Carbon-Chalcogenide Cross-Coupling Reactions in Water Atanu Mahata, Totan Roy, Animesh Mondal, and Debasish Kundu Bentham Science Publishers Ltd. : Over the past two decades, researchers have witnessed the synthesis of diaryl sulfides and diaryl selenides via transition metals-mediated carbon-heteroatom cross-coupling reactions in the presence of various organic and inorganic solvents. The use of water as a clean and environmentally friendly solvent in cross-coupling chemistry of C-S/Se bond formations has attracted profound interest owing to its availability, non-toxicity, low cost and renewability. The most commonly used solvents have been recognized as being of environmental concern, but the use of green and eco-friendly solvents like water is frequently considered with respect to the recovery of catalysts, isolation of products, and recycling. The fundamental interactions between the water and the transition metal catalysts or ligands are viewed from mechanistic aspects, which mostly favours the rational selection of high-performance and safe solvents. In this article, the authors intended to focus extensively on the critical role of water in various transition metals mediated C-S/Se cross-coupling methodologies.
Synthesis of Polynuclear Aromatic Hydrocarbons by Palladium-catalyzed C-H Bond Functionalization Mitali Dewan, Sachinath Bera, Shubhankar Samanta, Debasish Kundu, and Rathin Jana Bentham Science Publishers Ltd. : Nowadays palladium-catalyzed C–H bond activation is a useful approach for the synthetic transformation of organic compounds due to step economy, the use of non-prefunctionalized substrates and reduced chemical wastes. Among the various synthetic strategies, palladium catalyzed intra and inter-molecular C–H bond activation has recently drawn a lot of interest to synthesize the decorated π-conjugated polycyclic aromatic hydrocarbon. In this review, we have focused on recent progress along with previous strategies to synthesize various polynuclear aromatic hydrocarbons (PAHs) by the use of Pd-catalyzed C–H bond activation. We have also discussed the mechanistic details of the reaction intra and inter-molecular C–H bond activation.
Transition Metals Catalyzed Direct C-H Chalcogenation of Arenes and Heteroarenes Atanu Mahata, Madhusudan Garain, Totan Roy, Dilip Gorai, and Debasish Kundu Bentham Science Publishers Ltd. Abstract: Transition metals catalyzed C-H bond activation reactions have appeared as an emerg-ing field to introduce different functional groups in the inactivated saturated and unsaturated C-H bonds. C-S and C-Se bond constructions in aromatic scaffolds are very interesting due to the im-portant applications of organochalcogen reagents in pharmaceutical chemistry and the material world. The introduction of sulphur or selenium moiety to an inert C-H functionality of an arene under transition metal catalysis has become one of the prime challenges and targets in recent years. In this perspective, various transition metals such as Cu, Ni, Co, Pd, Rh, Ru etc. have been extensively studied. Aromatic arenes owning bearing suitable directing groups appeared as the most promising coupling partners to selectively synthesize differently substituted aryl sulfones and aryl sulfides/selenides. The synthetic strategies were highly convenient owing to the regiose-lectivity of products, broad substrate scope, mild reaction conditions and excellent functional group tolerance. The current review article comprehensively summarizes the extent of C-S/Se bond formation via transition metal-catalyzed C-H bond activation with the assistance of directing groups to govern the site selectivity.
Synthesis of Unsymmetrical Diaryl Tellurides Under Mechanical Ball Milling in Room Temperature Anup Roy, Subir Panja, Pradipta Kumar Basu, and Debasish Kundu Bentham Science Publishers Ltd. Abstract: An efficient transition metal catalyst-free protocol for the synthesis of unsymmetrical diaryl tellurides has been developed by the reaction of diaryl tellurides and aryl diazonium tetrafluoroborates under mechanical ball milling in the absence of any solvent and base under room temperature. InBr (Indium Bromide) plays an important role in generating the organotelluride nucleophile via the Te-Te bond cleavage of ditelluride. A library of diaryl tellurides bearing both electron-donating and withdrawing groups in the aromatic ring has been synthesized in good to excellent yields by this protocol. Despite very high synthetic importance of diaryl tellurides in the field of organic synthesis, very few protocols have been reported to date for their synthesis. The reactions were also performed on a gram scale without any considerable change in the yields, which surely broadened the applicability of this methodology in the industrial field.
