Recent progress and prospects in the organocatalytic Morita-Baylis-Hillman reaction.

The organocatalytic asymmetric Morita-Baylis-Hillman (MBH) reaction produces a significant carbon-carbon bond formation that involves the addition of α,ß-unsaturated carbonyl compounds to activated alkenes to give α-methylene-ß-hydroxycarbonyl compounds. Commercially available starting materials, excellent atom economy, mild reaction conditions, and flexible products are the major highlights of this method. In this review, we discuss the recent developments in the organocatalytic MBH reaction, covering literature from 2018 to 2023.

Montmorillonite-catalysed coupling reactions: a green overview.

Coupling reactions are widely significant in organic synthesis, and within the green chemistry perspective the utilization of montmorillonite clay as a catalyst offers a viable alternative to traditional coupling protocols. Montmorillonite clay is an effective, eco-friendly, economic and recyclable catalyst, and its heterogeneous nature facilitates easy isolation and reusability. The majority of coupling reactions executed with montmorillonite catalysts offer notable advantages over their homogeneous counterparts, including enhanced efficiency, selectivity, operational simplicity, elimination of toxic solvents and ligands, maintenance of mild reaction conditions, and cost-effectiveness. This review gives a comprehensive summary of the literature to date on coupling reactions catalysed by montmorillonite clay, while also outlining future prospects in this area.

Palladium N-Heterocyclic Carbene-Catalyzed Aminations: An Outline.

Amination reactions play a pivotal role in synthetic organic chemistry, facilitating the generation of nitrogen-containing scaffolds with broad applications in drug synthesis, material production, polymer formation, and the generation of amino acids and peptides. Amination offers the potential to fine tune the properties of natural products and produce functional materials for various applications. Palladium N-heterocyclic carbene (Pd-NHC) emerges as an innovative and highly effective catalyst in this context. Under favorable reaction conditions, this robust and simple catalyst efficiently facilitates the synthesis of a diverse range of compounds with varying complexity and utility. Pd-NHC complexes exhibit significant σ-electron donating potential, enhancing the ease of the oxidative addition process in their mechanistic pathway. Their steric topography further contributes to a rapid reductive elimination. These complexes demonstrate remarkable stability, a result of the strong Pd-ligand bond. The wide variety of Pd-NHC complexes has proven highly efficient in catalyzing reactions across a spectrum of complexities, from simple to intricate. The domain of aminations catalyzed by Pd-NHC has undergone significant diversification, presenting new opportunities, particularly in the realms of material chemistry and natural product synthesis. This review outlines the advancements in Pd-NHC-catalyzed amination reactions, covering literature up to date.

An Overview of Julia-lythgoe Olefination.

Julia-Lythgoe olefination (or simply Julia olefination) is an olefination process between phenyl sulfones and aldehydes (or ketones) to give alkenes after alcohol functionalization and reductive elimination using sodium amalgam or SmI2. It is mainly used to synthesize E-alkenes and is a key step in numerous total syntheses of many natural products. This review exclusively deals with the Julia-Lythgoe olefination and concentrates mainly on the applications of this reaction in natural product synthesis covering literature up to 2021.

Low-cost transition metal catalysed Negishi coupling: an update.

The Negishi coupling is a significant C-C bond-forming reaction to access synthetically valuable organic compounds. In recent years, researchers have developed sustainable first-row transition metal (Fe, Co, Ni and Cu) based complexes in place of the conventional Pd catalyst for this reaction. Several such low-cost metal-based catalysts showed high efficiency and potential application in natural product synthesis. This review focuses on the recent achievements in low-cost transition metal-based Negishi coupling reactions, covering reports from 2016.

Cu(ii)-catalyzed C-N coupling of 2-aminobenzothiazoles with boronic acids at room temperature.

