Band 7, Heft 4-5 - Special Issue: Organocatalysis_A green tool for sustainable developments; Guest Editors: Bimal Krishna Banik and Bubun Banerjee

An environmentally benign, stable yet efficient organocatalyst is highly desirable from the viewpoint of green chemistry and catalysis. Imidazole-based zwitterionic-type molten salts are a new type of organocatalysts with high catalytic application in various organic transformations with added advantage of room temperature ionic liquid (RTIL) property. Most importantly, these ionic-liquid catalysts are easily recyclable and subsequently reusable for multiple times without loss of significant catalytic efficiency. It has also been evident that C2–H of the imidazole has a vital role in catalyzing the reaction via electrophilic activation. Moreover, by changing the cations and/or anions, the properties of ILs can be tuned in many ways. In this article, the role of imidazolium zwitterionic molten salts as an organocatalyst for selective organic transformations including syn -selective aza-Henry reaction, Erlenmeyer reaction, synthesis of different heterocycles and their functionalization and regioselective ring-opening reactions has been elaborated chronically which will definitely be helping to the readers to explore this new class of organocatalyst for further applications.

The application of hypervalent iodine species generated in situ in organic transformations has emerged as a useful and powerful tool in organic synthesis, allowing for the construction of a series of bond formats via oxidative coupling. Among these transformations, the catalytic aryl iodide can be oxidized to hypervalent iodine species, which then undergoes oxidative reaction with the substrates and the aryl iodine regenerated again once the first cyclic cycle of the reaction is completed. This review aims to systematically summarize and discuss the main progress in the application of in situ- generated hypervalent iodine species, providing references and highlights for synthetic chemists who might be interested in this field of hypervalent iodine chemistry.

Saccharomyces cerevisiae , commonly known as baker’s yeast, has gained significant importance as a mild, low-cost, environmentally benign biocatalyst. Initially it was mostly employed as an efficient catalyst for the enantioselective reduction of carbonyl compounds. Over the last decade, baker’s yeast has found versatile catalytic applications in various organic transformations. Many multicomponent reactions were also catalyzed by baker’s yeast. Various heterocyclic scaffolds with immense biological activities were synthesized by employing baker’s yeast as catalyst at room temperature. In this communication, we have summarized baker’s yeast catalyzed various organic transformations focusing primarily on heterocyclic synthesis.

The utilization of small organic compounds as catalysts has advanced rapidly, and organocatalysis has emerged as a dominant technique complementary to metal-catalyzed organic conversions. The organocatalysis field has enhanced the progression of innovative approaches to make varied chiral molecules. Researchers have placed enormous effort towards designing and blending simpler organocatalysts to synthesize enantioselective molecules in good yields. This work emphasized the impact of enamine, iminium, hydrogen bonding, and phase transfer organocatalysts in organic synthesis. The monograph focused on the crucial methods to construct valuable molecules with high enantiomeric purity.

Organocatalysis has occupied sustainable position in organic synthesis as a powerful tool for the synthesis of enantiomeric-rich compounds with multiple stereogenic centers. Among the various organic molecules for organocatalysis, the formation of carbon–carbon is viewed as a challenging issue in organic synthesis. The asymmetric aldol and Michael addition reactions are the most significant methods for C–C bond forming reactions. These protocols deliver a valuable path to access chiral molecules, which are useful synthetic hybrids in biologically potent candidates and desirable versatile pharmaceutical intermediates. This work highlighted the impact of organocatalytic aldol and Michael addition reactions in abundant solvent media. It focused on the crucial methods to construct valuable molecules with high enantio- and diastereo-selectivity.

The treatment of various pathological conditions in human beings involves the use of safe and efficacious drug substances. But there are different complications associated with the treatment of various disease states including drug resistance, adverse drug reactions, toxicity, etc. To minimize these problems, there is an urgent need to develop new therapeutics with suitable pharmacokinetic and pharmacodynamic properties. So, the organocatalytic methods are emerged as a potential synthetic tool to accelerate the design of new drug candidates with improved physicochemical and pharmacological properties, selectivity, and efficiency for the treatment of life-threatening diseases. Organocatalytic reactions refer to the chemical reaction that is accelerated by organic catalysts instead of using organometallic catalysts. Organocatalysts are more advantageous in comparison to metallic catalysts because organocatalysts are cost-effective, stable, efficient, non-toxic, readily available, and easy to handle. In addition to this, the organocatalysis method involves an eco-friendly reaction by minimizing the formation of by-products and reducing the chemical hazards. Organocatalysts are categorized into four classes such as Lewis acids, Lewis bases, Bronsted acids, and Bronsted bases. These catalysts are generally involved in various reactions mechanisms such as Aldol reaction, Diels–Alder reactions, Michael Addition and Knoevenagal reactions, etc. The utility of organocatalyst in synthetic chemistry results in the development of medicinally active compounds with diverse structural features.