Recent Advances in Copper-Catalyzed Carbon Chalcogenides Cross-Coupling Reactions Debasish Kundu, Totan Roy, and Atanu Mahata Bentham Science Publishers Ltd. Abstract:Cu-catalyzed carbon-heteroatom bond formation is a powerful tool for in the field of Organic synthesis. In past two decades numerous Cu-based catalytic systems are developed in both homogeneous and heterogenous form. Important developments were reported on Cu-based catalytic systems in the field of C-Chalcogenide cross coupling in last few decades. Where homogeneous Cu/L based catalytic systems are found to perform reactions with high selectivity, heterogeneous supported-Cu and Cu-based nanoparticles are found to perform the reactions under sustainable conditions and high recyclability of catalytic systems. This present overview mainly focuses on the recent advances and applications in this fast-growing research field with an emphasis on copper catalyzed cross-coupling generations of carbon–chalcogenide (S/Se/Te) bonds
Bromoaldehyde as a Useful Starting Materials for the Synthesis of Various Hetero Cyclic and Carbocylic Molecules by Pd-catalyzed Reaction Mitali Dewan, Debasish Kundu, and Rathin Jana Bentham Science Publishers Ltd. Abstract: This short review presents an overview of the effectiveness of β-bromoaldehyde as synthetic tool in organic chemistry. Few groups have reported significant contributions on β-bromoaldehyde. The aim of our short review was to give an overview of the latest advances in the chemistry of βbromoaldehyde from their preparation to their transformations and applications in organic synthesis of some heterocyclic and carbocyclic molecules by using palladium-catalyzed reaction.
Synthesis of aryl/heteroaryl selenides using transition metals catalyzed cross coupling and c─h activation Debasish Kundu, Atanu Mahata, and Totan Roy Bentham Science Publishers Ltd. Abstract:Aryl and heteroaryl selenides are an important class of organic compounds and their synthesis has been widely studied all over the world in the last two decades. Transition metals catalysed cross-coupling and directed C─H activation in unactivated arenes in the presence of diselenides/aryl selenols are found to be the most important tools for their synthesis. In recent years different transition metal catalysts were found to be effective to perform C─Se crosscoupling in both aryl and heteroaryl rings. The present review article covers all the recent advances made in the last ten years in the field of the synthesis of aryl and heteroaryl selenides through homogeneous and heterogeneous transition metals catalyzed cross-coupling reactions and directed selenylation via C─H bond activations.
Reusable Iron/Iron Oxide-based Nanoparticles Catalyzed Organic Reactions Laksmikanta Adak, Debasish Kundu, Keya Roy, Malay Saha, and Anup Roy Bentham Science Publishers Ltd. ABSTRACT:The last decade has witnessed a remarkable progress in the field of nanoscience and nanotechnology. Nanoparticles have been extensively used in diverse areas, including medicine, sensor, and catalysis. The easy accessibility of nanoparticles (NPs) with different shapes, sizes and compositions has inspired researchers to investigate their applications in catalysis. Recently, magnetic nanoparticles, such as iron-based nanoparticles, have attracted much consideration due to their unique properties, such as superparamagnetism, greater surface area, surface-to-volume ratio, and easy separation methodology. They increase the competence of organic reactions in terms of activity, selectivity, yield, simplicity, and sustainability. In this review, we focus on the developments of iron/iron oxide-based nanoparticles-catalyzed organic reactions and some examples of magnetic iron oxide nanoparticles as carriers/support for the main catalyst in organic reactions. Owing to magnetic properties, these nanocatalysts can be easily recovered from the reaction mixture by an external magnet and reused for several runs without loss of catalytic activity. Iron-based nanoparticles are used in a wide range of catalytic processes and applications. Notable focus has been on the hydrogenation of alkenes and alkynes, and also the hydrogenation of nitroarenes to aniline. Other catalyzed organic reactions, such as hydroboration of aldehydes and ketones, oxidative dehydrogenation of N-heterocycles, azide-alkyne cycloaddition reactions, synthesis of various heterocyclic compounds, multicomponent reactions, and crosscoupling reactions for C–C and C–heteroatom bond formation have been covered.