A Cu(ii)-catalyzed, effective C-N coupling of 2-aminobenzothiazoles with boronic acids in acetonitrile under open vessel chemistry was achieved. This protocol demonstrates the N-arylation of 2-aminobenzothiazoles with a broad range of differently substituted phenylboronic acids at room temperature and accomplishes moderate to excellent yields of the desired products. Under the optimized condition, phenylboronic acids bearing halogen at the para and meta positions were found to be more fruitful.

Silver-catalyzed synthesis of nitrogen heterocycles: recent advancements.

Heterocyclic chemistry is an ever-expanding field without boundaries. Heterocycles play a significant role in medicinal and pharmaceutical chemistry, the agricultural industry and materials science. Among heterocycles, N-heterocycles constitute a large family. Their ubiquity in living and non-living systems makes them an endless topic for research. Being a part of the research community, we need to balance environmental concerns with scientific and economic development. So, research that is coherent with nature is a trending domain at all times. Silver catalysis possesses a greener face in organic synthesis. The simple, rich and extensive chemistry shown by silver makes it an attractive choice for catalysis. Inspired by its versatility and uniqueness we have compiled here recent developments in the silver-catalyzed synthesis of nitrogen-containing heterocycles since 2019. The high efficiency, regioselectivity, chemoselectivity, recyclability of the catalytic system, greater atom economy and simple reaction setup are the major highlights of this protocol. It is a hot research topic which is evident from the large number of works carried out for the fabrication of a range of N-heterocycles with varying complexities.

Ruthenium-catalyzed hydroarylation reactions as the strategy towards the synthesis of alkylated arenes and substituted alkenes.

Metal-catalyzed hydroarylation reactions are always powerful tools in organic synthesis since they can form C-C or C-heteroatom bonds in an atom and step economic manner. Medicinally and biologically relevant scaffolds can be easily and efficiently synthesized using this strategy. By tuning the directing groups that are present on the arenes, regioselectivity can be induced to the C-H activation. Metals like cobalt, rhodium and ruthenium are well known as catalysts in this type of reaction. But due to their easy availability and efficiency, Ru catalysts are found to be more preferable for hydroarylation purposes. In this review, the Ru-catalyzed hydroarylation of alkenes and alkynes, intramolecular Ru-catalyzed hydroarylation of olefin tethered arenes, modifications in the catalytic system to improve the catalytic efficiency, and carboxylate-assisted Ru-catalyzed hydroarylation reactions are discussed in detail, covering literature from 2016 to 2022.

Copper-catalyzed Sonogashira reactions: advances and perspectives since 2014.

Transition metal catalyzed Sonogashira coupling reaction has evolved as an efficient pathway for the construction of C-C bonds. Initially, palladium cooperating with copper was considered as the efficient catalytic system for this reaction. However, nowadays there have been astonishing progress in copper catalyzed Sonogashira coupling reactions. Copper catalyzed reactions have attained significant attention owing to the cost effective and environmentally benign characteristics of this metal compared to palladium. This review summarizes the recent developments in copper catalyzed Sonogashira coupling covering literature from 2014 to 2021.

Palladium-Catalyzed Aminocarbonylation of Aryl Halides.

Palladium-catalyzed organic reactions are ubiquitous due to their high efficiency in coupling reactions and have wide applications in synthetic chemistry. Their widespread use in organic synthesis has been attributed to moderate conditions associated with reactions and tolerance to different types of functional groups. Palladium-catalysts are extensively used in aminocarbonylation of aryl halides for the synthesis of amides and have found a wide variety of applications in pharmaceuticals, agrochemicals, petrochemicals, materials, polymers, etc. In this review, we summarize the recent advances in the synthesis of amides via palladium-catalyzed aminocarbonylation of aryl halides, and cover literature from 2010 to 2021.

Applications of iron pincer complexes in hydrosilylation reactions.

