Layered double hydroxides as heterogeneous catalyst systems in the cross-coupling reactions: an overview.

Layered double hydroxides (LDHs) are recognized as two-dimensional (2D) clay materials, which comprise the interlayer anions and host layers with a positive charge (brucite-like M(OH)6 octahedral). They have been used as effective and eco-friendly heterogeneous catalytic systems in cross-coupling reactions. In this review, we try to underscore the applications of (LDHs) as an efficient and green catalyst in some important name reactions, namely Suzuki, Heck, Sonogashira, and Ullmann cross-coupling reactions leading to carbon-carbon bond formations.

Applications of Transition-Metal-Catalyzed Asymmetric Allylic Substitution in Total Synthesis of Natural Products: An Update.

Metal-catalyzed asymmetric allylic substitution (AAS) reaction is one of the most synthetically useful reactions catalyzed by metal complexes for the formation of carbon-carbon and carbon-heteroatom bonds. It comprises the substitution of allylic substrates with a wide range of nucleophiles or SN 2'-type allylic substitution, which results in the formation of the above-mentioned bonds with high levels of enantioselective induction. AAS reaction tolerates a broad range of functional groups, thus has been successfully applied in the asymmetric synthesis of a wide range of optically pure compounds. This reaction has been extensively used in the total synthesis of several complex molecules, especially natural products. In this review, we try to highlight the applications of metal (Pd, Ir, Mo, or Cu)-catalyzed AAS reaction in the total synthesis of the biologically active natural products, as a key step, updating the subject from 2003 till date.

Recent Advances on Heteroatom-Doped Porous Carbon/Metal Materials: Fascinating Heterogeneous Catalysts for Organic Transformations.

Design and preparation of low-cost, effective, and novel catalysts are important topics in the field of heterogeneous catalysis from academic and industrial perspectives. Recently, heteroatom-doped porous carbon/metal materials have received significant attention as promising catalysts in divergent organic reactions. Incorporation of heteroatom into the carbon framework can tailor the properties of carbon, providing suitable interaction between support and metal, resulting in superior catalytic performance compared with those of traditional pure carbon/metal catalytic systems. In this review, we try to underscore the recent advances in the design, preparation, and application of heteroatom-doped porous carbon/metal catalysts towards various organic transformations.

Electrochemically Induced Diels-Alder Reaction: An Overview.

One of the most important name reactions in organic chemistry, is the Diels-Alder cycloaddition reaction. It is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile to construct a substituted cyclohexene derivative. It is the stereotypical example of a pericyclic reaction with a concerted mechanism. In synthesis, the use of electricity instead of stoichiometric amounts of oxidant or reducing agents is definitely appealing for economic, ecological and selective, reasons. In this review, we try to underscore the combination of the electrosynthesis with Diels-Alder cycloaddition reaction to establish of a powerful synthetic tool which may encourage synthetic organic chemists to use it in the future.

Synthesis of N-heterocycles containing 1,5-disubstituted-1H-tetrazole via post-Ugi-azide reaction.

Ugi-azide four-component reaction (UA-4CR) as development on Ugi four-component reaction (U-4CR) is the condensation reaction involving an aldehyde, an amine, an isocyanide, and an azide source. Nowadays, UA-4CR has been employed for the efficient and facile production of 1,5-disubstituted-1H-tetrazoles (1,5-DS-1H-Ts). Interestingly, the combination of 1,5-DS-1H-Ts with suitable post-transformations in a tandem manner results in the construction of various classes of heterocyclic compounds bearing 1,5-DS-1H-T moiety. This review aims to provide the application of diverse post-Ugi-azide reaction in the preparation of different N-heterocyclic compounds bearing 1,5-DS-1H-T such as substituted and fused 1,5-DS-1H-Ts.

Cascade process for direct synthesis of indeno[1,2-b]furans and indeno[1,2-b]pyrroles from diketene and ninhydrin.

