Next Article in Journal
In-Situ Functionalization of Cotton Fabric by TiO2: The Influence of Application Routes
Next Article in Special Issue
Highlights on the General Preference for Multi-Over Mono-Coupling in the Suzuki–Miyaura Reaction
Previous Article in Journal
Hydrogenolysis of Lignin and C–O Linkages Containing Lignin-Related Compounds over an Amorphous CoRuP/SiO2 Catalyst
Previous Article in Special Issue
Advances in Green Catalysis for the Synthesis of Medicinally Relevant N-Heterocycles
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Catalysts
Volume 12
Issue 11
10.3390/catal12111329
catalysts-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Review

Green Chemistry in Organic Synthesis: Recent Update on Green Catalytic Approaches in Synthesis of 1,2,4-Thiadiazoles

by
Laila Rubab
1,
Ayesha Anum
2,
Sami A. Al-Hussain
3,
Ali Irfan
4,
Sajjad Ahmad
5,
Sami Ullah
1,*,
Aamal A. Al-Mutairi
3 and
Magdi E. A. Zaki
3,*
1
Department of Chemistry, Sargodha Campus, The University of Lahore, Sargodha 40100, Pakistan
2
Hamdard Institute of Pharmaceutical Sciences, Islamabad Campus, Hamdard University of Pharmaceutical Sciences, Islamabad 44000, Pakistan
3
Department of Chemistry, College of Science, Imam Mohammad Ibn Saud Islamic University (IMSIU), Riyadh 11623, Saudi Arabia
4
Department of Chemistry, Government College University Faisalabad, Faisalabad 38000, Pakistan
5
Department of Health and Biological Sciences, Abasyn University, Peshawar 25000, Pakistan
*
Authors to whom correspondence should be addressed.
Catalysts 2022, 12(11), 1329; https://doi.org/10.3390/catal12111329
Submission received: 7 October 2022 / Revised: 23 October 2022 / Accepted: 24 October 2022 / Published: 29 October 2022
(This article belongs to the Special Issue Advances in Green Catalysis for Sustainable Organic Synthesis, 2nd Edition)
Browse Figures
Review Reports Versions Notes

Abstract

:
Green (sustainable) chemistry provides a framework for chemists, pharmacists, medicinal chemists and chemical engineers to design processes, protocols and synthetic methodologies to make their contribution to the broad spectrum of global sustainability. Green synthetic conditions, especially catalysis, are the pillar of green chemistry. Green chemistry principles help synthetic chemists overcome the problems of conventional synthesis, such as slow reaction rates, unhealthy solvents and catalysts and the long duration of reaction completion time, and envision solutions by developing environmentally benign catalysts, green solvents, use of microwave and ultrasonic radiations, solvent-free, grinding and chemo-mechanical approaches. 1,2,4-thiadiazole is a privileged structural motif that belongs to the class of nitrogen–sulfur-containing heterocycles with diverse medicinal and pharmaceutical applications. This comprehensive review systemizes types of green solvents, green catalysts, ideal green organic synthesis characteristics and the green synthetic approaches, such as microwave irradiation, ultrasound, ionic liquids, solvent-free, metal-free conditions, green solvents and heterogeneous catalysis to construct different 1,2,4-thiadiazoles scaffolds.

Graphical Abstract

1. Introduction

In 1991, the term “green chemistry” was first coined by Anatas, and the Environmental Protection Agency defined green chemistry or sustainable chemistry as “the designed chemical processes and products that eliminate or reduce the generation or use of hazardous substance” [1,2,3,4]. In the 1990s, green chemistry came into existence due to the prominent work of Warner, Trost, Anastas, Sheldon, Clarke and others [5,6,7,8,9]. Green chemistry is a new concept, introduced in the 20th century to develop new synthetic procedures, methodologies and chemical processes in the field of chemistry and chemical technology to accommodate the conventional existing procedures and strategies to make them environmentally benign and economical. This can be achieved by utilizing various approaches and strategies, such as ultrasound-assisted protocols, green solvents, solvent-free drugs synthesis, ionic liquids, microwave-assisted approaches, green reduction procedures, oxidation catalysts, solid acid–base catalysts and heterogeneous metal catalysis, etc. [10,11,12]. Anastas and Warner introduced the key criteria for green chemistry in a set of 12 principals that laid down the fundamentals of green chemistry [1,2,3,4,13], as illustrated in Figure 1 [14,15].

2. Green Approaches in Organic Synthesis

The concept of green chemistry introduced the environmentally benign synthetic protocols for the synthesis of heterocycles that has had a significant impact in many fields, such as the use of green solvents, solvent-free synthesis, sustainable catalytic materials, reduced energy consumption, improved atom economy, optimized reaction yields, the use of alternative energy sources, the introduction of multicomponent reactions (MCRs), ionic liquids and the design of high-efficiency and time-saving reactions that work at ambient temperatures [16,17,18,19,20,21,22,23,24,25]. Pollution and an increase in energy demands prompted the design of novel synthetic protocols to fulfill the requirements of green and sustainable chemistry to promote the synthesis of organic products in an ecofriendly environment [26,27]. The new green and sustainable synthetic approaches are listed below and have advantages over conventional synthetic approaches, as depicted in Figure 2 [28,29,30,31,32,33,34,35]:
  • Solvent-free approach;
  • Grinding approach;
  • Ball milling approach;
  • Solid–wet approach;
  • Ultrasonic-assisted approach;
  • Microwave-assisted approach;
  • MOF green synthesis approach;
  • Electrochemical green catalytic synthetic approach.
In organic synthesis, avoiding the use of harmful and toxic solvents, as well as catalysts, was quite a difficult and highly challenging objective achieved by modern synthetic chemists. In green and sustainable organic synthesis, the ideal synthesis consists in following rational design fetchers to comprehensively implement the green chemistry principles, as displayed in Figure 3 [36,37,38,39,40,41].

3. Green Catalysts in Organic Synthetic Approaches

The present study is a brief description of the role of catalysis in green synthetic transformations and green synthesis of drugs, chemical reagents, polymeric materials, nanomaterials and others organic materials for a sustainable future. Environmentally benign synthetic strategies are mainly possible due to the vital role of catalysts in lowering the activation energy, due to which reactions are possible at low heat energy or at room temperature and products are achieved in good-to-excellent yields by generating fever co-products, by-products and other waste substances. Catalysis is the pillar of green chemistry, and catalysts used in the green organic synthesis must be safe, easy to handle, reusable, biodegradable and cost-effective, recyclable, recovered efficiently and display a high reaction rate to afford products in maximum yields with shorter time duration and different types of green catalysts is depicted in Table 1 [42,43,44,45,46].

4. Green Solvents in Organic Synthetic Approaches

The major focus of green chemistry is the elimination of solvents from chemical processes and organic synthesis or replacement of hazardous solvents with ecofriendly solvents. The attention under the remit of green chemistry is ascribed to the large volume of solvents used in the manufacture of drugs, paints, textiles, polymers, solvent extractions and purification in final formulations and other industrial products that drastically damage the environment and living organism and that must be reduced, replaced and eliminated from processes and switched to greener processes and green solvents [147,148,149,150,151,152,153,154]. The green solvents that are mostly used in organic synthesis are mentioned in Table 2.

5. Green Synthetic Approaches for Synthesis of 1,2,4-Thiadiazoles

Green chemistry synthetic approaches are used to synthesize heterocyclic-pharmacophore-based bioactive therapeutic drugs, which have significant importance in medicinal and pharmaceutical chemistry. The versatile heterocyclic thiadiazole rings with different isomeric forms, such as 1,2,3-, 1,2,4-, 1,2,5- and 1,3,4-, display substantial therapeutic efficacy against a wide variety of diseases. The 1,2,4-thiadazole scaffolds represent a five-membered nitrogen–sulfur-containing significant class of core heterocyclic structures of great interest, mainly because of the part of the structural unit of biologically active molecules: a useful intermediate in medicinal chemistry and part of the clinical drugs, which are given in Figure 4 [232,233,234,235,236,237,238,239,240,241,242,243].
1,2,4-thiadiazole is a privileged pharmacophore that exhibits a diverse and broad spectrum of biological activities, such as human leukemia cell, antibacterial, anti-inflammatory, insecticidal, herbicidal and fungicidal agents, anticonvulsant, cardiovascular, cathepsin B inhibitors, dual 5-lipoxygenase and cyclooxygenase inhibitors, antidiabetic, antiulcerative and allosteric modulators [244,245,246,247,248,249,250,251,252]. Synthetic chemists and pharmacists are attracted to the 1,2,4-thiadiazole moiety due to its versatile biological and pharmacological profile, and R&D scientists are interested in developing new synthetic approaches and methodologies to afford 1,2,4-thiadiazole scaffolds. This review article covers green and ecofriendly synthetic routes to produce 1,2,4-thiadiazole hybrids and their medicinal significance from 2000 to 2022. The plethora of research about green approaches and medicinal importance cited in this review article will be helpful for researchers in future for drug discovery and the development of novel bioactive 1,2,4-thiadiazole drug candidates.
The following are different ecofriendly green synthetic strategies to produce 1,2,4-thiadiazole structural hybrids by utilizing various synthetic conditions to achieve products in high yields within a short period of time.

5.1. PIFA Catalyst for Formation of N–S Bond via Intramolecular Cyclization

Mariappan et al. developed a synthetic green and broad substrate scope protocol for S-N bond formation via intramolecular cyclization to afford substituted 5-amino-based 1,2,4-thiadiazole derivatives in the presence of hypervalent iodine (III) as an inexpensive catalyst (Scheme 1). The merit of this synthetic approach is that it is metal-free and has a short reaction time and good-to-excellent yield of products at ambient temperature. A mixture of N-(phenyl carbamothioyl) benzimidamide 2 was treated with phenyliodine (III) bis(trifluoroacetate) (PIFA) in 1,2-dichloroethane (DCE) to achieve the corresponding 1,2,4-thiadiazole derivatives 3, as depicted in Scheme 1. The plausible mechanism suggested that the PIFA was reacted with midoyl thiourea to generate an intermediate in which the NH nucleophilic group attacks the sulfur atom to afford the corresponding product with the removal of trifluoro acetic acid and iodobenzene. The advantage of this synthetic protocol is that the product yield is good: either substrate has electron-donating or electron-withdrawing groups, or both [253].

5.2. Molecular I2 Catalysis and Oxidative N–S Bond Formation

Wang et al. reported an efficient synthetic approach for the construction of 5-amino- and 3,5-diamino-substituted 1,2,4-thiadiazoles via oxidative N–S Bond formation in scalable fashion by utilizing molecular iodine as the sole oxidant as displayed in Scheme 2. This transition, metal-free, short reaction time and mild reaction conditions strategy transformed imidoyl and guanyl thiourea 4 into 1,2,4-thiadiazole 5 in the presence of K2CO3, acetonitrile and molecular iodine as a catalyst at room temperature. The products of gram-scale synthesis were afforded in excellent yields, 96–99%, as shown in Scheme 2. The diverse electron-donating, such as methyl (Me), and electron-withdrawing, such as Cl, Br, NO2 and CF3, substituents on the aryl group of aromatic thioamides were well-tolerated and afforded maximum yields of the respective products. As the aromatic thioamides were weaker in nucleophilicity, which resulted in relatively lower yields with strong electron-withdrawing groups [254].

5.3. Molecular I2 Catalysis for Regio-Specific and Expeditious Synthetic Approach

Mangarao et al. reported an expeditious approach to achieve the novel N-fused and 3,4-disubstituted 5-imino-1,2,4-thiadiazole hybrid structures (8,10) by treating substituted isothiocyanate 7 with 2-aminopyridine/amidine (6,9), which underwent intramolecular cyclization to form N-S bonds in the presence of an inexpensive I2 catalyst and acetonitrile as a solvent at ambient temperature as shown in Scheme 3. The merits of this facile and highly efficient regio-specific synthetic approach are insensitivity to moisture and air, being metal-free, highly efficient in product yield, gram-scale synthesis and wide substrate spectrum [255].

5.4. Molecular I2 Catalysis for One-Pot Green Protocol and Intramolecular Oxidative Coupling

Chai et al. afforded 3,5-disubstituted 1,2,4-thiadiazole 13 in an efficient and simple one-pot green protocol through the sequential intermolecular combination of alkyl substituted nitriles 12 with aryl substituted thiamide 11, through intramolecular oxidative coupling of N–H and S–H bonds in an aqueous medium and iodine as the sole oxidant catalyst as depicted in Scheme 4 [256].

5.5. Ultrasonic-Assisted Synthesis in Water

Chauhan et al. reported the conversion of thiobenzamide 11 with chloranil 14, under ultrasound irradiation in an aqueous medium at ambient temperature, to the corresponding 1,2,4-thiadiazole 15 with a metal-free, catalyst-free, convenient and environmentally benign one-pot protocol. The sequential intermolecular combination of thiomide 11 with chloranil 14 (oxidant) through intramolecular oxidative coupling of N-H and S-H bonds afforded 3,5-disubstituted 1,2,4-thiadiazoles in good-to-excellent yields as displayed in Scheme 5 [257].

5.6. HTACas PTC for Green Synthesis Using Molecular Oxygen as an Oxidant

Zhao et al. developed an efficient green methodology in which molecular oxygen is used as a terminal oxidant to furnish 1,2,4-thiadizoles as depicted in Scheme 6. The oxidative dimerization of alkyl and aryl thioamides 16 was achieved in the presence of I2 as a catalyst, hexadecyltrimethyl ammonium chloride (HTAC) as a phase transfer catalyst (PTC) and con. H2SO4 as a regenerative agent. The substituted thiomide underwent transformation into the substituted 1,2,4-thiadiazoles 17 in excellent yields via intramolecular oxidative coupling of N-H and N-S bonds. The lowest 35% yield indicated that the electron-withdrawing substituent on the benzene ring of benzothioamide failed to undergo the dimerization reaction compared with the electrodonating substituents [258].

5.7. Transition-Metal-Free Green Protocol Using Air as Oxidant

A novel and green approach was developed by Yang et al. with a broad substrate scope, mild reaction conditions, good functional group tolerance and high regioselectivity to construct the S-N bond of a 1,2,4-thiadiazole core via oxidative coupling. In this metal-free and gram-scale synthetic strategy, substituted amidines 18 and substituted isothiocyanates 19 were treated for the construction of the S-N bond via I2 mediated oxidative coupling to produce 5-amino-1,2,4-thiadiazole derivatives 20 in the presence of TMEDA (N,N,N′,N′-tetramethyl ethylene diamine), air (oxidant) and acetonitrile as the solvent. In this synthetic pathway, 1,2,4-thiadiazoles were afforded in moderate-to-excellent yields (Scheme 7) [259].

5.8. Solid–Solid Oxidative Coupling

Hassan Zali Boeini reported a novel, rapid, simple and efficient protocol for the conversion of the equimolar amount, pulverized thiobenzamide 21 and N-bezyl-DABCO-tribromide in wet solid–solid conditions to produce 1,2,4-thiadiazoles 22 in excellent yields compared with conventional methods (Scheme 8). In this green method, intramolecular oxidative coupling and efficient cyclization constructed the aryl-substituted 1,2,4-thiadiazoles. This short-term, ambient temperature and high yield are the key features of this environmentally benign approach compared with the conventional synthetic approach of 1,2,4-thiadiazoles [260].