Due to its abundance, low cost and low toxicity, the first-row transition metal, iron is widely preferred as a catalyst in organic synthesis. The only drawback of lower selectivity due to high reactivity and low stability of the metal centre is tuned by using pincer ligands of different types. The different iron pincer complexes thus prepared are extensively used in catalyzing different types of organic reactions with great selectivity and functional group tolerance under moderate reaction conditions. In this review, we focus on the applications of iron pincer complexes in hydrosilylation reactions, especially the hydrosilylation of carbonyl derivatives and alkene/alkynes.

A detailed theoretical investigation to unravel the molecular mechanism of the ligand-free copper-catalyzed Suzuki cross-coupling reaction.

The Suzuki-Miyaura coupling (SMC) represents a very efficacious method for constructing C-C bonds in organic synthesis. The ligand-free variants of SMC have been grabbing attention these days. Despite this momentousness, the mechanistic details of the ligand-free variants are scant in the literature. Herein, we have carried out a detailed mechanistic investigation into the ligand-free Cu-catalyzed SMC of unsaturated organic halides with aryl boronic acid with the aid of density functional theory (DFT) calculations employing the conductor-like polarizable continuum model (CPCM) method. The present study elucidates that in the absence of ancillary ligands on the metal, the substrates, base, and solvent molecules could act as pseudo-ancillary ligands to facilitate the cross-coupling reaction. The investigation further revealed that unsaturated halides like alkynyl halides/vinyl halides could act as good ancillary ligands for copper by forming a Cu-π intermediate and promoting a facile transmetalation process. However, regarding the oxidative addition and reductive elimination steps, a concerted pathway is observed contrary to Pd catalyzed Suzuki coupling, owing to the instability of Cu(III) species and the favourability of Csp2-Csp bond formation. In the whole set of mechanisms explored, oxidative addition/oxidative nucleophilic substitution was the rate-determining step in all the cases. A thermodynamically stable π-coordinated intermediate species where the substrate and base molecule are coordinated to the metal center is identified as the rate-determining species for the ligand-free Suzuki cross-coupling reaction. The presence of the aforesaid intermediate increases the energy span and consequently the activation barrier for the rate-determining step. This study unveiled a theoretical rationale for the high-temperature requirement in the ligand-free Cu-catalyzed SMC reaction.

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions.

Iron- and cobalt-catalyzed Sonogashira coupling reactions are becoming central areas of research in organic synthesis. Owing to their significant importance in the formation of carbon-carbon bonds, numerous green and nanoparticle protocols have emerged during the past decades. The non-toxic and inexpensive nature of catalysts gained much attention in recent times. In this context, their catalytic nature and activity in Sonogashira coupling reactions were well explored and compared. Most importantly, one of the highlights of this review is the emphasis given to green strategies. This is the first review on iron- and cobalt-catalyzed Sonogashira coupling reactions which comprehends literature up to 2020.

Recent advances and perspectives in ruthenium-catalyzed cyanation reactions.

The cyanation reaction has achieved rapid progress in recent times. The ability to exhibit multiple oxidation states increased the demand of ruthenium in the field of catalysis. These cyanation reactions have wide application in pharmacological and biological fields. This review gives an overview of the ruthenium-catalyzed cyanation reactions covering literature up to 2021.

Suitable acid groups and density in electrolytes to facilitate proton conduction.

Proton conducting materials suffer from low proton conductivity under low-relative humidity (RH) conditions. Previously, it was reported that acid-acid interactions, where acids interact with each other at close distances, can facilitate proton conduction without water movement and are promising for overcoming this drawback [T. Ogawa, H. Ohashi, T. Tamaki and T. Yamaguchi, Chem. Phys. Lett., 2019, 731, 136627]. However, acid groups have not been compared to find a suitable acid group and density for the interaction, which is important to experimentally synthesize the material. Here, we performed ab initio calculations to identify acid groups and acid densities as a polymer design that effectively causes acid-acid interactions. The evaluation method employed parameters based on several different optimized coordination interactions of acids and water molecules. The results show that the order of the abilities of polymer electrolytes to readily induce acid-acid interactions is hydrocarbon-based phosphonated polymers > phosphonated aromatic hydrocarbon polymers > perfluorosulfonic acid polymers ≈ perfluorophosphonic acid polymers > sulfonated aromatic hydrocarbon polymers. The acid-acid interaction becomes stronger as the distance between acids decreases. The preferable distance between phosphonate moieties is within 13 Å.