Progress in the Research of Naturally Occurring Biflavonoids: A Look Through Dilip Gorai, Shyamal K. Jash, and Debasish Kundu BENTHAM SCIENCE PUBLISHERS Biflavonoids are dimers of monomeric flavonoids and have reported to exhibit several pharmacological activities, like anti-microbial, anti-inflammatory, antienzymatic, antioxidant, anticancer, anti-Perkinson, anti-ulcer, anti-hypertensive, antidiabetic, anti-depressant and anti-protozoan. Extensive research work on this important segment of natural compounds is in progress. In this chapter, we report the progress of research on natural biflavonoids from the period of 2005 to early 2020; it includes enlisting newly isolated bioflavonoids from plant sources, biological activities exhibited by the known as well as new compounds and synthetic strategies developed for synthesizing such compounds. In this time period, a total of 247 biflavonoids have been reported either in terms of their first-time appearance or evaluation of their biological activities or both. Out of the reported 247 biflavonoids, 176 have been reported as new compounds from natural plant sources. They have been reported to exhibit a wide range of biological and pharmacological properties, including antimicrobial and antiviral, cytotoxic and anti-cancer, anti-diabetic, anti-anoxic, antioxidant, NO-inhibitory activity, anti-enzymatic, anti-HIV, anti thrombin, antiallergic, cytoprotective, neuroprotective and anti-inflammatory, which have been discussed in a comprehensive manner. Different synthetic strategies that have been reported for the synthesis of structurally different biflavonoids are also included. This chapter cites 177 references.
Transition Metal Catalyst, Solvent, Base Free Synthesis of Diaryl Diselenides under Mechanical Ball Milling Debasish Kundu, Anup Roy, and Subir Panja Bentham Science Publishers Ltd. Abstract: A convenient, efficient, and general procedure for the synthesis of diaryl diselenides has been developed by the reaction of aryl diazonium tetrafluoroborates and potassium selenocyanate on the surface of alumina under ball-milling in the absence of any solvent, transition metal catalyst, and base in room temperature. A wide range of functionalized diaryl diselenides are obtained in high purity and high yield by this procedure. Background: Synthesis of diaryl diselenides was restricted into only a few Cu-catalyzed C-Se cross-coupling protocols where the use of ligands, high reaction temp, long reaction time were required. Objective: The objective of this study is to achieve a sustainable protocol for the synthesis of diaryl diselenides. Method: Reaction of aryl diazonium fluoroborate with KSeCN was successfully performed under ball milling in the absence of any transition metal catalyst, ligands, base, and external heating to get diaryl diselenides. Results: A library of diaryl diselenides were obtained in good yields with different functional groups. Conclusion: First transition metal free protocol for the synthesis of diaryl diselenides has been developed successfully.
Nickel-copper Co-catalyzed Sustainable Synthesis of Diaryl-chalcogenides Debasish Kundu, Anup Roy, Abhijit Singha, and Subir Panja Bentham Science Publishers Ltd. In recent times, Nickel has become a powerful alternative transition metal catalyst for performing cross-coupling reactions due to its low cost and better sustainability. Thus, a sustainable Nicatalyzed C-Se cross coupling has been developed in the presence of catalytic amount of copper iodide as co-catalyst. A wide range of substituted diaryl selenides has been synthesized by this Ni-Cu dual catalyzed C-Se cross coupling. The reaction is following an oxidative addition and reductive elimination pathway where Cu is playing an important role in transmetalation. The mechanism of the reaction was established by several experimental techniques.