5.9. Green Synthesis in Wet-Paste Conditions

Hassan Zali Boeini developed another highly efficient and rapid synthetic methodology to produce diaryl substituted 1,2,4-thiadiazoles in wet-paste conditions. The N,N′-dibromo phenytoin 24 was used for the rapid conversion of aryl-substituted thiobenzamides 23 to the corresponding 1,2,4-thiadiazole 25 in excellent yields (88–99%) through efficient intramolecular cyclization as depicted in Scheme 9 [261].

5.10. Oxidative Dimerization Using CC–DMSO in PEG-400

Khosropour and Noei developed an efficient, ecofriendly and inexpensive synthetic protocol for the construction of the1,2,4-thiadiazole privileged structural motif. The structurally diverse 3,5-diaryl-substituted 1,2,4-thiadiazole structural hybrids 27 were afforded in excellent 88–96% yields due to intramolecular oxidative dimerization and cyclization of substituted aryl thioamides 26 with chloranil 14 by utilizing a green medium of 4,6-trichloro-1,3,5-triazine-DMSO (CC-DMSO) in PEG-400 (Scheme 10). The advantages of this preparatory protocol are simplicity, very short reaction times, generality, recyclability of solvent, environmentally benign, ambient temperature and elaboration of substituted 1,2,4-thiadiazoles with high-to-excellent yields [262].

5.11. Basic Alumina Catalyst for Synthesis of Substituted 1,2,4-Thiadiazoles via Grinding Approach

Xu et al. developed a solvent-free, environmentally benign synthetic approach to synthesize 3,5-disubstituted-1,2,4-thiadiazole structural hybrids 30 in excellent yields (90–99%) through the reaction of substituted thiomide 28 with NBS 29 in the presence of basic alumina and grinding this reaction mixture for 5–15 min at room temperature as shown in Scheme 11. This synthetic protocol displayed advantages over existing strategies to access substituted 1,2,4-thiadiazoles in terms of efficiency, higher yields, short duration of reaction time and neat conditions. This facile and highly efficient methodology showed compatibility with variety of functional groups such as the trifluoromethyl, methyl, methoxy, chloro, pyridyl and thienyl groups [263].

5.12. Synthesis of 1,2,4-Thiadiazole-5-Carboxylates by Microwave-Assisted Approach

Fordyce et al. generated the substituted ethyl 1,2,4-thiadiazole-5-carboxylate scaffolds 33 by the cycloaddition of 0.56 molar oxathiazolone 31 with 0.5 molar ethyl cyanoformate (ECF) 32 in the presence of p-xylene solvent under microwave-assisted heating at 160 °C for 10 min as represented in Scheme 12. The solvent and excessive ethyl cyanoformate were removed under reduced pressure, and residue was subjected to purification and spectroscopic characterizations. The merits of microwave-assisted green synthetic methodology were the shorter reaction time and easy work-up to produce ethyl-1,2,4-thiadiazole-5-carboxylate products in moderate-to-good yields [264].

5.13. Green Synthesis of 1,2,4-Thiadiazole via Ionic Liquids

Zali-Boeini et al. reported the synthesis of a new facile and efficient environmentally friendly methodology to afford 3,5-disubstituted-1,2,4-thiadiazole by using pentyl pyridinium tribromide ionic liquids as the solvents, as well as reagent to carry out the oxidative dimerization of aryl thiomide. An equimolar mixture of arythiomide and pentylpyridinium tribromide ionic liquids was mixed together and stirred for 3–7 min at ambient temperature to obtain substituted 1,2,4-thiadiazole structural motifs in excellent yields. The recyclable pentylpyridinium tribromide compound, named room-temperature ionic liquids (RTILs), can be used 4–5 times to carry out oxidative dimerization. This synthetic approach is smooth, rapid, clean and environmentally benign and achieved products in 88–97% yield (Scheme 13) [265].

5.14. Copper Salts as Catalyst for Green One-Pot Synthetic Protocol for N–S Bond Formation

Kim et al. described a one-pot environmentally benign synthetic approach to obtain 3-substituted-1,2,4-thiadizole under different solvents (THF, DMF and CH3CN), catalysts (CuI, CuCN, CuBr2, Cu(OAc)2·H2O, Cu(OTf)2, CuSO4) and Cs2CO3 as basic agents for the facilitation of the reaction. The substituted amidines 18 reacted with substituted isothiocyanates 35 or substituted thioureas 36 and directly underwent N–S Bond formation via intramolecular cyclization in the presence of Cu(OTf)2 catalyst, basic agent CsCO3 and solvents (THF and acetonitrile) to achieve substitute-1,2,4-thiadiazole structural hybrids 37 in moderate-to-good yields as shown in Scheme 14 [266].

5.15. Oxidative Dimerization of Thioamides by Using Oxone as Safe Oxidant

Yoshimura et al. selected the ecofriendly, inexpensive, safe and readily available oxone as an oxidative dimerization agent. They developed an efficient, novel synthetic protocol to furnish 1,2,4-thiadiazole 17 structural motifs in good-to-excellent yields through the treatment of substituted thioamide 16 with oxone as oxidant in the presence of DCM at ambient temperature, as displayed in Scheme 15. In the present synthetic protocol, both the EW and ED substituents furnished 1,2,4-thiadiazoles in good yields, which is the main advantage of this green strategy [267].

5.16. Molecular I2 as Catalyst for Synthesis of 1,2,4-Thiadiazoles via Oxidative N–S Bond Formation

Jatangi et al. reported a facile, efficient, environmentally benign and convenient synthetic approach for the synthesis of 3-substituted 5-amino-1,2,4-thiadiazole scaffolds in a scalable fashion. In this metal-free and high-substrate-tolerance methodology, the reaction of substituted isothiocynates 29 and substituted amidoximes 38 was carried out at 60 °C in the presence of I2, with potassium carbonate and water as green solvents, to afford substituted 1,2,4-thiadiazole derivatives 39 in good-to-high yields, as depicted in Scheme 16 [268].

5.17. Synthesis of N-Fused Imino-1,2,4-Thiadiazolo Isoquinoline via Montmorillonite K10-Catalyst

Chacko and Shivashankar for the first time reported the green, recoverable, inexpensive, nontoxic and efficient oxidizing montmorillonite K10-catalyst for the rapid construction of N–S Bond formation to afford 1,2,4-thiadiazolo isoquinoline structural hybrids in good yields. In this simple synthetic protocol, 3-aminoisoquinolines 40 were coupled with substituted isothiocyanates 35 to construct the N–S Bond of 1,2,4-thiadiazole core to achieve N-fused imino-1,2,4-thiadiazolo isoquinoline scaffolds in excellent yields as displayed in Scheme 17 [269].

5.18. H2O2-Catalyzed Synthesis of 1,2,4-Thiadiazoles

Cao et al. reported the hydrogen-peroxide-mediated synthetic transformations of substituted thiourea 4 into 1,2,4-thiadiazoles 5 through the construction of the N–S Bond under metal-free synthetic conditions with ethanol as the sole solvent at ambient temperature as shown in Scheme 18. The advantages of this synthetic strategy are large-scale preparation, operationally simple, ethanol as the green solvent and clean by-products. 1,2,4-thiadiazole structural hybrids were obtained in good-to-excellent yields [270].

6. Conclusions

Advances in green synthetic organic chemistry may result in a more ecofriendly future with the help of green technologies, processes and synthetic reaction conditions, such as green solvents, green catalysts, solvent-free and less energy-consuming strategies and microwave- and ultrasonic-assisted approaches that transform reactants into products with sustainability. The chemical industrial sector and academic research mostly rely on hazardous catalysis and solvents. Therefore, alternative green solvents and green catalysis are the future of our ecosystem in reducing or even eliminating these hazardous materials’ effects on the environment and can lead to the optimized yield of products in a shorter period of time, in accordance with all 12 principles of green chemistry. In this plethora of research, various green catalytic approaches have been applied to furnish different 1,2,4-thiadiazole structural hybrids in good-to-excellent yields by utilizing various green solvents, solvent-free procedures, ionic liquid approaches, grinding and chemo-mechanical protocols, microwave- and ultrasonic-assisted time reduction techniques. We think that the next decade will be a major mark of applying green and sustainable catalysis methodologies to promote organic transformations in academia and industry alike.

Author Contributions

Conceptualization, A.I. and M.E.A.Z.; project administration, M.E.A.Z.; supervision and resources, S.U.; data curation and visualization, A.A.; writing—original draft preparation, L.R., S.A.A.-H., A.I. and S.A.; writing—review and editing, L.R., S.A.A.-H., A.I., A.A.A.-M. and M.E.A.Z.; funding acquisition, A.A.A.-M. All authors have read and agreed to the published version of the manuscript.

Funding

The authors extend their appreciation to the Deanship of Scientific Research at Imam Mohammad Ibn Saud Islamic University for funding this work through Research Group No. RG 21-09-76.

Data Availability Statement

Data are available in the manuscript.