Novel and efficient multicomponent reactions (MCRs) involving diketene, ninhydrin (indane-1,2,3-trione) and one primary amine (3CR) or two different primary amines (4CR) were achieved for the successful synthesis of dihydro-4H-indeno[1,2-b]furan-3-carboxamides or tetrahydroindeno[1,2-b]pyrrole-3-carboxamides, respectively. The merits of this method are highlighted by using either commercially available or easily accessible starting materials, operational simplicity, facile workup procedure, efficient usage of all the reactants, tolerance of a variety of functional groups and ability to conduct under un-catalyzed reaction condition. The products were also isolated by just decantation of the solvent, and for the purification column chromatography was non-required.

Ag Nanoparticles Stabilized on Cyclodextrin Polymer Decorated with Multi-Nitrogen Atom Containing Polymer: An Efficient Catalyst for the Synthesis of Xanthenes.

In attempt to broaden the use of cyclodextrin polymer for catalytic purposes, a novel covalent hybrid system was prepared through growth of multi-nitrogen atom containing polymer (PMelamine) derived from reaction of ethylenediamine and 2,4,6-trichloro-1,3,5-triazine on the functionalized cyclodextrin polymer (CDNS). The resulting hybrid system was then utilized as a catalyst support for the immobilization of silver nanoparticles through using Cuscuta epithymum extract as a naturally-derived reducing agent. The catalytic activity of the catalyst, Ag@CDNS-N/PMelamine, for the synthesis of xanthenes through reaction of aldehydes and dimedone in aqueous media was examined. The results showed high catalytic activity and recyclability of the catalyst. It was believed that cyclodextrin in the backbone of the catalyst could act both as a capping agent for Ag nanoparticles and phase transfer agent to bring the hydrophobic substrates in the vicinity of the catalytic active sites and accelerate the reaction rate. Multi-nitrogen atoms on the polymer, on the other hand, could improve the Ag NPs anchoring and suppress their leaching.

Applications of Dainshefsky's Dienes in the Asymmetric synthesis of Aza-Diels-Alder Reaction.

Asymmetric hetero-Diels-Alder (AHDA) reactions provide a multitude of opportunities for the highly efficient, regio- and stereoselective construction of various heterocycles in enantiomerically pure form. The asymmetric aza-Diels-Alder (A-aza-DA) reaction using diversely hetero-dienophiles and hetero-dienes have been increasingly developed as a valuable method for the synthesis of functionalized nitrogen ring systems. The purpose of this review is to give a detailed discussion of the A-aza-DA reaction particularly, the stereoselective reactions of imines as dienophiles with Dainshefsky dienes to obtain optically pure aza-Diels-Alder products. The development of stereoselective variants of the reaction make use of imines as the dienophile and Dainshefsky dienes is at the forefront of these studies. This review updates the A-aza-DA reactions covering the literature from 1972 till date.

Electrochemically Induced Michael Addition Reaction: An Overview.

Due to its high potential for the formation of carbon-carbon bonds, Michael addition reaction is one of the closest reactions to the heart of synthetic organic chemists. Electrochemistry presents a very stimulating and divergent resource for selective oxidation and reduction in organic chemistry, generating activated species, for example radical anions or radical cations. In this review, we try to underscore usefulness of electrogenerated Michael addition reaction with the hope of encouraging synthetic organic chemists to contemplate it, as an efficient and green strategy when it is required in their designed multi-step reaction pathways.

Current progress in asymmetric Biginelli reaction: an update.

The Biginelli reaction, involving a three-component reaction of an aromatic aldehyde, urea and ethyl acetoacetate, has emerged as an extremely useful synthetic tool to organic chemists for the synthesis of 3,4-dihydropyrimidine-2-(1H)-ones and related heterocyclic compounds. In the past decades, the asymmetric variants of this reaction have been at the forefront of investigations in several research groups. In 2013, we highlighted the developments occurred in the asymmetric version of the Biginelli reaction. This review article focuses on the recent developments of asymmetric Biginelli reaction covers the literature going back to 2012.

