol and hydrogenation

[81-83]. Conversion of D-xylose into furfural [84], synthesis of imidazopyridine derivatives

[85], synthesis of 2-chlorophenylbenzoxazole [86] are performed in the presence of alumina

pillared clays. In particular, Al-Fe pillared clays have been reported as active catalysts in the

Baeyer–Villiger oxidation [87]. Zirconium pillared clay are used for Phenol Oxidation [88].

Furthermore, Zr-Al pillared clay have been used as catalyst for phenol hydroxylation [89]. In

addition, Cr-pillared clays have been used as catalyst to carry out various shape selective

reactions such as methylation of toluene, propene oxidation, acylation of alcohol, oxidation

of chlorinated hydrocarbon and carbon monoxide [90].

2. Zeolite : Structure, Properties, Application

By origin, zeolites can be natural or synthetic materials. Natural zeolite are found in volcanic

rocks [91]. Zeolite are usually hydrated aluminosilicates. They result from a regular three-

dimensional sequence of AlO4 and SiO4 tetrahedra pooling all their oxygen atoms (Figure 14).

The aluminate tetrahedra induce a negative charge in the structure of the zeolite. M cations

are present to stabilize the structure of the neutral material. The general formula for zeolites is

written as follows: Mx/n (AlO2)x (SiO2)y mH2O, where M is a cation of valence n (n≥1), which

ensures the electroneutrality of the whole. It is generally an alkali or alkaline earth metal (Na+,

Ca2+

, K+) but it can also be a heavy metal (lead, copper, nickel, cobalt, cesium.), Non-metallic

(H+, NH4

+) or organic. The cation M is in particular responsible for the cation exchange

properties of the zeolite [92-94].

Figure 14. Chemical structure of zeolite.

Based on the pore size and absorption properties, zeolites are among the most important

inorganic cation exchangers and are used in industrial applications for water and waste water

treatment, catalysis, nuclear waste, agriculture, animal feed additives, and in biochemical

applications [95-98]. Natural zeolite can be modified by several methods such as acid

treatment, ion exchange, and surfactant functionalisation, making the modified zeolites

achieving higher adsorption capacity for organics and anions [99]. Indeed, naturally occurring

zeolites are rarely phase-pure and are contaminated to varying degrees by other minerals

(Fe2+

, SO4-, quartz, other zeolites, and amorphous glass). For this reason, naturally occurring

zeolites are excluded from many important commercial applications where uniformity and

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purity are essential. Synthetic zeolites hold some key advantages over their natural analogs.

The synthetics can, of course, be manufactured in a uniform, phase-pure state [100,101].

Synthetic zeolites have higher surface areas, higher micropore volumes, lack impurities and

can be specially manufactured for a specific task [102]. A large number of different zeolites

with varying functional groups have been synthetically produced for specific purposes, the

most common are zeolites A, X, Y and ZSM-5.

Zeolites, as solid acids, have become extremely successful as catalysts and have been

employed for a wide variety of reactions, such as the cracking of carbon-carbon bonds [103],

solketal isomerizations [104], polymerization [105], aromatic alkylation with alkenes or

alcohols [106], and other acid catalysed reactions. Subsequent studies reported by the team of

Katkar [107] have shown that ZnO-beta zeolite used as an effective and resuable

heterogenous catalyst for the one-pot synthesis of polyhydroquinolines.

Scheme 6. Synthesis of polyhydroquinolines catalyzed by ZnO-beta zeolite.

In the same context, Moliner and al [108] have shown that Tin-containing zeolites effectively

catalyses the isomerization of glucose.

Scheme 7. Isomerization of glucose.

Recently, the Feng research group [109] have reported that zeolite EU-12 shows excellent

catalytic performance for carbonylation reactions.

Scheme 8. Dimethyl ether carbonylation over the EU-12 zeolite.

On the other hand, Huang [110] described the synthesis of quinoline compounds catalyzed by

USY zeolite-based catalysts.

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Scheme 9. Synthesis of quinoline.

In 2018, Magar and al [111] showed that Ce-ZSM-11 Zeolite used as efficinet catalyst for the

synthesis of 1,8-dioxo-octahydroxanthenes derivatives.

Scheme 10. Synthesis of 1,8-dioxo-octahydroxanthenes derivatives.

In the same context, the Shekhar team [112] took an interest in the study of zeolite (ZSM-5)

as a highly efficient and heterogeneous catalyst for the synthesis of β-enaminones and β-

enamino esters.

Scheme 11. Synthesis of β-enaminones catalysed by zeolite (ZSM-5).

Conclusion

The discovery of solid materials with high catalytic performance is crucial for most chemical

processes by allowing the replacement of homogeneous polluting catalysts by heterogeneous

reusable catalysts. In this review, we comprehensively summarizes the chemical structure of

various heterogenous catalyts and their effecient catalytic activity in organic synthesis.

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DESIGN OF HETEROGENOUS CATALYSIS IN ORGANIC SYNTHESIS

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