Acknowledgments

Authors acknowledge the support and literature facilities provided by the Government College University Faisalabad (GCUF)-Faisalabad and UOL Sargodha Campus-Sargodha-Pakistan.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Deligeorgiev, T.; Gadjev, N.; Vasilev, A.; Kaloyanova, S.; Vaquero, J.J.; Alvarez-Builla, J. Green Chemistry in Organic Synthesis. Mini-Rev. Org. Chem. 2010, 7, 44–53. [Google Scholar]
  2. Wardencki, W.; Curylo, J.; Namiesnic, J. Green chemistry—Current and future. Pol. J. Environ. Stud. 2005, 14, 389–395. [Google Scholar]
  3. Williams, T.M.; Blacker, J. The Importance of Green Chemistry in Process Research and Development, Pharmaceutical Process Development: Current Chemical and Engineering Challenges; Royal Society of Chemistry: London, UK, 2011. [Google Scholar]
  4. The Full Definition Is: Green Chemistry, Also Known as Sustainable Chemistry, Is the Design of Chemical Products and Processes that Reduce or Eliminate the Use or Generation of Hazardous Substances. Available online: https://www.epa.gov/greenchemistry/basics-green-chemistry (accessed on 8 February 2011).
  5. Anastas, T.P.; Warner, C.J. Green Chemistry applies across the life cycle of a chemical product, including its design, manufacture and use. In Green Chemistry Theory and Practice; Oxford University Press: Oxford, UK, 1998. [Google Scholar]
  6. Clarke, H.J. Green chemistry: Challenges and opportunities. Green Chem. 1999, 1, 1–8. [Google Scholar] [CrossRef]
  7. Sheldon, A.R. The E Factor: Fifteen years on. Green Chem. 2007, 9, 1273–1283. [Google Scholar] [CrossRef]
  8. Sheldon, A.R. Green chemistry and resource efficiency: Towards a green economy. Green Chem. 2016, 18, 3180–3183. [Google Scholar] [CrossRef]
  9. Trost, B. The Atom Economy—A Search for Synthetic Efficiency. Science 1991, 254, 1471–1477. [Google Scholar] [CrossRef]
  10. Draye, M.; Chatel, G.; Duwald, R. Ultrasound for Drug Synthesis: A Green Approach. Pharmaceuticals 2020, 13, 23. [Google Scholar] [CrossRef] [Green Version]
  11. Chatel, G.; Leclerc, L.; Narechoux, E.; Bas, C.; Kardos, N.; Goux-Henry, C.; Andrioletti, B.; Draye, M. Ultrasonic Properties of Hydrophobic Bis(trifluoromethylsulfonyl)imide-Based Ionic Liquids. J. Chem. Eng. Data. 2012, 57, 3385–3390. [Google Scholar] [CrossRef]
  12. Tan, D.A.; Kulkarnia, A.; Torok, B. Environmentally benign synthesis of heterocyclic compounds by combined microwave-assisted heterogeneous catalytic approaches. Green Chem. 2012, 14, 17–37. [Google Scholar] [CrossRef]
  13. Ahluwalia, V.K.; Kidwai, M. New Trends in Green Chemistry; Kluwer, Academic Publishers: Dordrecht, The Netherlands, 2004. [Google Scholar]
  14. Anastas, P.; Eghbali, N. Green Chemistry: Principles and Practise. Chem. Soc. Rev. 2020, 29, 301–312. [Google Scholar] [CrossRef]
  15. Kurniawan, S.Y.; Priyangga, A.T.P.K.; Krisbiantoro, A.; Imawan, C.A. Green Chemistry Influences in Organic Synthesis: A Review. J. Multidiscip. Appl. Nat. Sci. 2021, 1, 1–12. [Google Scholar] [CrossRef]
  16. Cioc, R.C.; Ruijter, E.; Orru, R.V.A. Multicomponent reactions: Advanced tools for sustainable organic synthesis. Green Chem. 2014, 16, 2958–2975. [Google Scholar] [CrossRef]
  17. Varma, R.S. Journey on greener pathways: From the use of alternate energy inputs and benign reaction media to sustainable applications of nano-catalysts in synthesis and environmental remediation. Green Chem. 2014, 16, 2027–2041. [Google Scholar] [CrossRef]
  18. Gawande, M.J.; Bonifacio, V.D.B.; Luque, R.; Branco, P.S.; Varma, R.S. Benign by design: Catalyst-free in-water, on-water green chemical methodologies in organic synthesis. Chem. Soc. Rev. 2013, 42, 5522–5551. [Google Scholar] [CrossRef] [PubMed]
  19. Tang, S.L.Y.; Smith, R.L.; Poliakoff, M. Principles of green chemistry: PRODUCTIVELY. Green Chem. 2005, 7, 761–762. [Google Scholar] [CrossRef]
  20. Ganem, B. Strategies for innovation in multicomponent reaction design. Acc. Chem. Res. 2009, 42, 463–472. [Google Scholar] [CrossRef] [Green Version]
  21. Ryabukhin, S.V.; Panov, D.M.; Plaskon, A.S.; Grygorenko, O.O. Approach to the library of 3-hydroxy-1,5-dihydro-2h-pyrrol-2-ones through a three-component condensation. ACS Comb. Sci. 2012, 14, 631–635. [Google Scholar] [CrossRef] [PubMed]
  22. Graaff, C.; Ruijter, E.; Orru, R.V.A. Recent developments in asymmetric multicomponent reactions. Chem. Soc. Rev. 2012, 41, 3969–4009. [Google Scholar] [CrossRef]
  23. Toure, B.B.; Hall, D.G. Natural product synthesis using multicomponent reaction strategies. Chem. Rev. 2009, 109, 4439–4486. [Google Scholar] [CrossRef]
  24. Trost, B.M. On inventing reactions for atom economy. Acc. Chem. Res. 2002, 35, 695–705. [Google Scholar] [CrossRef] [PubMed]
  25. Cho, H.Y.; Morken, J.P. Catalytic bismetallative multicomponent coupling reactions: Scope, applications, and mechanisms. Chem. Soc. Rev. 2014, 43, 4368–4380. [Google Scholar] [CrossRef] [PubMed]
  26. Duvauchelle, V.; Meffre, P.; Benfodda, Z. Green methodologies for the synthesis of 2-aminothiophene. Environ. Chem. Lett. 2022, 1–25. [Google Scholar] [CrossRef] [PubMed]
  27. Hafez, A.A.E.; Al-Mousawi, M.S.; Moustafa, S.M.; Sadek, U.K.; Elnagdi, H.M. Green methodologies in organic synthesis: Recent developments in our laboratories. Green Chem. Lett. Rev. 2013, 6, 89–210. [Google Scholar] [CrossRef] [Green Version]
  28. Banik, B.K.; Sahoo, B.M.; Kumar, B.V.V.R.; Panda, K.C.; Jena, J.; Mahapatra, M.K.; Borah, P. Green Synthetic Approach: An Efficient Eco-Friendly Tool for Synthesis of Biologically Active Oxadiazole Derivatives. Molecules 2021, 26, 1163. [Google Scholar] [CrossRef] [PubMed]
  29. Horváth, I.T.; Anastas, P.T. Innovations and green chemistry. Chem Rev. 2007, 107, 2169–2173. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  30. Horváth, I.T.; Anastas, P.T. Introduction: Green chemistry. Chem Rev. 2007, 107, 2167–2168. [Google Scholar] [CrossRef] [Green Version]
  31. Das, A.; Banik, K. Dipole moment of medicinally active compounds: A sustainable approach in medicinal research: Green and sustainable approach. In Green Approaches in Medicinal Chemistry for Sustainable Drug Design, 1st ed.; Elsevier: Amsterdam, The Netherlands, 2020; Volume 26, pp. 921–964. [Google Scholar]
  32. Varma, S.R. Greener and Sustainable Trends in Synthesis of Organics and Nanomaterials, ACS Sustainable Chemistry & Engineering. ACS Sustain. Chem. Eng. 2016, 4, 5866–5878. [Google Scholar] [CrossRef]
  33. Kim, Y.; Li, C.-J. Perspectives on green synthesis and catalysis. Green Synth. Catal. 2020, 1, 1–11. [Google Scholar] [CrossRef]
  34. Dai, S.; Tissot, A.; Serre, C. Metal-Organic Frameworks: From Ambient Green Synthesis to Applications. Bull. Chem. Soc. Jpn. 2021, 94, 2623–2636. [Google Scholar] [CrossRef]
  35. Cheng, X.; Lei, A.; Mei, T.-S.; Xu, H.-C.; Xu, K.; Zeng, C. Recent Applications of Homogeneous Catalysis in Electrochemical Organic Synthesis. CCS Chem. 2022, 4, 1120–1152. [Google Scholar] [CrossRef]
  36. Shrikhande, J.J.; Gawande, M.B.; Jayaram, R.V. Cross-aldol and Knoevenagel condensation reactions in aqueous micellar media. Catal. Commun. 2008, 9, 1010–1016. [Google Scholar] [CrossRef]
  37. Butler, R.N.; Coyne, A.G. Water: Nature’s Reaction Enforcer—Comparative Effects for Organic Synthesis “In-Water” and “On-Water”. Chem. Rev. 2010, 110, 6302–6337. [Google Scholar] [CrossRef] [PubMed]
  38. Sachdeva, H.; Khaturia, S. A mini-review on organic synthesis in water. MOJ Biorg. Org. Chem. 2017, 1, 239–243. [Google Scholar] [CrossRef] [Green Version]
  39. Nasri, S.; Bayat, M.; Miankooshki, F.R.; Samet, N.H. Recent developments in green approaches for sustainable synthesis of indole-derived scaffolds. Mol. Divers. 2022. [Google Scholar] [CrossRef]
  40. Casti, F.; Basoccu, F.; Mocci, R.; De Luca, L.; Porcheddu, A.; Cuccu, F. Appealing Renewable Materials in Green Chemistry. Molecules 2022, 27, 1988. [Google Scholar] [CrossRef] [PubMed]
  41. Martínez, J.; Cortés, J.F.; Miranda, R. Green Chemistry Metrics, A Review. Processes 2022, 10, 1274. [Google Scholar] [CrossRef]
  42. Onuegbu, T.U.; Ogbuagu, A.S.; Ekeoma, M.O. The role of catalysts in green synthesis of chemicals for sustainable future. J. Basic Phy. Res. 2011, 2, 86–92. [Google Scholar]
  43. Kharissova, O.V.; Kharisov, B.I.; Oliva, G.C.M.; Méndez, Y.P.; López, I. Greener synthesis of chemical compounds and materials. R. Soc. Open Sci. 2019, 6, 191378. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  44. Anastas, T.P.; Kirchhoff, M.M.; Williamson, C.T. Catalysis as a foundational pillar of green chemistry. Appl. Catal. A-Gen. 2001, 221, 3–13. [Google Scholar] [CrossRef]
  45. Delidovich, I.; Palkovits, R. Catalytic versus stoichiometric reagents as a key concept for Green Chemistry. Green Chem. 2016, 18, 590–593. [Google Scholar] [CrossRef]
  46. Ruslan, A.A.A.N.; Kan, S.-K.; Hamzah, S.A.; Chia, W.P. Natural food additives as green catalysts in organic synthesis: A review. Environ. Chem. Lett. 2021, 19, 3359–3380. [Google Scholar] [CrossRef]
  47. Matsuo, J.; Tsuchiya, T.; Odashima, K.; Kobayashi, S. Lewis Acid Catalysis in Supercritical Carbon Dioxide. Use of Scandium Tris(heptadecafluorooctanesulfonate) as a Lewis Acid Catalyst in Diels-Alder and Aza Diels-Alder Reactions. Chem. Lett. 2000, 29, 178. [Google Scholar] [CrossRef]
  48. Kobayashi, S.; Manabe, K. Green Lewis acid catalysis in organic synthesis. Pure Appl. Chem. 2000, 72, 1373–1380. [Google Scholar] [CrossRef]
  49. Chassaing, S.; Beneteau, V.; Louis, B.; Pale, P. Zeolites as Green Catalysts for Organic Synthesis: The Cases of H-, Cu- & Sc-Zeolites. Curr. Org. Chem. 2017, 21, 779–793. [Google Scholar] [CrossRef]
  50. Itoha, T.; Hanefeld, U. Enzyme catalysis in organic synthesis. Green Chem. 2017, 19, 331–332. [Google Scholar] [CrossRef]
  51. Rinaldi, R.; Palkovits, R.; Schüth, F. Depolymerization of cellulose using solid catalysts in ionic liquids. Angew. Chem. Int. Ed. 2010, 47, 8047–8050. [Google Scholar] [CrossRef]
  52. Akiyama, G.; Matsuda, R.; Sato, H.; Takata, M.; Kitagawaet, S. Cellulose hydrolysis by a new porous coordination polymer decorated with sulfonic acid functional groups. Adv. Mater. 2011, 23, 3294–3297. [Google Scholar] [CrossRef] [PubMed]
  53. Wu, Y.; Fu, Z.; Yin, D.; Xu, Q.; Liu, F.; Lu, C.; Mao, L. Microwave-assisted hydrolysis of crystalline cellulose catalyzed by biomass char sulfonic acids. Green Chem. 2010, 12, 696–700. [Google Scholar] [CrossRef]
  54. Pang, J.; Wang, A.; Zheng, M.; Zhang, T. Hydrolysis of cellulose into glucose over carbons sulfonated at elevated temperatures. Chem. Commun. 2010, 46, 6935–6937. [Google Scholar] [CrossRef] [PubMed]
  55. Zhang, F.; Deng, X.; Fang, Z.; Zeng, H.; Tian, X.; Kozinski, J. Hydrolysis of microcrystalline cellulose over Zn-Ca-Fe oxide catalyst. Petrochem. Technol. 2011, 40, 43–48. [Google Scholar] [CrossRef]
  56. Tian, J.; Fang, C.; Cheng, M.; Wang, X. Hydrolysis of cellulose over CsxH3−xPW12O40 (x = 1–3) heteropoly acid catalysts. Chem. Eng. Technol. 2011, 34, 482–486. [Google Scholar] [CrossRef]
  57. Tian, J.; Wang, J.H.; Zhao, S.; Jiang, C.Y.; Zhang, X.; Wang, X.H. Hydrolysis of cellulose by the heteropoly acid H3PW12O40. Cellulose 2010, 17, 587–594. [Google Scholar] [CrossRef]
  58. Kobayashi, H.; Komanoya, T.; Hara, K.; Fukuoka, A. Water tolermesoporous-carbon-supported ruthenium catalysts for the hydrolysis of cellulose to glucose. ChemSusChem 2010, 3, 440–443. [Google Scholar] [CrossRef] [PubMed]
  59. Lai, D.M.; Deng, L.; Guo, Q.X.; Fu, Y. Hydrolysis of biomass by magnetic solid acid. Energy. Environ. Sci. 2011, 4, 3552–3557. [Google Scholar] [CrossRef]
  60. Komanoya, T.; Kobayashi, H.; Hara, K.; Chun, W.J.; Fukuoka, A. Catalysis and characterization of carbon-supported ruthenium for cellulose hydrolysis. Appl. Catal. A Gen. 2011, 407, 188–194. [Google Scholar] [CrossRef] [Green Version]
  61. Ogasawara, Y.; Itagaki, S.; Yamaguchi, K.; Mizuno, N. Saccharification of natural lignocellulose biomass and polysaccharides by highly negativecharged heteropolyacids in concentrated aqueous solution. ChemSusChem 2011, 4, 519–525. [Google Scholar] [CrossRef] [PubMed]
  62. Luo, X.; Wu, H.; Li, C.; Li, Z.; Li, H.; Zhang, H.; Li, Y.; Su, Y.; Yang, S. Heteropoly Acid-Based Catalysts for Hydrolytic Depolymerization of Cellulosic Biomass. Front. Chem. 2020, 8, 580146. [Google Scholar] [CrossRef] [PubMed]
  63. Rostamian, R.; Khalilzadeh, A.M.; Zareyee, D. Wood ash biocatalyst as a novel green catalyst and its application for the synthesis of benzochromene derivatives. Sci. Rep. 2022, 12, 1145. [Google Scholar] [CrossRef] [PubMed]
  64. Dekamin, M.G.; Ilkhanizadeh, S.; Latifidoost, Z.; Daemi, H.; Karimi, Z.; Barikani, M. Alginic acid: A highly efficient renewable and heterogeneous biopolymeric catalyst for one-pot synthesis of the Hantzsch 1,4-dihydropyridines. RSC Adv. 2014, 4, 56658–56664. [Google Scholar] [CrossRef]
  65. Dekamin, M.G.; Karimi, Z.; Latifidoost, Z.; Ilkhanizadeh, S.; Daemi, H.; Naimi-Jamal, M.R.; Barikani, M. Alginic acid: A mild and renewable bifunctional heterogeneous biopoly mericorgano catalyst for efficient and facile synthesis of polyhydroquinolines. Int. J. Biol. Macromol. 2018, 108, 1273–1280. [Google Scholar] [CrossRef]
  66. Hosseinzadeh, Z.; Ramazani, A.; Razzaghi-Asl, N.; Slepokura, K.; Lis, T. Boric acid as an efficient and green catalyst for the synthesis of 2-amino-4,6-diarylnicotinonitrile under microwave irradiation in solvent-freeconditions. Turk. J. Chem. 2019, 43, 464–474. [Google Scholar] [CrossRef]
  67. Mohamadpour, F.; Maghsoodlou, M.T.; Lashkari, M.; Heydari, R.; Hazeri, N. Green synthesis of polysubstitutedquinolines and xanthene derivatives promoted by tartaric acid as a naturally green catalyst under solvent-free conditions. Chem. J. Mold. 2018, 13, 74–86. [Google Scholar] [CrossRef]
  68. Singh, A.K.; Dar, B.; Ahad, A.; Pardeshi, R.K. An efficient tartaric acid catalyzed green protocol for the synthesis of 2,3- dihydroquinazolin-4(1H)-ones in aqueous medium. Int. J. Chem. Sci. 2018, 16, 247. [Google Scholar]
  69. Ahankar, H.; Ramazani, A.; Ślepokura, K.; Lis, T.; Joo, S.W. Synthesis of pyrrolidinone derivatives from aniline, an aldehyde and diethylacetylenedicarboxylate in an ethanolic citric acid solution under ultrasound irradiation. Green Chem. 2016, 18, 3582–3593. [Google Scholar] [CrossRef]
  70. Shokrollahi, S.; Ramazani, A.; Rezaei, S.J.T.; Malekzadeh, A.M.; Asiabi, P.A.; Joo, S.W. Citric acid as an efficient and green catalyst for the synthesis of hexabenzylhexaazaisowurtzitane (HBIW). Iran. J. Catal. 2016, 6, 65–68. [Google Scholar]