A Novel and Efficient Five-Component Synthesis of Pyrazole Based Pyrido[2,3-d]pyrimidine-diones in Water: A Triply Green Synthesis.

A novel one pot synthesis of pyrazolo[4',3':5,6]pyrido[2,3-d]pyrimidine-diones, via a five-component reaction, involving, hydrazine hydrate, ethyl acetoacetate, and 1,3-dimethyl barbituric acid, an appropriate aryl aldehydes and ammonium acetate catalyzed via both of heterogeneous and homogeneous catalysis in water, is reported.

Current advances in the synthesis and biological potencies of tri- and tetra-substituted 1H-imidazoles.

In this report, we review the current chemistry progress and in particular the synthesis approaches of tri- and tetra-substituted imidazoles.

Application of poly 1,8-diaminonaphthalene/multiwalled carbon nanotubes-COOH hybrid material as an efficient sorbent for trace determination of cadmium and lead ions in water samples.

Poly 1,8-diaminonaphthalene/multiwalled carbon nanotubes-COOH hybrid material as an effective sorbents in solid phase extraction has been developed for the separation and preconcentration of Cd(II) and Pb(II) at trace levels in environmental water samples. The results indicate that the novel nanocomposite show a high affinity for these heavy metals due to the presence of several good extractive sites, which are introduced to the synthesized nanocomposite The maximum adsorption capacity of the synthesized sorbent for cadmium and lead ions was found to be 101.2 and 175.2 mg g(-1) , respectively. The detection limits of this method were 0.09 and 0.7 ng ml(-1) for Cd(II) and Pb(II), respectively.

Recent advances in C-heteroatom bond forming by asymmetric Michael addition.

In this review, we try to highlight the recently reported stereoselective Michael conjugate additions of heteroatom nucleophiles to electron-deficient alkenes. The topic is divided based on the nature of the nucleophile employed (nitrogen-, oxygen-, sulfur-, or phosphorus-centered) and then subdivided to distinguish between catalyst-controlled and substrate/reagent-controlled methods which is necessary to achieve asymmetric synthesis.

Negishi coupling: an easy progress for C-C bond construction in total synthesis.

Negishi cross-coupling reactions were used extensively in total synthesis. The expansion of substrate scope, the development of mild reaction conditions, the advancement of the methods to improve the stereo- and regio-selectivity of carbon-carbon bond formation, the maturity of a large number of sequential processes, and the development of non-toxic reactions signify the importance of Negishi coupling. The following review illustrates a strategic role of this reaction in constructing carbon-carbon bonds in the recent total synthesis of natural products.

Sulfonic acid-functionalized chitosan-metal-organic framework composite for efficient and rapid conversion of fructose to 5-hydroxymethylfurfural.

In pursuit of designing a bio-based catalyst for the dehydration of biomass (i.e., fructose) to 5-hydroxymethylfurfural, a novel catalytic composite was prepared by in-situ formation of an Al-based metal-organic framework in the presence of chitosan. To enhance the acidity of the as-prepared catalyst, it was sulfonated with chlorosulfonic acid. Various characterization techniques, including XRD, XPS, FTIR, SEM/EDX, TGA, and elemental mapping analysis were applied to validate the formation of the acidic composite. Fructose dehydration conditions were also optimized using Response Surface Method (RSM) and it was found that reaction in the presence of catalyst (23 wt%) in DMSO, at 110 °C for 40 min led to the formation of HMF in 97.1%. Noteworthy, the catalyst was recyclable and stable up to five runs with a minor reduction in its activity.

Facile Cu-MOF-derived Co3O4 mesoporous-structure as a cooperative catalyst for the reduction nitroarenes and dyes.