Copper-Silver Dual Catalyzed Decyanative C–Se Cross-Coupling Nirmalya Mukherjee, Debasish Kundu, and Brindaban C. Ranu Wiley AbstractTraditionally, a metal‐catalyzed cross‐coupling reaction is governed by displacement of leaving groups such as halogens, tosylates, etc. by different nucleophiles leading to the formation of carbon‐carbon and carbon‐heteroatom bonds. Besides displacement of traditional leaving groups in coupling reactions decyanative cross‐coupling has also received current attention. The objective of this work is to develop a decyanative cross‐coupling through metal‐assisted nucleophilic displacement, which is less explored so far. Thus, a decyanative cross‐coupling of aryl selenocyanate with aryl‐/alkylacetylenes, boronic acids and silanes has been accomplished by a copper‐assisted nucleophilic displacement reaction for an easy access to a series of diaryl, aryl alkyl, aryl vinyl and aryl alkynyl selenides. The best yield of product was obtained using 5 mol% of Cu(OAc)2, Ag2CO3 (20 mol%) and Cs2CO3 (1 equiv.) at 100 °C for 8 h in N‐methylpyrrolidinone (NMP). The advantages of simple operation, high yields and general applicability make this procedure more attractive. A mechanistic pathway has been proposed. Silver plays a key role in the decyanation process. A plausible mechanistic pathway of this decyanative carbon‐selenium cross‐coupling has been proposed based on UV, EPR, HR‐MS and IR analytical data along with results obtained from control experiments.magnified image
Pd(0)-catalyzed intramolecular Heck reaction: A general route for fused oxepine derivatives Arup Kumar Adak, Arabinda Mandal, Susanta Kumar Manna, Suresh Kumar Mondal, Akash Jana, Dipesh Ghosh, Debasish Kundu, Shubhankar Samanta, and Jayanta K. Ray Informa UK Limited ABSTRACT A simple and facile approach for the synthesis of various structurally different tricyclic bent oxepine frameworks from a readily accessible precursor has been introduced. The synthesis of substituted oxepine derivative involved Pd(0)-catalyzed Heck reaction. This methodology enriches the literature for the large ring formation. GRAPHICAL ABSTRACT
Palladium-Catalyzed Decarboxylative Selective Acylation of 4H-Benzo[d][1,3]oxazin-4-one Derivatives with α-Oxo Carboxylic acids via Preferential Cyclic Imine-N-Directed Aryl C-H Activation Biju Majhi, Debasish Kundu, Tubai Ghosh, and Brindaban C. Ranu Wiley AbstractThe benzoxazine scaffolds are of much interest as they are found in a large array of natural products and pharmaceutical drugs with diverse activities. We have developed a palladium‐catalyzed decarboxylative selective mono‐ and bis‐acylation of 4H‐benzo[d][1,3]oxazin‐4‐one derivatives with α‐oxo carboxylic acids via preferential cyclic imine‐N‐directed C−H activation. 2‐Aryl‐4H‐benzo[d][1,3]oxazin‐4‐one was acylated with a variety of substituted phenylglyoxylic acids to produce the corresponding products. It was observed that electron‐donating groups (CH3, OCH3) at any position of the aromatic ring of phenylglyoxylic acid provided good to excellent yields, whereas phenylglyoxylic acids containing electron‐withdrawing groups (COCH3, CN, NO2) gave the products in moderate yields. Interestingly when the reaction was performed with silver triflate (AgOTf) in place of silver nitrate (AgNO3) in the presence of 4 equivalents of glyoxylic acid, the bis‐acylated product was obtained together with a small amount of mono‐acylated product. This is the first report of acylation of 2‐aryl‐4H‐benzo[d][1,3]oxazin‐4‐ones via C−H activation. The notable features of this reaction are acylation with more challenging heteroarene‐oxo carboxylic acids and alkyl oxo carboxylic acids. This new protocol provides an easy and efficient access to a variety of o‐acyl‐4H‐benzo[d][1,3]oxazin‐4‐one derivatives which are of pharmaceutical importance.magnified image
Cobalt catalysed, copper assisted C(sp<sup>2</sup>)-P cross coupling Tubai Ghosh, Pintu Maity, Debasish Kundu, and Brindaban C. Ranu Royal Society of Chemistry (RSC) An efficient C(sp2)–P cross coupling has been achieved using a Co/Cu catalytic system for access to vinyl and aryl phosphonates.