  71. Shaikh, K.A.; Chaudhar, U.N.; Ningdale, V.B. Citric acid catalyzedsynthesis of amidoalkylnaphthols under solvent-free condition:an eco-friendly protocol. IOSR J. Appl. Chem. 2014, 7, 90–93. [Google Scholar] [CrossRef]
  72. Kangani, M.; Hazeri, N.; Maghsoodlou, M.T. A mild and environmentally benign synthesis of tetrahydrobenzo[b]pyrans and pyrano[c]chromenes using pectin as a green and biodegradable catalyst. J. Chin. Chem. Soc. 2016, 63, 896–901. [Google Scholar] [CrossRef]
  73. Sangshetti, J.N.; Dharmadhikari, P.P.; Chouthe, S.R.; Fatema, B. Water mediated oxalic acid catalyzed one pot synthesis of 1,8-dioxodecahydroacridines. Arab. J. Chem. 2017, 10, S10–S12. [Google Scholar] [CrossRef] [Green Version]
  74. Sangshetti, J.N.; Kalam, K.F.A.; Chouthe, R.S.; Zaheer, Z.; Ahmed, R.Z. Water-mediated oxalic acid catalysed one-pot synthesis of 2-(substituted phenyl) phthalazin-1(2 H)-ones. J. Taibah Univ. Sci. 2015, 9, 548–554. [Google Scholar] [CrossRef] [Green Version]
  75. Sarkate, A.P.; Sangshetti, J.N.; Dharbale, N.B.; Wakte, P.S.; Shinde, D.B. Solvent free oxalic acid catalyzed synthesis of 1,5-benzodiazepines. J. Chil. Chem. Soc. 2013, 58, 2200–2203. [Google Scholar] [CrossRef] [Green Version]
  76. Mohamadpour, F.; Maghsoodlou, M.T.; Heydari, R.; Lashkari, M. Saccharin: A green, economical and efficient catalyst for the one-pot, multi-component synthesis of 3,4-dihydropyrimidin-2-(1H)-one derivatives and 1H-pyrazolo [1,2-b] phthalazine-5,10-dione derivatives and substituted dihydro-2-oxypyrrole. J. Iran. Chem. Soc. 2016, 13, 1549–1560. [Google Scholar] [CrossRef]
  77. Moradi, L.; Aghamohammad, S.M. Sodium saccharin as an effective catalyst for rapid one-pot pseudo-five component synthesis of dihydropyrano[2,3-g]chromenes under microwave irradiation. Acta Chim. Slov. 2017, 64, 506–512. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  78. Häring, M.; Pettignano, A.; Quignard, F.; Tanchoux, N.; Díaz, D.D. Keratin protein-catalyzed nitroaldol (henry) reaction and comparison with other biopolymers. Molecules 2016, 21, 1122. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  79. Wang, S.; Zhang, Z.; Chi, C.; Wu, G.; Ren, J.; Wang, Z.; Huang, M.; Jiang, Y. Asymmetric hydration of ortho- or para-substituted styrenes catalyzed by biopolymer-metal complex wool-Pd. React. Funct. Polym. 2008, 68, 424–430. [Google Scholar] [CrossRef]
  80. Wang, X.; Sui, D.; Huang, M.; Jiang, Y. Highly effective hydration of olefins using a wool-palladium complex as a catalyst. Polym. Adv. Technol. 2006, 17, 163–167. [Google Scholar] [CrossRef]
  81. Zheng, M.; Li, X.X.; Mao, S.F.; Huang, M.Y.; Jiang, Y.Y. Hydrogenation of anisol and benzaldehyde catalyzed by chicken feather-palladium complex. Polym. Adv. Technol. 1997, 8, 638–640. [Google Scholar] [CrossRef]
  82. Jafari, Z.; Seyedi, S.M.; Sadeghian, H. Application of Magnetic Chicken Feather Powder-Cu to the Click Synthesis of 1,2,3-Triazoles. Polycycl. Aromat. Compd. 2020, 40, 245–256. [Google Scholar] [CrossRef]
  83. Patnam, P.L.; Bhatt, M.; Singh, R.; Saran, S.; Jain, S.L. Magnetically separable chicken feathers: A biopolymer based heterogeneous catalyst for the oxidation of organic substrates. RSC Adv. 2016, 6, 60888–60895. [Google Scholar] [CrossRef]
  84. Padma Latha, P.; Bhatt, M.; Jain, S.L. Sustainable catalysis using magnetic chicken feathers decorated with Pd(0) for Suzuki-cross coupling reaction. Tetrahedron Lett. 2015, 56, 5718–5722. [Google Scholar] [CrossRef]
  85. Rizzo, G.; Albano, G.; Lo Presti, M.; Milella, A.; Omenetto, F.G.; Farinola, G.M. Palladium Supported on Silk Fibroin for Suzuki–Miyaura Cross-Coupling Reactions. Eur. J. Org. Chem. 2020, 2020, 6992–6996. [Google Scholar] [CrossRef]
  86. Rizzo, G.; Albano, G.; Sibillano, T.; Giannini, C.; Musio, R.; Omenetto, F.G.; Farinola, G.M. Silk–Fibroin-Supported Palladium Catalyst for Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides. Eur. J. Org. Chem. 2022, 2022, 60–70. [Google Scholar] [CrossRef]
  87. Clavé, G.; Pelissier, F.; Campidelli, S.; Grison, C. Ecocatalyzed Suzuki cross coupling of heteroaryl compounds. Green Chem. 2017, 19, 4093–4103. [Google Scholar] [CrossRef]
  88. Grison, C.; Grison, C.; Escande, V.; Petit, E.; Garoux, L. Psychotriadouarrei and Geissois pruinosa, novel resources for the plant-based catalytic chemistry. RSC Adv. 2013, 3, 22340–22345. [Google Scholar] [CrossRef]
  89. Abu-Dief, M.A.; Abdel-Fatah, M.S. Development and functionalizatituron of magnetic nanoparticles as powerful and green catalysts for organic synthesis. Beni-Suef Univ. J. Basic Appl. Sci. 2018, 7, 55–67. [Google Scholar]
  90. Kim, D.K.; Mikhaylova, M. Anchoring of phosphonate and phosphinate coupling molecules on titania particles. Chem. Mater. 2003, 15, 1617–1627. [Google Scholar] [CrossRef]
  91. Khojastehnezhad, A.; Rahimizadeh, M.; Eshghi, H.; Moeinpour, F.; Bakavoli, M. Ferric hydrogen sulfate supported on silica-coated nickel ferrite nanoparticles as new and green magnetically separable catalyst for 1,8 dioxodecahydroacridine synthesis. Chin. J. Catal. 2014, 35, 376–382. [Google Scholar] [CrossRef]
  92. Venkatachalapathy, C.; Pitchumani, K. Fries re-arrangement of esters in montmorillonite clays: Steric control on selectivity. Tetrahedran 1997, 53, 17171–17176. [Google Scholar] [CrossRef]
  93. Dhakshinamoorthy, A.; Kanagaraj, K.; Pitchumani, K. Zn2+-K10-clay (clayzic) as an efficient water-tolerant, solid acid catalyst for the synthesis of benzimidazoles and quinoxalines at room temperature. Tetrahedron Lett. 2011, 52, 69–73. [Google Scholar] [CrossRef]
  94. Carrado, K.A.; Hayatsu, R.; Botto, R.E.; Winans, R. Reactivity of anisoles on clay and pillared clay surfaces. Clays Clay Miner. 1990, 38, 250–256. [Google Scholar] [CrossRef]
  95. Guzman, J.; Gates, B.C. Structure and Reactivity of a Mononuclear Gold-Complex Catalyst Supported on Magnesium Oxide. Angew. Chem. Int. Ed. 2003, 42, 690–693. [Google Scholar] [CrossRef]
  96. Walkey, C.; Das, S.; Seal, S.; Erlichman, J.; Heckman, K.; Ghibelli, L.; Traversa, E.; McGinnis, J.F.; Self, W.T. Catalytic Properties and Biomedical Applications of Cerium Oxide Nanoparticles. Environ. Sci. Nano 2015, 2, 33–53. [Google Scholar] [CrossRef] [Green Version]
  97. Layek, K.; Kantam, M.L.; Shirai, M.; Nishio-Hamane, D.; Sasaki, T.; Maheswaran, H. Gold Nanoparticles Stabilized on Nanocrystalline Magnesium Oxide as an Active Catalyst for Reduction of Nitroarenes in Aqueous Medium at Room Temperature. Green Chem. 2012, 14, 3164–3174. [Google Scholar] [CrossRef]
  98. Lopez, N.; Nørskov, J.K. Catalytic CO Oxidation by a Gold Nanoparticle: A Density Functional Study. J. Am. Chem. Soc. 2002, 124, 11262–11263. [Google Scholar] [CrossRef]
  99. Martínez-Méndez, S.; Henríquez, Y.; Domínguez, O.; D’Ornelas, L.; Krentzien, H. Catalytic Properties of Silica Supported Titanium, Vanadium and Niobium Oxide Nanoparticles towards the Oxidation of Saturated and Unsaturated Hydrocarbons. J. Mol. Catal. A Chem. 2006, 252, 226–234. [Google Scholar] [CrossRef]
  100. Dupont, J.; Fonseca, G.S.; Umpierre, A.P.; Fichtner, P.F.P.; Teixeira, S.R. Transition-Metal Nanoparticles inImidazolium Ionic Liquids: Recycable Catalysts for Biphasic Hydrogenation Reactions. J. Am. Chem. Soc. 2002, 124, 4228–4229. [Google Scholar] [CrossRef] [PubMed]
  101. Sun, X.; Zhu, Q.; Kang, X.; Liu, H.; Qian, Q.; Zhang, Z.; Han, B. Molybdenum-Bismuth Bimetallic Chalcogenide Nanosheets for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Methanol. Angew. Chem. Int. Ed. 2016, 55, 6771–6775. [Google Scholar] [CrossRef]
  102. You, D.J.; Kwon, K.; Pak, C.; Chang, H. Platinum-Antimony Tin Oxide Nanoparticle as Cathode Catalyst for Direct Methanol Fuel Cell. Catal. Today 2009, 146, 15–19. [Google Scholar] [CrossRef]
  103. Safaei-Ghomi, J.; Ghasemzadeh, M.A.; Mehrabi, M. Calcium Oxide Nanoparticles Catalyzed One-Step Multicomponent Synthesis of Highly Substituted Pyridines in Aqueous Ethanol Media. Sci. Iran. 2013, 20, 549–554. [Google Scholar]
  104. Seabra, A.B.; Durán, N. Nanotoxicology of Metal Oxide Nanoparticles. Metals 2015, 5, 934–975. [Google Scholar] [CrossRef] [Green Version]
  105. Mazumder, V.; Sun, S. Oleylamine-Mediated Synthesis of Pd Nanoparticles for Catalytic Formic Acid Oxidation. J. Am. Chem. Soc. 2009, 131, 4588–4589. [Google Scholar] [CrossRef]
  106. Sakthivel, S.; Kisch, H. Daylight Photocatalysis by Carbon-Modified Titanium Dioxide. Angew. Chem. Int. Ed. 2003, 42, 4908–4911. [Google Scholar] [CrossRef]
  107. Pipelzadeh, E.; Babaluo, A.A.; Haghighi, M.; Tavakoli, A.; Derakhshan, M.V.; Behnami, A.K. Silver Dopingon TiO2 Nanoparticles Using a Sacrificial Acid and Its Photo-catalytic Performance under Medium Pressure Mercury UV Lamp. Chem. Eng. J. 2009, 155, 660–665. [Google Scholar] [CrossRef]
  108. Baricelli, J.P.; Rodríguez, G.; Rodríguez, A.; Lujano, E.; López-Linares, F. Synthesis, characterization and aqueous-biphase hydrogenation of olefins by the ruthenium complexes Ru(CO)3(TPPMS)2 and RuH2(CO)(TPPMS)3. Appl. Catal. A Gen. 2003, 239, 25–34. [Google Scholar] [CrossRef]
  109. Baricelli, J.P.; Lzaguirre, L.; López, J.; Lujano, E.; López-Linares, F. Synthesis, characterization and catalytic hydrogenation in aqueous-biphasic system of a new water soluble complex RuH(CO)(NCMe)(TPPMS)3[BF4]. J. Mol. Catal. A Chem. 2004, 208, 67–72. [Google Scholar] [CrossRef]
  110. Kotzabasakis, V.; Georgopoulou, E.; Pitsikalis, M.; Hadjichristidis, N.; Papadogianakis, G. Catalytic conversions in aqueous media: A novel and efficient hydrogenation of polybutadiene-1,4-block-poly(ethylene oxide) catalyzed by Rh/TPPTS complexes in mixed micellar nanoreactors. J. Mol. Catal. A Chem. 2005, 231, 93–101. [Google Scholar] [CrossRef]
  111. Zhu, Y.; Carpenter, K.; Ching, C.; Bahnmueller, S.; Chan, P. (R)-Binap-Mediated Asymmetric Hydrogenation with a Rhodacarborane Catalyst in Ionic-Liquid Media. Angew. Chem. Int. Ed. 2003, 42, 3792–3795. [Google Scholar]
  112. Ngo, L.H.; Hu, A.; Lin, W. Catalytic asymmetric hydrogenation of aromatic ketones in room temperature ionic liquids. Tetrahedron Lett. 2005, 46, 595–597. [Google Scholar] [CrossRef]
  113. Xiong, W.; Lin, Q.; Ma, H.; Zheng, H.; Chen, H.; Li, X. Asymmetric hydrogenation of aromatic ketones in ionic-liquid media catalyzed by Ru-TPPTS–(1S,2S)-DPENDS complexes. Tetrahedron Asymm. 2005, 16, 1959–1962. [Google Scholar] [CrossRef]
  114. Ackermann, L.; Vicente, R. Catalytic Direct Arylations in Polyethylene Glycol (PEG): Recyclable Palladium(0)Catalyst for C−H Bond Cleavages in the Presence of Air. Org. Lett. 2009, 11, 4922–4925. [Google Scholar] [CrossRef]
  115. Reddy, C.G.; Balasubramanyam, P.; Salvanna, N.; Das, B. Copper-Mediated C–H Activation of 1,3,4-Oxadiazoles with 1,1-Dibromo-1-alkenes Using PEG-400 as a Solvent Medium: Distinct Approach for the Alkynylation of 1,3,4-Oxadiazoles. Eur. J. Org. Chem. 2011, 2012, 471–474. [Google Scholar] [CrossRef]
  116. Yang, F.; Koeller, J.; Ackermann, L. Photo-induced Copper-Catalyzed C−H Arylation at Room Temperature. Angew. Chem. Int. Ed. 2016, 55, 4759–4762. [Google Scholar] [CrossRef] [PubMed]
  117. Zhu, C.; Oliveira, A.C.J.; Shen, Z.; Huang, H.; Ackermann, L. Manganese(II/III/I)-Catalyzed C–H Arylations in Continuous Flow. ACS Catal. 2018, 8, 4402–4407. [Google Scholar] [CrossRef]
  118. Chen, X.; Souvanhthong, B.; Wang, H.; Zhang, H.; Wang, X.; Huo, M. Polyoxometalate-based ionic liquid as thermoregulated and environmentally friendly catalyst for starch oxidation. Appl. Catal. B Environ. 2013, 161, 138–139. [Google Scholar] [CrossRef]
  119. Ding, Y.; Zhao, W. The oxidation of pyridine and alcohol using the Keggin-type lacunary polytungstophosphate as a temperature-controlled phase transfer catalyst. J. Mol. Catal. A Chem. 2011, 337, 45–51. [Google Scholar] [CrossRef]
  120. Rafiee, E.; Kahrizi, M. Mechanistic investigation of Heck reaction catalyzed by new catalytic system composed of Fe3O4@OA–Pd and ionic liquids as co-catalyst. J. Mol. Liq. 2016, 218, 625–631. [Google Scholar] [CrossRef]
  121. Vekariya, L.R. A Review of Ionic Liquids: Applications towards catalytic organic transformations. J. Mol. Liq. 2016, 227, 44–60. [Google Scholar] [CrossRef]
  122. Penín, L.; López, M.; Santos, V.; Parajó, J.C. Evaluation of acidic ionic liquids as catalysts for furfural production from eucalyptus nitens wood. Molecules 2022, 27, 4258. [Google Scholar] [CrossRef]
  123. Liu, S.; Wang, K.; Yu, H.; Li, B.; Yu, S. Catalytic preparation of levulinic acid from cellobiose via Brønsted-Lewis acidic ionic liquids functional catalysts. Sci. Rep. 2019, 9, 1810. [Google Scholar] [CrossRef] [PubMed]
  124. Wang, Y.; Zhao, D.; Chen, G.; Liu, S.; Ji, N.; Ding, H.; Fu, J. Preparation of phosphotungsticacid based poly (ionic liquid) and its application toesterification of palmitic acid. Renew. Energy 2019, 133, 317–324. [Google Scholar] [CrossRef]
  125. Wang, Y.; Zhao, D.; Wang, L.; Wang, X.; Li, L.; Xing, Z.; Ji, N.; Liu, S.; Ding, H. Immobilized phosphotungstic acid based ionic liquid: Application for heterogeneous esterification of palmitic acid. Fuel 2018, 216, 364–370. [Google Scholar] [CrossRef]
  126. Feng, Y.; Li, L.; Wang, X.; Yang, J.; Qiu, T. Stable poly (ionic liquid) with unique crosslinked microsphere structure as efficient catalyst for transesterification of soapberry oil to biodiesel. Energy Convers. Manag. 2017, 153, 649–658. [Google Scholar] [CrossRef]
  127. Han, M.; Li, Y.; Gu, Z.; Shi, H.; Chen, C.; Wang, Q.; Wan, H.; Guan, G. Immobilization of thiol-functionalized ionic liquids onto the surface of MIL-101 (Cr) frameworks by SCr coordination bond for biodiesel production. Colloids Surf. A Physicochem. Eng. Asp. 2018, 553, 593–600. [Google Scholar] [CrossRef]
  128. Xie, W.; Wan, F. Basic ionic liquid functionalized magnetically responsive Fe3O4@ HKUST-1 composites used for biodiesel production. Fuel 2018, 220, 248–256. [Google Scholar] [CrossRef]
  129. Xie, W.; Wan, F. Immobilization of polyoxometalate-based sulfonated ionic liquids on UiO-66-2COOH metal-organic frameworks for biodiesel production via one-pot transesterification-esterification of acidicvegetable oils. Chem. Eng. J. 2019, 365, 40–50. [Google Scholar] [CrossRef]
  130. Xie, W.; Wang, H. Synthesis of heterogenized polyoxometalate-based ionic liquids with brønsted-lewis acid sites: A magnetically recyclable catalyst for biodiesel production from low-quality oils. J. Ind. Eng. Chem. 2020, 87, 162–172. [Google Scholar] [CrossRef]
  131. Zhang, Q.; Hu, Y.; Li, S.; Zhang, M.; Wang, Y.; Wang, Z.; Peng, Y.; Wang, M.; Li, X.; Pan, H. Recent advances in supported acid/base ionic liquids as catalysts for biodiesel production. Front. Chem. 2022, 10, 999607. [Google Scholar] [CrossRef] [PubMed]