Nickel catalysts in Sonogashira coupling reactions.

Nickel has emerged as a desirable substitute for palladium in Sonogashira coupling reactions due to its abundance, less toxicity and high catalytic activity. Ni complexes have been developed to catalyse C(sp)-C(sp2) and C(sp)-C(sp3) Sonogashira couplings that find applications in the synthesis and modifications of biologically relevant molecules. This review focuses on the catalytic potential and mechanistic details of various Ni complexes employed in the Sonogashira coupling. These include homogeneous catalytic systems with Ni-phosphorus and Ni-nitrogen catalysts, ligand-free catalysts, and carbonylative coupling strategies. Various heterogeneous catalytic systems using supported Ni complexes, Ni nanoparticles and Pd-Ni bimetallic catalysts have also been discussed. This is the first review reported so far dealing exclusively with Ni-catalysed Sonogashira coupling reactions. This review illustrates the current strategies and potential of Ni-catalysed Sonogashira coupling reactions in both homogeneous and heterogeneous systems, and covers the literature up to 2020.

Applications of aryl-sulfinamides in the synthesis of N-heterocycles.

Enantiopure aryl-sulfinamides are important chiral auxiliaries in the asymmetric synthesis of amines and their derivatives. Here, we provide an overview of arylsulfinamide mediated asymmetric methods towards N-heterocycle synthesis. This methodology through sulfinylimines offers general access to structurally diverse piperidines, pyrrolidines, aziridines and their derivatives which represent the structural motif of many natural products and therapeutically important compounds. The review covers articles from 2006-2020 and we have categorized the review based on the ring size as 3-, 5-, and 6- membered heterocycles and their derivatives.

Transition metal-catalyzed synthesis of spirooxindoles.

Spirooxindole is a principal bioactive agent and is observed in several natural products including alkaloids. They are broadly studied in the pharmaceutical field and have a significant role in the evolution of drugs such as anti-viral, anti-cancer, anti-microbial etc. In organic chemistry, an indispensable role is presented by transition metal catalysts. An effective synthetic perspective to spirooxindoles is the use of transition metals as the catalyst. This review discusses the synthesis of spirooxindoles catalyzed by transition metals and covers literature up to 2020.

Recent advances and prospects in the Zn-catalysed Mannich reaction.

Zn-catalysed reactions are ubiquitously important due to their inexpensive, generally less toxic and atom-economic nature. According to the modern criteria of sustainability, their use in a catalytic manner is a highly desirable goal, especially when using chiral ligands. Considering the relevance of well-established zinc-mediated C-C bond formation reactions, it is relatively surprising that the use of Zn as a catalyst is still underdeveloped, especially in comparison with other transition metals. The vast majority of natural molecules, including proteins, nucleic acids and most biologically active compounds, contain nitrogen. Consequently, developing new synthetic methods for the construction of nitrogenous molecules receives great attention from organic chemists. The Mannich reaction is a very basic and very useful platform for the development of several such nitrogen-containing molecules. In this review, we summarise the recent advancements in the Zn-catalysed Mannich reaction, covering the literature from 2011 to 2020.

Recent developments and perspectives in the copper-catalyzed multicomponent synthesis of heterocycles.

Heterocyclic compounds have become an inevitable part of organic chemistry due to their ubiquitous presence in bioactive compounds. Copper-catalyzed multicomponent synthesis of heterocycles has developed as the most convenient and facile synthetic route towards complex heterocyclic motifs. In this review, we discuss the advancements in the field of copper-catalyzed multicomponent reactions for the preparation of heterocycles since 2018.