The combination of one-pot methodologies to asymmetric organocatalysis allow a green and direct access to many types of complex highly functionalized chiral products, including important key intermediates in total syntheses of important bioactive compounds. A series of chiral organocatalysts have already been successfully applied to such syntheses. This report collects major developments in the total synthesis of biologically active products based on the use of enantioselective organocatalytic domino/tandem reactions as key steps. It is divided into two parts dealing successively with reactions based on the use of proline-derived catalysts and other organocatalysts.

Small organic molecules predominantly containing C, H, O, N, S and P element are found promising molecule to accelerate chemical reactions and are named organocatalysis. In addition, these organocatalysts are easy availability, stable in water and air, inexpensive, and low toxicity, which confer a huge direct application in organic synthesis when compared to transition metal catalyzed reactions and becoming powerful tools in the construction of a selective chiral product. Interest on organocatalysis is spectacularly increased since last two decades, due to the novelty of the concept and selectivity. Based on the nature of the organocatalysts used, they are classified in to four major classes, among them one of the types is amino acids derived organocatalysts. Natural amino acids are playing important role in building blocks of protein construction, and also intermediate products of the metabolism. α -Amino acid is a molecule, that contains both amine and carboxyl functional group. Their particular structural characteristic determines their role in protein synthesis, and bifunctional asymmetric catalysts for stereoselective synthesis. Two functional groups present on a single carbon acting as an acid and base, which promote chemical transformations in concert similar to the enzymatic catalysis. The post translational derivatives of natural α -amino acids include 4-hydroxy-L-proline and 4-amino-L-proline scaffolds, and its synthetic variants based organocatalysts, whose catalytic activity is well documented. This chapter discussed past and present development of the organocatalysts derived from natural and modified amino acids for various important organic transformations reviewed.

Organic transformations using efficient, atom-economical, cost-effective and environmentally benign strategies for the construction of diversified molecules have attracted synthetic chemists worldwide in recent years. These processes often minimize the waste production and avoid the use of hazardous flammable organic solvents. Among various green protocols, the procedures using surfactant-based catalytic systems have received a considerable attention in organic synthesis. In this context, Bronsted acidic surfactants have emerged as efficient catalysts for various C–C, C–O, C–N and C–S bond forming reactions. Many of these reactions occur in water, as Bronsted acidic surfactants have a unique ability of creating hydrophobic pocket through micelle formation in aqueous medium and the substrate molecules react efficiently to afford the targeted products in good yields. In the past, Bronsted acidic surfactant combined catalysts successfully displayed their potential to accelerate the reaction rates of diverse organic transformations. This chapter presents a complete overview on Bronsted acidic surfactants catalyzed organic reactions to construct a variety of aromatic and heteroaromatic molecular frameworks.

Microwaves in the presence of enzymes are used to execute a number of reactions for the preparation of biologically active compounds. The success of microwave-induced enzymatic reactions depends on frequencies, field strength, waveform, duration, and modulation of the exposure. Enzymes under microwave irradiation become activated and this activation is sufficient to investigate simple to complex reactions that were not reported under these reaction conditions before. Enzymatic catalysis together with microwave technology and solvent-free chemical reaction is a nature-friendly procedure. The most interesting reactions that are performed by enzymes in the microwave are documented here with reference to examples that are related to medicinally active molecules.

The present review summarizes various organic transformations carried out by using sulfonated β-cyclodextrins such as β-cyclodextrin sulfonic acid, β-cyclodextrin propyl sulfonic acid, and β-cyclodextrin butyl sulfonic acid as an efficient, supramolecular reusable catalyst under diverse reaction conditions.

Enzymes are proteins that functions as biological catalyst. It is now a known fact that enzyme can catalyze many synthetic operations better than the conventional reagents. Not only in the synthesis of natural products, they can also be applied for construction of varieties of unnatural compounds. In this chapter, Pariyar and Ghosh have discussed in brief synthesis of various biologically active heterocyclic compounds using different enzymes as catalysts. Among various enzymes, laccases, trypsin, α-amylase and Bakers’ yeast are few that are easily available and have been extensively explored for various synthetic strategies. This chapter will definitely serve as valuable source of information to the readers in the field of enzyme-catalyzed reactions.