  132. Verma, C.; Ebenso, E.E.; Quraishi, M.A. Transition metal nanoparticles in ionic liquids: Synthesis and stabilization. J. Mol. Liq. 2019, 276, 826–849. [Google Scholar] [CrossRef]
  133. Ma, L.; Haynes, C.J.E.; Grommet, A.B.; Walczak, A.; Parkins, C.C.; Doherty, C.M.; Longley, L.; Tron, A.; Stefankiewicz, A.R.; Bennett, T.D.; et al. Coordination cages as permanently porous ionic liquids. Nat. Chem. 2020, 12, 270–275. [Google Scholar] [CrossRef]
  134. Bartlewicz, O.; Dabek, I.; Szymańska, A.; Maciejewski, H. Heterogeneous Catalysis with the participation of ionic liquids. Catalysts 2020, 10, 1227. [Google Scholar] [CrossRef]
  135. Maciejewski, H. Ionic liquids in Catalysis. Catalysts 2021, 11, 367. [Google Scholar] [CrossRef]
  136. McNeice, P.; Marr, C.P.; Marr, C.A. Basic ionic liquids for catalysis: The road to greater stability. Catal. Sci. Technol. 2021, 11, 726. [Google Scholar] [CrossRef]
  137. Singh, J.; Sharma, S.; Sharma, A. Photocatalytic carbonylation strategies: A recent trend in organic synthesis. J. Org. Chem. 2020, 86, 24–48. [Google Scholar] [CrossRef] [PubMed]
  138. Qian, Y.; Zhang, F.; Pang, H. A review of MOFs and their composites-based photocatalysts: Synthesis and applications. Adv. Funct. Mater. 2021, 31, 2104231. [Google Scholar] [CrossRef]
  139. Gisbertz, S.; Pieber, B. Heterogeneous photocatalysis in organic synthesis. ChemPhotoChem 2020, 4, 456–475. [Google Scholar] [CrossRef] [Green Version]
  140. Markushyna, Y.; Savateev, A. Light as a tool in organic photocatalysis: Multi-photon excitation and chromoselective reactions. Eur. J. Org. Chem. 2022, 2022, e202200026. [Google Scholar] [CrossRef]
  141. Michelin, C.; Hoffmann, N. Photocatalysis applied to organic synthesis—A green chemistry approach. Curr. Opin. Green Sustain. Chem. 2018, 10, 40–45. [Google Scholar] [CrossRef]
  142. Aghapoor, K.; Mohsenzadeh, F.; Sayahi, H.; Rastgar, S.; Darabi, R.H. Green synthesis of 1,3-dihydrobenzimidazol-2-ones from aromatic diamines by microwave in a tetrabutylammonium bromide–ethanol molten salt paste. Environ. Chem. Lett. 2018, 16, 1109–1116. [Google Scholar] [CrossRef]
  143. Filippov, A.S.; Amosova, S.V.; Albanov, A.I.; Potapov, V.A. Regioselective synthesis of novel functionalized dihydro-1,4-thiaselenin-2-ylsufanyl derivatives under phase transfer catalysis. Catalysts 2022, 12, 889. [Google Scholar] [CrossRef]
  144. Banik, B.K.; Banerjee, B.; Kaur, G.; Saroch, S.; Kumar, R. Tetrabutyl ammonium bromide (TBAB) catalyzed synthesis of bioactive heterocycles. Molecules 2020, 25, 5918. [Google Scholar] [CrossRef]
  145. Liu, S.; Zhu, W. A minireview of phase-transfer catalysis and recent trends. Biomed. J. Sci. Tech. Res. 2022, 45, BJSTR.MS.ID.007237. [Google Scholar] [CrossRef]
  146. Jaśkowska, J.; Drabczyk, A.K.; Michorczyk, P.; Kułaga, D.; Zaręba, P.; Jodłowski, P.; Majka, Z.; Jakubski, J.; Pindelska, E. Mechanochemical synthesis method for drugs used in the treatment of CNS diseases under PTC conditions. Catalysts 2022, 12, 464. [Google Scholar] [CrossRef]
  147. Ghosh, A.D. Green solvents for sustainable organic synthesis. IJSR 2015, 6, 2154–2157. [Google Scholar] [CrossRef]
  148. Shanab, K.; Neudorfer, C.; Schirmer, E.; Spreitzer, H. Green solvents in organic synthesis: An overview. Curr. Org. Chem. 2013, 17, 1179–1187. [Google Scholar] [CrossRef]
  149. Breeden, S.W.; Clark, J.H.; Macquarrie, D.J.; Sherwood, J.; Zhang, W.; Cue, B.W., Jr. Green Solvents. Green Techniques for Organic Synthesis and Medicinal Chemistry; Wiley: Chichester, UK, 2012; pp. 241–246. [Google Scholar]
  150. Earle, M.J.; Seddon, K.R. Ionic liquids green solvents for the future. Pure Appl. Chem. 2000, 72, 1391–1398. [Google Scholar] [CrossRef] [Green Version]
  151. Pena-Pereira, F.; Kloskowski, A.; Namieśnik, J. Perspectives on the replacement of harmful organic solvents in analytical methodologies: A framework toward the implementation of a novel generation of ecofriendly alternatives. Green Chem. 2015, 17, 3687–3705. [Google Scholar] [CrossRef]
  152. Clark, J.H.; Farmer, T.J.; Hunt, A.J.; Sherwood, J. Opportunities for biobased solvents created as petrochemical and fuel products transition towards renewable resources. Int. J. Mol. Sci. 2015, 16, 17101–17159. [Google Scholar] [CrossRef]
  153. Abou-Shehada, S.; Clark, J.H.; Paggiola, G.; Sherwood, J. Tunable solvents: Shades of green. Chem. Eng. Process 2016, 99, 88–96. [Google Scholar] [CrossRef]
  154. Constable, D.J.C.; Jimenez-Gonzalez, C.; Henderson, R.K. Perspective on solvent use in the pharmaceutical industry. Org. Process Res. Dev. 2007, 11, 133–137. [Google Scholar] [CrossRef]
  155. Dunn, P. Water as a green solvent for pharmaceutical applications. In Handbook of Green Chemistry; Anastas, P.T., Ed.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2010. [Google Scholar]
  156. Breslow, R. The Principles of and Reasons for Using Water as a Solvent for Green Chemistry. In Handbook of Green Chemistry; Anastas, P.T., Ed.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2010. [Google Scholar]
  157. Blackmond, D.G.; Armstrong, A.; Coombe, V.; Wells, A. Wasser in organokatalytischen Prozessen: Ein Mythos wird entschleiert. Angew. Chem. Int. Ed. 2007, 119, 3872–3874. [Google Scholar] [CrossRef]
  158. Burk, J.M.; Feng, S.; Gross, F.M.; Tumas, W. Asymmetric catalytic hydrogenation reactions in supercritical carbon dioxide. J. Am. Chem. Soc. 1995, 117, 8277–8278. [Google Scholar] [CrossRef]
  159. Morita, K.D.; Pesiri, R.D.; David, A.S.; Glaze, H.W.; Tumas, W. Palladium-catalyzed cross-coupling reactions in supercritical carbon dioxide. Chem. Commun. 1998, 13, 1397–1398. [Google Scholar] [CrossRef]
  160. Horvàth, I.T. Fluorous Biphase Chemistry. Acc. Chem. Res. 1998, 31, 641–650. [Google Scholar] [CrossRef]
  161. Horváth, I.T. Facile catalyst separation without water: Fluorous biphase hydroformylation of olefins. Science 1994, 266, 72–75. [Google Scholar] [CrossRef] [PubMed]
  162. Schäffner, B.; Schäffner, F.; Verevkin, S.P.; Borner, A. Organic carbonates as solvents in synthesis and catalysis. Chem. Rev. 2010, 110, 4554–4581. [Google Scholar] [CrossRef]
  163. Ross, S.D.; Finkelstein, M.; Petersen, R.C. Solvent effects in the reactions of N-bromosuccinimide with toluene, fluorene and acenaphthene; Evidence for a polar mechanism in propylene carbonate. J. Am. Chem. Soc. 1958, 80, 4327–4330. [Google Scholar] [CrossRef]
  164. Kronick, P.L.; Fuoss, R.M. Quaternization kinetics. II. Pyridine and 4-picoline in propylene carbonate. J. Am. Chem. Soc. 1955, 77, 6114. [Google Scholar] [CrossRef]
  165. Morcillo, M.; North, M.; Villuendas, P. Amino acid catalysed aldol reactions in cyclic carbonate solvents. Synthesis 2012, 12, 918–1925. [Google Scholar]
  166. Beattie, C.; North, M.; Villuendas, P. Proline-catalysed amination reactions in cyclic carbonate solvents. Molecules 2011, 16, 3420–3432. [Google Scholar] [CrossRef] [Green Version]
  167. Miao, X.; Fischmeister, C.; Bruneau, C.; Dixneuf, P.H. Dimethyl carbonate: An eco-friendly solvent in ruthenium-catalyzed olefin metathesis transformations. ChemSusChem 2008, 1, 813–816. [Google Scholar] [CrossRef] [PubMed]
  168. Arockiam, P.; Poirier, V.; Fischmeister, C.; Bruneau, C.; Dixneuf, P.H. Diethyl carbonate as a solvent for ruthenium catalysed C–H bond functionalization. Green Chem. 2009, 11, 1871–1875. [Google Scholar] [CrossRef]
  169. Torborg, C.; Huang, J.; Schulz, T.; Schäffner, B.; Zapf, A.; Spannenberg, A.; Borner, A.; Beller, M. Improved palladium-catalyzed Sonogashira coupling reactions of aryl chlorides. Chem. Eur. J. 2009, 15, 1329–1336. [Google Scholar] [CrossRef] [PubMed]
  170. Roger, J.; Verrier, C.; Le Goff, R.; Hoarau, C.; Doucet, H. Carbonates: Eco-friendly solvents for palladium-catalyzed direct 2-arylation of oxazole derivatives. ChemSusChem 2009, 2, 951–956. [Google Scholar] [CrossRef]
  171. Schäffner, B.; Holz, J.; Verevkin, S.P.; Börner, A. Rhodium-catalyzed asymmetric hydrogenation with self-assembling catalysts in propylene carbonate. Tetrahedron Lett. 2008, 49, 768–771. [Google Scholar] [CrossRef]
  172. Schäffner, B.; Holz, J.; Verevkin, S.P.; Börner, A. Organic carbonates as alternative solvents for palladium-catalyzed substitution reactions. ChemSusChem 2008, 1, 249–253. [Google Scholar] [CrossRef]
  173. Biliel, H.; Hamdi, N.; Zagrouba, F.; Fischmesiter, C.; Bruneau, C. Cross-metathesis transformations of terpenoids in dialkyl carbonate solvents. Green Chem. 2011, 13, 1448–1452. [Google Scholar] [CrossRef]
  174. Earle, M.J.; Noè, M.; Perosa-Seddon, A.K.R. Improved synthesis of tadalafil using dimethyl carbonate and ionic liquids. RSC Adv. 2014, 14, 1204–1211. [Google Scholar] [CrossRef]
  175. Lee, K.H.; Park, C.-H.; Lee, E.Y. Biosynthesis of glycerol carbonate from glycerol by lipase in dimethyl carbonate as the solvent. Bioprocess Biosyst. Eng. 2010, 33, 1059–1065. [Google Scholar] [CrossRef]
  176. Wan, J.P.; Cao, S.; Jing, Y. Copper-catalyzed homo- and cross-coupling reactions of terminal alkynes in ethyl lactate. Appl. Organomet. Chem. 2014, 28, 631–634. [Google Scholar] [CrossRef]
  177. Liu, Y.; Wang, H.; Wang, C.; Wan, J.-P. Bio-based green solvent mediated disulfide synthesis via thiol couplings free of catalyst and additive. RSC Adv. 2013, 3, 21369–21372. [Google Scholar] [CrossRef]
  178. Wan, J.-P.; Zhong, S.; Xie, L.; Cao, X.; Liu, Y.; Wei, L. KIO3-catalyzed aerobic cross-coupling reactions of enaminones and thiophenols: Synthesis of polyfunctionalized alkenes by metal-free C-H sulfenylation. Org. Lett. 2016, 18, 584–587. [Google Scholar] [CrossRef]
  179. Pereira, C.S.M.; Silva, V.M.T.M.; Rodrigues, A.E. Ethyl lactate as a solvent: Properties, applications and production processes—A review. Green Chem. 2011, 13, 2658–2671. [Google Scholar] [CrossRef]
  180. Bennett, J.S.; Charles, K.L.; Miner, M.R.; Heuberger, C.F.; Spina, E.J.; Bartels, M.F.; Foreman, T. Ethyl lactate as a tunable solvent for the synthesis of aryl aldimines. Green Chem. 2009, 11, 166–168. [Google Scholar] [CrossRef]
  181. Ghosh, P.P.; Paul, S.; Das, A.R. Light induced synthesis of symmetrical and unsymmetrical dihydropyridines in ethyl lactate–water under tunable conditions. Tetrahedron Lett. 2013, 54, 138–142. [Google Scholar] [CrossRef]
  182. Yang, J.; Tana, J.-N.; Gu, Y. Lactic acid as an invaluable bio-based solvent for organic reactions. Green Chem. 2012, 14, 3304–3317. [Google Scholar] [CrossRef]
  183. Cascone, R. Biobutanol—A replacement for bioethanol? Chem. Eng. Prog. 2008, 104, S4–S9. [Google Scholar]
  184. Fleckenstein, C.A.; Plenio, H. Efficient Suzuki−Miyaura coupling of (hetero)aryl chlorides with thiophene- and furanboronic acids in aqueous n-butanol. J. Org. Chem. 2008, 73, 3236–3244. [Google Scholar] [CrossRef]
  185. Fleckenstein, C.A.; Plenio, H. Highly efficient Suzuki–Miyaura coupling of heterocyclic substrates through rational reaction design. Chem. Eur. J. 2008, 14, 4267–4279. [Google Scholar] [CrossRef]
  186. Chemat, S.; Tomao, V.; Chemat, F. Limonene as green solvent for extraction of natural products. In Green Solvents I: Properties and Applications in Chemistry; Mohammad, A., Inamuddin, Eds.; Springer: Dordrecht, The Netherlands, 2012. [Google Scholar]
  187. Virot, M.; Tomao, V.; Ginies, C.; Visinoni, F.; Chemat, F. Green procedure with a green solvent for fats and oils’ determination: Microwave-integrated Soxhlet using limonene followed by microwave Clevenger distillation. J. Chromatogr. A 2008, 1196–1197, 147–152. [Google Scholar] [CrossRef]
  188. Rasina, D.; Kahler-Quesada, A.; Ziarelli, S.; Warratz, S.; Cao, H.; Santoro, S.; Ackermann, L.; Vaccaro, L. A biomass-derived safe medium to replace toxic dipolar solvents and access cleaner Heck coupling reactions. Green Chem. 2016, 18, 5025–5030. [Google Scholar] [CrossRef] [Green Version]
  189. Pongrácz, P.; Kollárb, L.; Mika, L.T. A step towards hydroformylation under sustainable conditions:platinum-catalysed enantioselective hydroformylation of styrene in gamma-valerolactone. Green Chem. 2016, 18, 842–847. [Google Scholar] [CrossRef]
  190. Song, J.; Zhou, B.; Liu, H.; Xie, C.; Meng, Q.; Zhang, Z.; Han, B. Biomass-derived γ-valerolactone as an efficient solvent and catalyst for the transformation of CO2 to formamides. Green Chem. 2016, 18, 3956–3961. [Google Scholar] [CrossRef]
  191. Durand, M.; Zhu, Y.; Molinier, V.; Feron, T.; Aubry, J.-M. Solubilizing and hydrotropic properties of isosorbide monoalkyl- and dimethyl-ethers. J. Surfact. Deterg. 2009, 12, 371–378. [Google Scholar] [CrossRef]
  192. Mesnager, J.; Quettier, C.; Lambin, A.; Rataboul, F.; Pinel, C. Telomerization of butadiene with starch under mild conditions. ChemSusChem 2009, 2, 1125–1129. [Google Scholar] [CrossRef]
  193. Sambiagio, C.; Munday, R.H.; Blacker, A.J.; Marsden, S.P.; McGowan, P.C. Green alternative solventsfor the copper-catalysed arylation of phenols and amides. RSC Adv. 2016, 6, 70025–70032. [Google Scholar] [CrossRef]
  194. Mouret, A.; Leclercq, L.; Mühlbauer, A.; Nardello-Rataj, V. Eco-friendly solvents and amphiphilic catalytic polyoxometalate nanoparticles: A winning combination for olefin epoxidation. Green Chem. 2014, 16, 269–278. [Google Scholar] [CrossRef]
  195. Zia, H.; Ma, J.K.H.; O’Donnell, J.P.; Luzzi, L.A. Cosolvency of dimethyl isosorbide for steroid solubility. Pharm. Res. 1991, 8, 502–504. [Google Scholar] [CrossRef] [PubMed]
  196. Moity, L.; Molinier, V.; Benazzouz, A.; Joosen, B.; Gerbaud, V.; Aubrey, J.-M. A “top-down” in silico approach for designing ad hoc bio-based solvents: Application to glycerol-derived solvents of nitrocellulose. Green Chem. 2016, 18, 3239–3249. [Google Scholar] [CrossRef] [Green Version]
  197. García, J.I.; García-Marín, H.; Pires, E. Glycerol based solvents: Synthesis, properties and applications. Green Chem. 2014, 16, 1007–1033. [Google Scholar] [CrossRef] [Green Version]
  198. Mottu, F.; Laurent, A.; Rufenacht, D.A.; Doelker, E. Organic solvents for pharmaceutical parenterals and embolic liquids: A review of toxicity data. PDA J. Pharm. Sci. Technol. 2000, 54, 456–469. [Google Scholar]
  199. Taygerly, J.P.; Miller, L.M.; Yee, A.; Peterson, E.A. A convenient guide to help select replacement solvents for dichloromethane in chromatography. Green Chem. 2012, 14, 3020–3025. [Google Scholar] [CrossRef]
  200. Sherwood, J.; Parker, H.L.; Moonen, K.; Farmer, T.J.; Hunt, A.J. N-Butylpyrrolidinone as a dipolar aprotic solvent for organic synthesis. Green Chem. 2016, 18, 3990–3996. [Google Scholar] [CrossRef]
