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      Organoselenium ligands for heterogeneous and nanocatalytic systems: development and applications

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          Abstract

          Organoselenium ligands have attracted great attention among researchers during the past two decades.

          Abstract

          Organoselenium ligands have attracted great attention among researchers during the past two decades. Various homogeneous, heterogeneous and nanocatalytic systems have been designed using such ligands. Although reports on selenium ligated homogeneous catalysts are quite high in number, significant work has also been done on the development of heterogeneous and nanocatalytic systems using organoselenium ligands. A review article, focusing on the utility of organoselenium compounds in the development of catalytic systems, was published in 2012 (A. Kumar, G. K. Rao, F. Saleem and A. K. Singh, Dalton Trans., 2012, 41, 11949). Moreover, it mainly covered the homogeneous catalysts. There are no review articles in the literature on heterogeneous and nanocatalytic systems designed using organoselenium compounds and their applications. Hence, this perspective aims to cover the developments pertaining to the synthetic aspects of such catalytic systems (using organoselenium compounds) and their applications in catalysis of a variety of chemical transformations. Salient features and advantages of organoselenium compounds have also been highlighted to justify the rationale behind their use in catalyst development. Their performance in various chemical transformations [ viz. Suzuki–Miyaura coupling, Heck coupling, Sonogashira coupling, O-arylation of phenol, transfer hydrogenation of aldehydes and ketones, aldehyde–alkyne–amine (A 3) coupling, hydration of nitriles, conversion of aldehydes to amides, cross-dehydrogenative coupling (CDC), photodegradation of substrates (formic acid, methylene blue), reduction of nitrophenols, electrolysis (hydrogen evolution reaction and oxygen reduction reactions), organocatalysis and dye sensitized solar cells] and relevant aspects of catalytic processes (such as recyclability, substrate scope and green aspects) have been critically analyzed. Future perspectives have also been discussed.

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          Most cited references134

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          Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations.

          Synthetic chemists aspire both to develop novel chemical reactions and to improve reaction conditions to maximize resource efficiency, energy efficiency, product selectivity, operational simplicity, and environmental health and safety. Carbon-carbon bond formation is a central part of many chemical syntheses, and innovations in these types of reactions will profoundly improve overall synthetic efficiency. This Account describes our work over the past several years to form carbon-carbon bonds directly from two different C-H bonds under oxidative conditions, cross-dehydrogenative coupling (CDC). We have focused most of our efforts on carbon-carbon bonds formed via the functionalization of sp(3) C-H bonds with other C-H bonds. In the presence of simple and cheap catalysts such as copper and iron salts and oxidants such as hydrogen peroxide, dioxygen, tert-butylhydroperoxide, and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), we can directly functionalize various sp(3) C-H bonds by other C-H bonds without requiring preactivation. We demonstrate (1) reaction of alpha-C-H bonds of nitrogen in amines, (2) reaction of alpha-C-H bonds of oxygen in ethers, (3) reaction of allylic and benzylic C-H bonds, and (4) reaction of alkane C-H bonds. These CDC reactions can tolerate a variety of functional groups, and some can occur under aqueous conditions. Depending on the specific transformation, we propose the in situ generation of different intermediates. These methods provide an alternative to the separate steps of prefunctionalization and defunctionalization that have traditionally been part of synthetic design. As a result, these methods will increase synthetic efficiencies at the most fundamental level. On an intellectual level, the development of C-C bond formations based on the reaction of only C-H bonds (possibly in water) challenges us to rethink some of the most fundamental concepts and theories regarding chemical reactivities. A successful reaction requires the conventionally and theoretically less reactive C-H bonds to react selectively in the presence of a variety of functional groups. With further investigation, we expect that C-C bond formations based on cross-dehydrogenative coupling will have a positive economic and ecological impact on the next generation of chemical syntheses.
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            The Role of Ligands in the Chemical Synthesis and Applications of Inorganic Nanoparticles

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              Nanocatalysts for Suzuki cross-coupling reactions.

              This critical review deals with the applications of nanocatalysts in Suzuki coupling reactions, a field that has attracted immense interest in the chemical, materials and industrial communities. We intend to present a broad overview of nanocatalysts for Suzuki coupling reactions with an emphasis on their performance, stability and reusability. We begin the review with a discussion on the importance of Suzuki cross-coupling reactions, and we then discuss fundamental aspects of nanocatalysis, such as the effects of catalyst size and shape. Next, we turn to the core focus of this review: the synthesis, advantages and disadvantages of nanocatalysts for Suzuki coupling reactions. We begin with various nanocatalysts that are based on conventional supports, such as high surface silica, carbon nanotubes, polymers, metal oxides and double hydroxides. Thereafter, we reviewed nanocatalysts based on non-conventional supports, such as dendrimers, cyclodextrin and magnetic nanomaterials. Finally, we discuss nanocatalyst systems that are based on non-conventional media, i.e., fluorous media and ionic liquids, for use in Suzuki reactions. At the end of this review, we summarise the significance of nanocatalysts, their impacts on conventional catalysis and perspectives for further developments of Suzuki cross-coupling reactions (131 references). This journal is © The Royal Society of Chemistry 2011
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                Author and article information

                Contributors
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                Journal
                ICHBD9
                Dalton Transactions
                Dalton Trans.
                Royal Society of Chemistry (RSC)
                1477-9226
                1477-9234
                June 29 2021
                2021
                : 50
                : 25
                : 8628-8656
                Affiliations
                [1 ]Department of Chemistry
                [2 ]School of Physical Sciences
                [3 ]Doon University
                [4 ]Dehradun
                [5 ]India
                [6 ]Amity School of Applied Sciences
                [7 ]Amity University Haryana (AUH)
                [8 ]Gurgaon
                Article
                10.1039/D1DT00082A
                67a7ef65-bc16-4054-bfbd-e4a8b6a2c05d
                © 2021

                http://rsc.li/journals-terms-of-use

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