Nickel-Copper-Catalyzed C(sp<sup>2</sup>)- N Cross-Coupling of Cyclic and Bridged Amides: An Access to Cyclic Enamides and Alkenyl Vince Lactams Pintu Maity, Debasish Kundu, and Brindaban C. Ranu Wiley AbstractAn efficient C(sp2)N cross‐coupling of styrenyl and vinyl halides with cyclic and bridged amides catalyzed by nickel acetonylacetonate [Ni(acac)2] and copper(I) iodide (CuI) in the absence of any ligand has been developed. The reaction conditions are optimized to give the maximum yield of products using cesium carbonate (Cs2CO3) (2.0 equiv.) in N‐methyl‐2‐pyrrolidinone (NMP) at 110 °C under argon in the presence of Ni(acac)2/CuI (10 mol% each). A series of alkenyl derivatives of Vince lactams (bridged amides) and cyclic amides are obtained by this procedure. Halogen‐containing styrenyl bromides also underwent coupling with amides to provide the products. The coupling is highly chemoselective as during the reactions the halogens (Br, Cl, F) on the aromatic ring remained intact and these can be used for further functionalization to make these enamides more useful. Although the (E)‐styrenyl halides produced the corresponding (E)‐styrenyl enamides, reactions with (Z)‐styrenyl halides produced 1,3‐di‐ynes instead of (Z)‐styrenyl enamides. This may be explained by the possibility of E2 type elimination of (Z)‐styrenyl halides in the presence of a strong base like cesium carbonate followed by homocoupling. This catalyst system works efficiently for the N‐arylation too along with N‐styrenylation and vinylation. The bridged as well as cyclic amides successfully coupled with substituted aryl halides to provide the corresponding products. In general, the reactions are clean and high yielding. The operations are very simple and the products are obtained pure by standard column chromatography. The reaction is compatible with variety of amides and alkenyl bromides. The roles of nickel acetonylacetonate and copper(I) iodide in this reaction have been established and a possible reaction pathway has been outlined. The significant feature of this protocol is the alkenylation of Vince lactams via C(sp2)N cross‐coupling, which has not been reported so far and these products may have much potential in the pharmaceutical industry.magnified image
Ascorbic Acid Promoted Oxidative Arylation of Vinyl Arenes to 2-Aryl Acetophenones without Irradiation at Room Temperature under Aerobic Conditions Biju Majhi, Debasish Kundu, and Brindaban C. Ranu American Chemical Society (ACS) A convenient and general protocol for oxidative arylation of vinyl arenes by aryl radicals generated in situ from arene diazonium fluoroborates promoted by ascorbic acid in air at room temperature has been developed in the absence of any additive and visible light irradiation. A series of diversely substituted 2-aryl acetophenones have been obtained in good yields by this procedure.
Cobalt-catalyzed intermolecular C(sp<sup>2</sup>)-O cross-coupling Debasish Kundu, Manisha Tripathy, Pintu Maity, and Brindaban C. Ranu Wiley AbstractCobalt(II)‐catalyzed C(sp2)O cross‐coupling between aryl/heteroaryl alcohols and vinyl/aryl halides in the presence of CuI has been achieved under ligand‐free conditions. In this reaction, copper plays a significant role in transmetalation rather than being directly involved in the CO coupling. This unique Co/Cu‐dual catalyst system provides an easy access to a library of aryl–vinyl, heteroaryl–styryl, aryl–aryl, and heteroaryl–heteroaryl ethers in the absence of any ligand or additive.
Visible-Light-Photocatalyzed Metal-Free C–H Heteroarylation of Heteroarenes at Room Temperature: A Sustainable Synthesis of Biheteroaryls Pintu Maity, Debasish Kundu, and Brindaban C. Ranu Wiley AbstractAn efficient C–H heteroarylation of heteroarenes is achieved through visible‐light photoredox‐catalyzed diazotization of heteroarylamines in situ by tBuONO at room temperature. A library of functionalized biheteroaryls is obtained by using this protocol. The reaction avoids the use of transition‐metal catalysts, additives, and acidic reaction medium.