  201. Sherwood, J.; De Bruyn, M.; Constantinou, A.; Moity, L.; McElroy, C.R.; Farmer, T.J.; Duncan, T.; Raverty, W.; Hunt, A.J.; Clark, J.H. Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents. Chem. Commun. 2014, 50, 9650–9652. [Google Scholar] [CrossRef] [PubMed]
  202. Menges, N.; Şahin, E. Metal- and base-free combinatorial reaction for C-acylation of 1,3-diketo compounds in vegetable oil: The effect of natural oil. ACS Sustain. Chem. Eng. 2014, 2, 226–230. [Google Scholar] [CrossRef]
  203. Savile, C.K.; Janey, J.M.; Mundorff, E.C.; Moore, J.C.; Tam, S.; Jarvis, W.R.; Colbeck, J.C.; Krebber, A.; Fleitz, F.J.; Brands, J.; et al. Biocatalytic asymmetric synthesis of chiral amines from ketones applied to sitagliptin manufacture. Science 2010, 329, 305–309. [Google Scholar] [CrossRef] [Green Version]
  204. McCombs, N.L.; Smirnova, T.; Ghiladi, R.A. Oxidation of pyrrole by dehaloperoxidase-hemoglobin: Chemoenzymatic synthesis of pyrrolin-2-ones. Catal. Sci. Technol. 2017, 7, 3104–3118. [Google Scholar] [CrossRef]
  205. Gu, Y.; Barrault, J.; Jerome, F. Glycerol as an efficient promoting medium for organic reactions. Adv. Synth. Catal. 2008, 350, 2007–2012. [Google Scholar] [CrossRef]
  206. Shaik, B.B.; Seboletswe, P.; Mohite, B.S.; Katari, K.N.D.; Bala, D.M.P.; Karpoormath, R.P.; Singh, P.P. Lemon juice: A versatile biocatalyst and green solvent in organic transformations. ChemistrySelect 2022, 7, e202103701. [Google Scholar] [CrossRef]
  207. Campos, J.F.; Berteina-Raboin, S. Eucalyptol, an All-purpose product. Catalysts 2022, 12, 48. [Google Scholar] [CrossRef]
  208. Jordan, A.; Hall, J.G.C.; Thorp, R.L.; Sneddon, F.H. Replacement of less-preferred dipolar aprotic and ethereal solvents in synthetic organic chemistry with more sustainable alternatives. Chem. Rev. 2022, 122, 6749–6794. [Google Scholar] [CrossRef]
  209. Winterton, N. The green solvent: A critical perspective. Clean Technol. Environ. Policy 2021, 23, 2499–2522. [Google Scholar] [CrossRef]
  210. Pace, V.; Hoyos, P.; Castoldi, L.; Dominguez de Maria, P.; Alcantara, A.R. 2-Methyltetrahydrofuran(2-MeTHF): A biomass-derived solvent with broad application in organic chemistry. ChemSusChem 2012, 5, 1369–1379. [Google Scholar] [CrossRef] [PubMed]
  211. Mondal, M.; Bora, U. Eco-friendly Suzuki-Miyaura coupling of arylboronic acids to aromatic ketones catalyzed by the oxime-palladacycle in biosolvent 2-MeTHF. New J. Chem. 2016, 40, 3119–3123. [Google Scholar] [CrossRef]
  212. Ripin, D.; Vetelino, M. 2-Methyltetrahydrofuran as an alternative to dichloromethane in 2-phase reactions. Synlett 2003, 15, 2353. [Google Scholar] [CrossRef]
  213. Wang, Z.Y.; Du, W.Y.; Duan, Z.Q.; Yang, R.L.; Bi, Y.H.; Yuan, X.T.; Mao, Y.Y.; Zhao, Y.P.; Wu, J.; Jia, J.B. Efficient regioselective synthesis of the crotonyl polydatin prodrug by Thermomyces lanuginosus lipase: A kinetics study in eco-friendly 2-methyltetrahydrofuran. Appl. Biochem. Biotechnol. 2016, 179, 1011–1022. [Google Scholar] [CrossRef] [PubMed]
  214. Watanabe, K.; Yamagiwa, N.; Torisawa, Y. Cyclopentyl methyl ether as a new and alternative process solvent. Org. Process Res. Dev. 2007, 11, 251–258. [Google Scholar] [CrossRef]
  215. Watanabe, K. The toxicological assessment of cyclopentyl methyl ether (CPME) as a green solvent. Molecules 2013, 18, 3183–3194. [Google Scholar] [CrossRef] [Green Version]
  216. Antonucci, V.; Coleman, J.; Ferry, J.B.; Johnson, N.; Mathe, M.; Scott, J.P.; Xu, J. Toxicological assessment of 2-methyltetrahydrofuran and cyclopentyl methyl ether in support of their use in pharmaceutical chemical process development. Org. Process Res. Dev. 2011, 15, 939–941. [Google Scholar] [CrossRef]
  217. Montanino, M.; Moreno, M.; Alessandrini, F.; Appetecchi, G.B.; Passerini, S.; Zhou, Q.; Henderson, W.A. Physical and electrochemical properties of binary ionic liquid mixtures: (1 − x) PYR14TFSI–(x) PYR14IM14. Electrochim. Acta 2012, 60, 163–169. [Google Scholar] [CrossRef]
  218. Domańska, U. Physico-chemical properties and phase behavior of pyrrolidinium-based ionic liquids. Int. J. Mol. Sci. 2010, 11, 1825–1841. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  219. Bonhôte, P.; Dias, P.A.; Papageorgiou, N.; Kalyanasundaram, K.; Grätzel, M. Hydrophobic, highly conductive ambient-temperature molten salts. Inorg. Chem. 1996, 35, 1168–1178. [Google Scholar] [CrossRef] [PubMed]
  220. Walkoli1, T.A.; Sonawane, D.P.D. Ionic liquids: Eco-friendly solvent. RRBB 2022, 9, 9–13. [Google Scholar] [CrossRef]
  221. Dupont, J.; De Souza, R.F.; Suarez, P.A.Z. Ionic liquid (molten salt) phase organometallic catalysis. Chem. Rev. 2002, 102, 3667–3692. [Google Scholar] [CrossRef] [PubMed]
  222. Davis, J.H., Jr. Task-specific ionic liquids. Chem. Lett. 2004, 33, 1072–1077. [Google Scholar] [CrossRef]
  223. Welton, T. Room-temperature ionic liquids. Solvents for synthesis and catalysis. Chem Rev. 1999, 99, 2071–2084. [Google Scholar] [CrossRef] [PubMed]
  224. Dyson, J.P.; Geldbach, J.T. Interface-Ionic Liquids. In The Electrochemical Society Interface; Spring: Chicago, IL, USA, 2007. [Google Scholar]
  225. Ivaništšev, V.; Fedorov, M.V. Interfaces between Charged Surfaces and Ionic Liquids: Insights from Molecular Simulations. Electrochem. Soc. Interface 2014, 23, 65. [Google Scholar] [CrossRef] [Green Version]
  226. Hossain, M.M.; Rawal, A.; Aldous, L. Aprotic vs. Protic Ionic Liquids for Lignocellulosic Biomass Pretreatment: Anion Effects, Enzymatic Hydrolysis, Solid-State NMR, Distillation, and Recycle. ACS Sustain. Chem. Eng. 2019, 7, 11928–11936. [Google Scholar] [CrossRef]
  227. Van Osch, D.J.G.P.; Zubeir, L.F.; Van den Bruinhorst, A.; Rocha, M.A.A.; Kroon, M.C. Hydrophobic deep eutectic solvents as water-immiscible extractants. Green Chem. 2015, 17, 4518–4521. [Google Scholar] [CrossRef] [Green Version]
  228. Cao, J.; Su, E. Hydrophobic deep eutectic solvents: The new generation of green solvents for diversified and colorful applications in green chemistry. J. Clean. Prod. 2021, 314, 127965. [Google Scholar] [CrossRef]
  229. Liu, X.; Chen, M.; Meng, Z.; Qian, H.; Zhang, S.; Lu, R.; Gao, H.; Zhou, W. Extraction of benzoylurea pesticides from tea and fruit juices using deep eutectic solvents. J. Chromatogr. B 2020, 1140, 121995. [Google Scholar] [CrossRef]
  230. Werner, J. Novel deep eutectic solvent-based ultrasounds-assisted dispersive liquid-liquid microextraction with solidification of the aqueous phase for hplc-uv determination of aromatic amines in environmental samples. Microchem. J. 2020, 153, 104405. [Google Scholar] [CrossRef]
  231. Riveiro, E.; Gonzalez, B.; Domínguez, Á. Extraction of adipic, levulinic and succinic acids from water using topo-based deep eutectic solvents. Separ. Purif. Technol. 2020, 241, 116692. [Google Scholar] [CrossRef]
  232. Tahghighi, A.; Babalouei, F. Thiadiazoles: The appropriate pharmacological scaffolds with leishmanicidal and antimalarial activities: A review. Iran. J. Basic Med. Sci. 2017, 20, 613–622. [Google Scholar] [CrossRef] [PubMed]
  233. Iizawa, Y.; Okonogi, K.; Hayashi, R.; Iwahi, T.; Yamazaki, T.; Imada, A. Therapeutic Effect of Cefozopran (SCE-2787), a New Parenteral Cephalosporin, against Experimental Infections in Mice. Antimicrob. Agents Chemother. 1993, 37, 100–105. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  234. Frija, T.M.L.; Pombeiro, L.J.A.; Kopylovich, N.M. Building 1,2,4-Thiadiazole: Ten Years of Progress. Eur. J. Org. Chem. 2017, 2017, 2670–2682. [Google Scholar] [CrossRef]
  235. Irfan, A.; Batool, F.; Ahmad, S.; Ullah, R.; Sultan, A.; Sattar, R.; Nisar, B.; Rubab, L. Recent trends in the synthesis of 1,2,3-thiadiazoles. Phosphorus Sulfur Silicon Relat. Elem. 2019, 194, 1098–1115. [Google Scholar] [CrossRef]
  236. Irfan, A.; Ullah, S.; Anum, A.; Jabeen, N.; Zahoor, A.F.; Kanwal, H.; Kotwica-Mojzych, K.; Mojzych, M. Synthetic Transformations and Medicinal Significance of 1,2,3-Thiadiazoles Derivatives: An Update. Appl. Sci. 2021, 11, 5742. [Google Scholar] [CrossRef]
  237. Decking, U.K.; Hartmann, M.; Rose, H.R.; Meil, J.B.; Schrader, J. Cardioprotective actions of KC 12291. I. Inhibition of voltage-gated Na+ channels in ischemia delays myocardial Na+ overload. Naunyn Schmiedeberg’s Arch. Pharmacol. 1998, 358, 547–553. [Google Scholar] [CrossRef] [PubMed]
  238. Proshin, A.N.; Serkov, I.V.; Petrova, L.N.; Bachurin, O.S. 5-Amino-3-(2-aminopropyl)-1,2,4-thiadiazoles as the basis of hybrid multifunctional compounds. Russ. Chem. Bull. 2014, 63, 1148–1152. [Google Scholar] [CrossRef]
  239. Fawzi, A.B.; Macdonald, D.; Benbow, L.L.; Smith-Torhan, A.; Zhang, H.T.; Weig, B.C.; Ho, G.; Tulshian, D.; Linder, M.E.; Graziano, M.P. SCH-202676: An allosteric modulator of both agonist and antagonist binding to G protein-coupled receptors. Mol. Pharmacol. 2001, 59, 30. [Google Scholar] [CrossRef] [PubMed]
  240. Hartmann, M.; Decking, U.K.M.; Schrader, J. Cardioprotective actions of KC 12291 II. Delaying Na+ overload in ischemia improves cardiac function and energy status in reperfusion. Naunyn Schmiedeberg’s Arch. Pharmacol. 1998, 358, 554. [Google Scholar] [CrossRef] [PubMed]
  241. Martínez, A.; Alonso, M.; Castro, A.; Pérez, C.; Moreno, F.J. First Non-ATP Competitive Glycogen Synthase Kinase 3 â (GSK-3â) Inhibitors: Thiadiazolidinones (TDZD) as Potential Drugs for the Treatment of Alzheimer’s Disease. J. Med. Chem. 2002, 45, 1292–1299. [Google Scholar] [CrossRef]
  242. Kumar, D.; Kumar, N.-M.; Chang, K.-H.; Shah, K. Synthesis and anticancer activity of 5-(3-indolyl)-1,3,4-thiadiazoles. Eur. J. Med. Chem. 2010, 45, 4664–4668. [Google Scholar] [CrossRef] [PubMed]
  243. Romagnoli, R.; Baraldi, G.P.; Carrion, D.M.; Cruz-Lopez, O.; Preti, D.; Tabrizi, A.M.; Fruttarolo, F.; Heilmann, F.; Bermejo, J.; Estevez, F. Hybrid molecules containing benzo[4,5]imidazo-[1,2-d][1,2,4]thiadiazole and a-bromoacryloyl moieties as potent apoptosis inducers on human myeloid leukaemia cells. Bioorg. Med. Chem. Lett. 2007, 17, 2844. [Google Scholar] [CrossRef] [PubMed]
  244. Camoutsis, c.; Geronikaki, A.; Ciric, A.; Soković, M.; Zoumpoulakis, P.; Zervou, M. Sulfonamide-1,2,4-thiadiazole derivatives as antifungal and antibacterial agents: Synthesis, biological evaluation, lipophilicity, and conformational studies. Chem. Pharm. Bull. 2010, 58, 160. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  245. Song, Y.T.; Connor, D.T.; Sercel, A.D.; Sorenson, R.J.; Doubleday, R.; Unangst, P.C.; Roth, B.D.; Beylin, V.G.; Gilbertsen, R.B.; Chan, K.; et al. Synthesis, Structure–Activity Relationships, and in Vivo Evaluations of Substituted Di-tert-butylphenols as a Novel Class of Potent, Selective, and Orally Active Cyclooxygenase-2 Inhibitors. 2. 1,3,4- and 1,2,4-Thiadiazole Series. J. Med. Chem. 1999, 42, 1161. [Google Scholar] [CrossRef] [PubMed]
  246. Leung-Toung, R.; Tam, F.T.; Zhao, Y.; Simpson, D.C.; Li, W.; Desilets, D.; Karimian, K. Synthesis of 3-substituted bicyclic imidazo[1,2-d][1,2,4]thiadiazoles and tricyclic benzo[4,5]imidazo[1,2-d][1,2,4]thiadiazoles. J. Org. Chem. 2005, 70, 6230–6241. [Google Scholar] [CrossRef]
  247. Gupta, A.; Mishra, P.; Pandeya, S.N.; Kashaw, S.K.; Kashaw, V.; Stables, J.P. Synthesis and anticonvulsant activity of some substituted 1,2,4-thiadiazoles. Eur. J. Med. Chem. 2009, 44, 1100–1105. [Google Scholar] [CrossRef]
  248. Shen, L.; Zhang, Y.; Wang, A.; Sieber-McMaster, E.; Chen, X.; Pelton, P.; Xu, J.Z.; Yang, M.; Zhu, P.; Zhou, L.; et al. Synthesis and Identification of [1,2,4]Thiadiazole Derivatives as a New Series of Potent and Orally Active Dual Agonists of Peroxisome Proliferator-Activated Receptors α and δ. J. Med. Chem. 2007, 50, 3954. [Google Scholar] [CrossRef]
  249. Nieuwendijk, D.V.; Pietra, D.; Heitman, L.; Göblyös, A.; Ijzerman, A.P. Synthesis and Biological Evaluation of 2,3,5-Substituted [1,2,4]Thiadiazoles as Allosteric Modulators of Adenosine Receptors. J. Med. Chem. 2004, 47, 663. [Google Scholar] [CrossRef]
  250. Unangst, P.C.; Shrum, G.P.; Connor, D.T.; Dyer, R.D.; Schrier, D.J. Novel 1,2,4-oxadiazoles and 1,2,4-thiadiazoles as dual 5-lipoxygenase and cyclooxygenase inhibitors. J. Med. Chem. 1992, 35, 3691. [Google Scholar] [CrossRef]
  251. Tam, T.F.; Leung-Toung, R.; Li, W.; Spino, M.; Karimian, K. Medicinal chemistry and properties of 1,2,4-thiadiazoles. Mini Rev. Med. Chem. 2005, 5, 367–379. [Google Scholar] [CrossRef] [PubMed]
  252. Li, Y.; Geng, J.; Liu, Y.; Yu, S.; Zhao, G. Thiadiazole-a Promising Structure in Medicinal Chemistry. ChemMedChem 2013, 8, 27–41. [Google Scholar] [CrossRef] [PubMed]
  253. Mariappan, A.; Rajaguru, K.; Noufal, M.C.; Muthusubramanian, S.; Bhuvanesh, N. Hypervalent Iodine(III) Mediated Synthesis of 3-Substituted 5-Amino-1,2,4-thiadiazoles through Intramolecular Oxidative S–N Bond Formation. J. Org. Chem. 2016, 81, 6573. [Google Scholar] [CrossRef] [PubMed]
  254. Wang, B.; Meng, Y.; Zhou, Y.; Ren, L.; Wu, J.; Yu, W.; Chang, J. ynthesis of 5-Amino and 3,5-Diamino Substituted 1,2,4-Thiadiazoles by I2-Mediated Oxidative N–S Bond Formation. J. Org. Chem. 2017, 82, 5898. [Google Scholar] [CrossRef]
  255. Tumula, N.; Jatangi, N.; Palakodety, K.R.; Balasubramanian, S.; Nakka, M. I2-Catalyzed Oxidative N–S Bond Formation: Metal-Free Regiospecific Synthesis of N-Fused and 3,4-Disubstituted 5-Imino-1,2,4-thiadiazoles. J. Org. Chem. 2017, 82, 5310. [Google Scholar] [CrossRef]
  256. Chai, L.; Xu, Y.; Ding, T.; Fang, S.; Zhang, W.; Wang, Y.; Lu, M.; Xu, H.; Yang, X. One-pot synthesis of 3,5-disubstituted 1,2,4-thiadiazoles from nitriles and thioamides via I2-mediated oxidative formation of an N–S bond. Org. Biomol. Chem. 2017, 15, 8410. [Google Scholar] [CrossRef]
  257. Chauhan, S.; Verma, P.; Mishra1, A.; Srivastava, V. An Expeditious Ultrasound-Initiated Green Synthesis of 1,2,4-Thiadiazoles in Water. Chem. Heterocycl. Comp. 2020, 56, 123. [Google Scholar] [CrossRef]
  258. Zhao, J.-W.; Xu, J.-X.; Guo, X.-Z. Green synthesis of 1,2,4-thiadizoles from thioamides in water using molecular oxygen as an oxidant. Chin. Chem. Lett. 2014, 25, 1499. [Google Scholar] [CrossRef]
  259. Yang, Z.; Cao, T.; Liu, S.; Li, A.; Liu, K.; Yang, T.; Zhou, C. Transition-metal-free S–N bond formation: Synthesis of 5-amino-1,2,4-thiadiazoles from isothiocyanates and amidines. New J. Chem. 2019, 43, 6465. [Google Scholar] [CrossRef]
  260. Boeini, Z.H. Green Protocol for Synthesis of the 3,5-disubstituted 1,2,4-thiadiazoles Using N-benzyl-DABCO-tribromide in Aqueous Media. J. Iran. Chem. Soc. 2009, 6, 547. [Google Scholar] [CrossRef]