The present study describes the environmentally friendly and cost-effective synthesis of magnetic, mesoporous structure-Co3O4 nanoparticles (m-Co3O4) utilizing almond peel as a biotemplate. This straightforward method yields a material with high surface area, as confirmed by various characterization techniques. Subsequently, the utilization of m-Co3O4, graphene oxide (GO), Cu(II)acetate (Cu), and asparagine enabled the successful synthesis of a novel magnetic MOF, namely GO-Cu-ASP-m-Co3O4 MOF. This catalyst revealed remarkable stability that could be easily recovered using a magnet for consecutive use without any significant decline in activity for eight cycles in nitro compound reduction and organic dye degradation reactions. Consequently, GO-Cu-ASP-m-Co3O4 MOF holds immense potential as a catalyst for reduction reactions, particularly in the production of valuable amines with high industrial value, as well as for the elimination of toxic-water pollutants such as organic dyes.

Clay-supported bio-based Lewis acid ionic liquid as a potent catalyst for the dehydration of fructose to 5-hydroxymthylfurfural.

Caffeine and halloysite nanoclay mineral that are bio-based compounds were utilized to synthesize a novel Lewis acid heterogeneous catalyst. To this aim, halloysite was functionalized with 2,4,6-trichloro-1,3,5-triazine and reacted with caffeine, which was then converted to ionic liquid via a reaction with ZnCl2. The catalyst was applied for promoting the dehydration of fructose to 5-hydroxymethylfurfural. To investigate the effects of the reaction variables, response surface methodology was used. The product was achieved in 98.5% in 100 min using a catalyst loading of 30 wt% at 100 °C. Moreover, the catalyst was recyclable up to six runs with slight zinc leaching. Comparison of the catalytic activity of the catalyst with that of halloysite and a control catalyst with one caffeine-based Lewis acid ionic liquid confirmed the superior activity of the former and the important role of 2,4,6-trichloro-1,3,5-triazine for increasing the number of the grafted caffeine and thus the acidic sites of the catalyst. A plausible reaction mechanism was proposed, and the activity of the catalyst for other carbohydrates was also studied. According to the results, this catalyst catalyzed the reaction of other substrates to furnish 5-hydroxymethylfurfural in low to moderate yields. According to the kinetic studies, the activation energy was estimated to be 22.85 kJ/mol.

Sulfonic acid-functionalized k-carrageenan/Cr-based metal-organic framework: An efficient and recyclable catalyst for fructose conversion to 5-hydroxymethylfurfural.

A novel bio-based catalyst was developed by in-situ forming Chromium(III) (Cr)-based metal-organic framework, MIL-101(Cr), in the presence of k-carrageenan (k-Car) and followed by a post-synthetic modification to introduce additional -SO3H functional groups into the composite structure of k-Car/MIL-101(Cr). Different analyses were conducted to confirm the successful catalyst formation. The catalyst performance was evaluated in the solid acid catalyzed dehydration of fructose to 5-hydroxymethylfurfural. The Response Surface Method (RSM) optimization determined that employing 33 wt% of the catalyst at 105 °C for 40 min resulted in a remarkable 97.8 % yield. The catalyst demonstrated suitable recyclability, maintaining its catalytic efficiency over four cycles. Comparative studies with k-Car and the non-sulfonated composite highlighted the superior activity of the catalyst, emphasizing the synergy between the k-Car, MIL-101(Cr) and the influence of -SO3H post-functionalizing on the catalytic performance.

Recent progress in asymmetric Biginelli reaction.

The Biginelli reaction, which involves the interaction of ethyl acetoacetate, urea, and an appropriate aryl aldehyde, was first discovered by Pietro Biginelli about 120 years ago. The Biginelli products (3,4-dihydropyrimidin-2(1H)-ones) are interesting materials due to their significant pharmacological and structural profiles. In the last decades, the asymmetric synthesis as a powerful tool has an effective impact on the Biginelli products and has increased their potencies and applications as drugs. Having the importance of this subject in mind, in this review we wish to present the recent rapid progress of asymmetric Biginelli reaction.