  261. Boeini, Z.H. Highly Efficient Synthesis of 3,5-Diaryl-1,2,4-thiadiazoles in Water–Wet Paste Conditions. Synth. Commun. 2011, 41, 2932. [Google Scholar] [CrossRef]
  262. Khosropour, R.A.; Noei, J. Monatsh. A convenient strategy for the synthesis of 3,5-diaryl-1,2,4-thiadiazoles: Oxidative dimerization of arylthioamides using CC–DMSO in PEG-400. Monatshefte für Chemie 2010, 141, 649. [Google Scholar] [CrossRef]
  263. Xua, Y.; Chena, J.; Gao, W.; Jina, H.; Dinga, J.; Wua, H. Solvent-free synthesis of 3,5-di(hetero)aryl-1,2,4-thiadiazoles by grinding of thioamides under oxidative conditions. J. Chem. Res. 2010, 34, 151–153. [Google Scholar] [CrossRef]
  264. Fordyce, A.F.E.; Morrison, A.J.; Sharp, R.D.; Paton, M.R. Microwave-induced generation and reactions of nitrile sulfides: An improved method for the synthesis of isothiazoles and 1,2,4-thiadiazole. Tetrahedron 2010, 66, 7192–7197. [Google Scholar] [CrossRef]
  265. Zali-Boeinia, H.; Shokrolahib, A.; Zalib, A.; Ghanib, K. Highly efficient synthesis of 3,5-disubstituted 1,2,4-thiadiazoles using pentylpyridinium tribromide as a solvent/reagent ionic liquid. J. Sulphur Chem. 2012, 33, 165–170. [Google Scholar] [CrossRef]
  266. Kim, H.-Y.; Kwak, H.S.; Lee, G.-H.; Gong, Y.-D. Copper-catalyzed synthesis of 3-substituted-5-amino-1,2,4-thiadiazoles via intramolecular NeS bond formation. Tetrahedron 2014, 70, 8737–8743. [Google Scholar] [CrossRef]
  267. Yoshimura, A.; Todora, D.A.; Kastern, J.B.; Koski, R.S.; Zhdankin, V.V. Synthesis of 1,2,4-Thiadiazoles by Oxidative Dimerization of Carbothioamides by Using Oxone. Eur. J. Org. Chem. 2014, 2014, 5149–5152. [Google Scholar] [CrossRef]
  268. Jatangi, N.; Tumula, N.; Palakodety, K.R.; Nakka, M. I2-Mediated oxidative C-N and N-S bond formation in water:A metal-free synthesis of 4,5-disubstituted/N-fused 3-amino-1,2,4-triazoles and 3-substituted 5-amino-1,2,4-thiadiazoles. J. Org. Chem. 2018, 83, 5715–5723. [Google Scholar] [CrossRef]
  269. Chacko, P.; Shivashankar, K. Montmorillonite K10-catalyzed synthesis of N-fused imino-1,2,4-thiadiazolo isoquinoline derivatives. Synth. Commun. 2018, 48, 1363–1376. [Google Scholar] [CrossRef]
  270. Cao, X.-T.; Zheng, Z.-L.; Liu, J.; Hu, Y.-H.; Yu, H.-Y.; Cai, S.; Wang, G. H2O2-Mediated Synthesis of 1,2,4-Thiadiazole Derivatives in Ethanol at Room Temperature. Adv. Synth. Catal. 2022, 364, 689–694. [Google Scholar] [CrossRef]
Catalysts 12 01329 g001 550
Figure 1. Twelve principles of green chemistry.
Figure 1. Twelve principles of green chemistry.
Catalysts 12 01329 g001
Catalysts 12 01329 g002 550
Figure 2. Green approaches and their advantages over conventional approaches.
Figure 2. Green approaches and their advantages over conventional approaches.
Catalysts 12 01329 g002
Catalysts 12 01329 g003 550
Figure 3. Characteristics of ideal green synthetic approach.
Figure 3. Characteristics of ideal green synthetic approach.
Catalysts 12 01329 g003
Catalysts 12 01329 g004 550
Figure 4. Bioactive thiadiazole scaffolds.
Figure 4. Bioactive thiadiazole scaffolds.
Catalysts 12 01329 g004
Catalysts 12 01329 sch001 550
Scheme 1. Synthesis of 1,2,4-thiadiazoles 3 via intramolecular cyclization.
Scheme 1. Synthesis of 1,2,4-thiadiazoles 3 via intramolecular cyclization.
Catalysts 12 01329 sch001
Catalysts 12 01329 sch002 550
Scheme 2. Synthesis of 1,2,4-thiadiazoles 5 via molecular I2 as sole oxidant.
Scheme 2. Synthesis of 1,2,4-thiadiazoles 5 via molecular I2 as sole oxidant.
Catalysts 12 01329 sch002
Catalysts 12 01329 sch003 550
Scheme 3. Regio-specific synthesis of 3,4-disubstituted 5-imino-1,2,4-thiadiazole hybrids 8, 10.
Scheme 3. Regio-specific synthesis of 3,4-disubstituted 5-imino-1,2,4-thiadiazole hybrids 8, 10.
Catalysts 12 01329 sch003
Catalysts 12 01329 sch004 550
Scheme 4. One-pot green synthesis of 3,5-disubstituted 1,2,4-thiadiazoles.
Scheme 4. One-pot green synthesis of 3,5-disubstituted 1,2,4-thiadiazoles.
Catalysts 12 01329 sch004
Catalysts 12 01329 sch005 550
Scheme 5. Ultrasonic-assisted synthesis of 1,2,4-thiadiazoles 15.
Scheme 5. Ultrasonic-assisted synthesis of 1,2,4-thiadiazoles 15.
Catalysts 12 01329 sch005
Catalysts 12 01329 sch006 550
Scheme 6. Synthesis of 1,2,4-thiadiazoles 17 using molecular oxygen as oxidant.
Scheme 6. Synthesis of 1,2,4-thiadiazoles 17 using molecular oxygen as oxidant.
Catalysts 12 01329 sch006
Catalysts 12 01329 sch007 550
Scheme 7. Green region-selective synthesis of 5-amino-1,2,4-thiadiazoles 20.
Scheme 7. Green region-selective synthesis of 5-amino-1,2,4-thiadiazoles 20.
Catalysts 12 01329 sch007
Catalysts 12 01329 sch008 550
Scheme 8. Green synthesis of substituted 1,2,4-thiadiazoles 22 in solid–solid wet conditions.
Scheme 8. Green synthesis of substituted 1,2,4-thiadiazoles 22 in solid–solid wet conditions.
Catalysts 12 01329 sch008
Catalysts 12 01329 sch009 550
Scheme 9. Green synthesis of substituted 1,2,4-thiadiazoles 25.
Scheme 9. Green synthesis of substituted 1,2,4-thiadiazoles 25.
Catalysts 12 01329 sch009
Catalysts 12 01329 sch010 550
Scheme 10. Green synthesis of substituted diaryl-1,2,4-thiadiazoles 27.
Scheme 10. Green synthesis of substituted diaryl-1,2,4-thiadiazoles 27.
Catalysts 12 01329 sch010
Catalysts 12 01329 sch011 550
Scheme 11. Green synthesis of substituted diaryl-1,2,4-thiadiazoles 30 via grinding.
Scheme 11. Green synthesis of substituted diaryl-1,2,4-thiadiazoles 30 via grinding.
Catalysts 12 01329 sch011
Catalysts 12 01329 sch012 550
Scheme 12. Microwave-assisted synthesis of substituted-1,2,4-thiadiazoles 33.
Scheme 12. Microwave-assisted synthesis of substituted-1,2,4-thiadiazoles 33.
Catalysts 12 01329 sch012
Catalysts 12 01329 sch013 550
Scheme 13. Synthesis of 1,2,4-thiadiazoles 27 via RTIL.
Scheme 13. Synthesis of 1,2,4-thiadiazoles 27 via RTIL.
Catalysts 12 01329 sch013
Catalysts 12 01329 sch014 550
Scheme 14. Green synthesis of 5-amino-1,2,4-thiadiazoles via copper catalysis.
Scheme 14. Green synthesis of 5-amino-1,2,4-thiadiazoles via copper catalysis.
Catalysts 12 01329 sch014
Catalysts 12 01329 sch015 550
Scheme 15. Green synthesis of 1,2,4-thiadiazoles 17 via oxone as safe oxidant.
Scheme 15. Green synthesis of 1,2,4-thiadiazoles 17 via oxone as safe oxidant.
Catalysts 12 01329 sch015
Catalysts 12 01329 sch016 550
Scheme 16. Green strategy for synthesis of5-amino-1,2,4-thiadiazoles 39.
Scheme 16. Green strategy for synthesis of5-amino-1,2,4-thiadiazoles 39.
Catalysts 12 01329 sch016
Catalysts 12 01329 sch017 550
Scheme 17. Green synthesis of N-fused imino-1,2,4-thiadiazolo isoquinolines 41.
Scheme 17. Green synthesis of N-fused imino-1,2,4-thiadiazolo isoquinolines 41.
Catalysts 12 01329 sch017
Catalysts 12 01329 sch018 550
Scheme 18. Green synthesis of 1,2,4-thiadoazole derivatives 5.
Scheme 18. Green synthesis of 1,2,4-thiadoazole derivatives 5.
Catalysts 12 01329 sch018
Table
Table 1. Types of catalysts used in green organic synthesis.
Table 1. Types of catalysts used in green organic synthesis.
Green Catalyst TypeExamples
Lewis acids catalysts in waterScandium tris(heptadecafluorooctanesulfonate) (Sc(O3 SC8 F17)3) in supercritical carbon dioxide (scCO2), cationic surfactant, cetyltrimethylammonium bromide (CTAB), Sc(OTf)3–SDS and rare earth metal triflates can be used in carbon–carbon bond-forming reactions in aqueous media [47,48].
Zeolites as green catalystsH-, Cu- and Sc-zeolites as green Lewis catalysts for the carbonylation, glycosylation, aldolization, click reactions, multicomponent reactions, halogenation, cycloadditions, coupling reactions and cyclization [49].
Enzyme catalysisEnzymatic redox catalyst, lipases, aldolases, transaminases, hydroxynitrile lyases and hydrolases [50].
Heteropoly acid-based (HPAs) catalysisHPAs can be designed in homogeneous and heterogeneous systems such as Amberlyst-15, PCPs–SO3H, BC–SO3H, CMK-3-SO3H, Zn–Ca–Fe, CsH2PW12O40, Ru/CMK-3, Fe3O4-SBA–SO3H, CaFe2O4, H3PW12O40, H5BW12O40, H5AlW12O40, H5GaW12O40 and H6CoW12O40 [46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62].
Natural materials and foods as catalystsWood ash biocatalyst [63], alginic acid [64,65], boric acid [66], tartaric acid [67,68], citric acid [69,70,71], pectin [72], oxalic acid [73,74,75], saccharin [46,76,77], wool and keratin deriving from wool fibers [78,79,80], feathers [81,82,83,84], silk [85,86], plant derivatives, lemon juice [87,88].
Nano particles (NPs)/materials as catalystsMagnetic nano catalysts (magnetic Fe3O4, magnetic zinc ferrite ZnFe2O4, CuFe2O4, CoFe2O4, NiFe2O4, NiFe2O4@Cu) and oxides; ferrites with a shell; metallic with a shell [89,90,91,92], K10 clay, K10 montmorillonite and clayfen [93,94], magnesium oxide NPs, cerium oxide NPs, gold NPs, silica titanium oxide NPs, silica vanadium oxide NPs, iridium oxide NPs, molybdenum–bismuth bimetallic chalcogenide NPs, platinum–antimony tin oxide NPs, calcium oxide NPs, palladium NPs, tin oxide NPs [95,96,97,98,99,100,101,102,103,104,105,106,107]
Transition metals as green catalystsRu(CO)3(TPPMS)2 (TPPMS = (C6H5)2P(m-C6H4SO3Na)), RuH2(CO)(TPPMS)3, [RuH(CO)(NCMe)(TPPMS)3][BF4], Rh/TPPTS complexes, Ru/(R)-BINAP,Ru/(R)-13-[(S,S)-DPEN]Cl2, Ru/(S)-BINAP, Pd-DPPP, Pd(OAc)2, CuI,MnBr(CO)5 [108,109,110,111,112,113,114,115,116,117]
Ionic liquids as catalystsPOM-based ILs (POM-ILs) such as (4-sulfonic acid) butyltributyl amine (TBABS) such as cations and H5PMo10V2O40 (Mo10V2) such as anion (3-sulfonic acid) propylpyridine (PyPS), (4-sulfonic acid) butylpyridine (PyBS), palladium deposited oleic acid coated-Fe3O4 NPs (Fe3O4@OA–Pd) and (4-sulfonic acid) butyltrimethyl amine (TMABS) [118,119,120,121]. Acidic ionic liquids such as [HO3S-(CH2)3-mim] Cl-FeCl3 and Brønsted Lewis acidic ILs, (1-butyl-3-methylimidazolium hydrogen sulfate or 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate) ILs [122,123]. Following different ionic liquids also used as catalysts for the productions of biodiesel, which are: SBA- IL-3, PIL-3, P(VB-VS)HSO4, MIL-101(Cr)@ MBIAILs, Fe3O4@HKUST-1, AILs/HPW/UiO-66-2COOH and CoFe2O4/MIL-88B(Fe)-NH2/(Py-Ps)PMo [124,125,126,127,128,129,130,131]. Ionic liquids are classified into three groups: solid catalyst with ionic liquid layers (SCILL), porous ionic liquids and supported ionic liquid phase catalyst (SILPC). Binary alkoxide ionic liquids catalyzed organic reaction and examples of such ILs are ([Pyrr1,4][NTf2]x[OiPr] 1,3-butylmethylimidazolium hydroxide([BMIM][OH]) and [C2DABCO][NTf2] [132,133,134,135,136].
Photocatalyst (PC)Carbonylation approaches in organic synthesis were mediated by photocatalysts, such as [Ir(4-Fppy)2(bpy)]+, Ru(bpy)32+, fac-Ir(ppy)3, 4-CzIPN, fluorescein, Ir[(dF(CF3)(ppy)]2(dtbbpy)+, eosin and various MOFs composite-based photocatalyst were afforded for their applications in different synthetic approaches such as PCN-250-Fe3, Uio-68-TZDC, MIL-88A(Fe), ZIF-8, Ni-MOF and Ru(bpy)3@NKMOF-7. Following, different heterogeneous photocatalysis have been used in organic synthesis such as TiO2, TiO2 P25, dye-sensitized TiO2, metal doped TiO2, bismuth (III) oxide-based PCs, cadmium sulfide and cadmium-selenide-based PCs, lead halide perovskites and graphitic carbon nitrides (g-CN) PCs, [137,138,139,140,141].
Phase transfer catalyst (PTC)Tetrabutylammonium bromide (TBAB), triethylbenzylammonium chloride (TEBAC) and tetrabutylammonium iodide (TBAI) are famous phase-transfer green catalysts used in organic synthetic transformations. The types of PTC are the following: onium salt phase-transfer catalysts, crown ether and polyether phase-transfer catalyst and supported phase-transfer catalysts [142,143,144,145,146].
Table
Table 2. Green solvents in organic synthesis.
Table 2. Green solvents in organic synthesis.
Type of Green SolventExamples
Aqueous and super critical carbon dioxideH2O, scCO2, scCO2 + H2O [121,122,123,124,125,155,156,157,158,159].
Fluorous solvents1,1,1-trifluoroethanol,perfluoromethyl cyclohexane/toluene—[160,161].
Organic carbonatesButylene carbonate, propylene carbonate, diethyl
Carbonate and dimethyl carbonate (CH3OCOOCH3) [162,163,164,165,166,167,168,169,170,171,172,173,174,175].
Lactates and general solventsLactic acid, ethyl lactate, lactate dehydrogenase, transaminase and n-butanol [176,177,178,179,180,181,182,183,184,185].
Natural and biosolventsLimonene and P-cymene as solvent, γ-valerolactone (GVL), sugar-derived dimethylisosorbide (DMI), glycerol and glycerol derivatives as solvents such as glycerol carbonate, glycerol-derived acetals and ketals, 2,3-propanediol, 1,3-propanediol, monoacylglycerol MAGs, diacylglycerols DAGs, triacylglycerols TAGs, glycidyl monoalkyl ethers, glycidyl dialkyl ethers, glycidyl trialkyl ethers and dihydrolevoglucosenone (cyrene), etc. [186,187,188,189,190,191,192,193,194,195,196,197,198,199,200,201]. Corn oil, glycerol, oxidoreductases, transferases, hydrolases, lyases, isomerases, ligases, dehaloperoxidase (DHP), lemon juice as solvent and eucalyptol used as solvent for the synthesis of N, O and S heterocycles, cygnet a family of green solvents and dimethyl isosorbide (DMI) solvent derived from cellulose [202,203,204,205,206,207,208,209].
Archetypal green solvents2-methyl tetrahydrofuran (2-MeTHF) and cyclopentyl methyl ether (CPME), etc. [210,211,212,213,214,215,216].
Ionic liquids as solvents1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), sodium dicyanamide, sodium thiocyanate, silver nitrate, sodium nitrate, chloroauric acid, 1-ethyl-3-methyl-(EMIM), 1-butyl-3-methyl-(BMIM), 1-octyl-3 methyl (OMIM), 1-decyl-3-methyl-(DMIM), 1-dodecyl-3-methyl- docecylMIM), 1-ethyl-3-methyl imidazolium salts, etc. [217,218,219,220,221,222,223,224,225,226,227].
Deep eutectic solvents (DESs)The classification and general examples of DES are as follows: Class I Cat + X-zMClx, M = Zn, Sn, Fe, Al, Ga. Class II Cat + X-zMClx• yH2O, M = Cr, Co, Cu, Ni, Fe. Class III Cat + X-zRZ Z = CONH2, COOH, OH. Class IV MClx + RZ = MClx-1 + ⋅RZ + MClx+ -1 M = Al, Zn and Z = CONH2, OH. New type Class V RZ + RP Z = CONH2, COOH, OH and P––C6H4OH, CO, NH2. Hydrophobic deep eutectic solvents (HDESs) play a role in green chemistry. The first HDESs (cecanoic acid (DecA)) were synthesized by Osch et al. The following solvents (tetradecyl) phosphonium tetrafluoroborate (P14,666Cl), trioctylphosphine oxide (TOPO) and N-didodecylammonium chloride (DDDACl) have been developed as green HDESs [228,229,230,231].
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Rubab, L.; Anum, A.; Al-Hussain, S.A.; Irfan, A.; Ahmad, S.; Ullah, S.; Al-Mutairi, A.A.; Zaki, M.E.A. Green Chemistry in Organic Synthesis: Recent Update on Green Catalytic Approaches in Synthesis of 1,2,4-Thiadiazoles. Catalysts 2022, 12, 1329. https://doi.org/10.3390/catal12111329

AMA Style

Rubab L, Anum A, Al-Hussain SA, Irfan A, Ahmad S, Ullah S, Al-Mutairi AA, Zaki MEA. Green Chemistry in Organic Synthesis: Recent Update on Green Catalytic Approaches in Synthesis of 1,2,4-Thiadiazoles. Catalysts. 2022; 12(11):1329. https://doi.org/10.3390/catal12111329

Chicago/Turabian Style

Rubab, Laila, Ayesha Anum, Sami A. Al-Hussain, Ali Irfan, Sajjad Ahmad, Sami Ullah, Aamal A. Al-Mutairi, and Magdi E. A. Zaki. 2022. "Green Chemistry in Organic Synthesis: Recent Update on Green Catalytic Approaches in Synthesis of 1,2,4-Thiadiazoles" Catalysts 12, no. 11: 1329. https://doi.org/10.3390/catal12111329

APA Style

Rubab, L., Anum, A., Al-Hussain, S. A., Irfan, A., Ahmad, S., Ullah, S., Al-Mutairi, A. A., & Zaki, M. E. A. (2022). Green Chemistry in Organic Synthesis: Recent Update on Green Catalytic Approaches in Synthesis of 1,2,4-Thiadiazoles. Catalysts, 12(11), 1329. https://doi.org/10.3390/catal12111329

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop