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Fibrous nanosilica: A new family of high‐surface‐area silica nanospheres (KCC‐1) have been prepared (see picture). KCC‐1 features excellent physical properties, including high surface area, unprecedented fibrous surface morphology, high thermal (up to 950 °C) and hydrothermal stabilities, and high mechanical stability.

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).

A nonclassical heating technique using microwaves, termed "Bunsen burner of the 21st century", is rapidly becoming popular and is dramatically reducing reaction times. The significant outcomes of microwave (MW)-assisted green chemistry endeavors, which have resulted in the development of synthetic protocols for drugs and fine chemicals synthesis that are relatively more sustainable, are summarized. The use of emerging microwave-assisted chemistry techniques in conjunction with greener reaction media is dramatically reducing chemical waste and reaction times in several organic syntheses and chemical transformations. A brief historic account of our own experiences in developing MW-assisted organic transformations, which involve various benign alternatives, such as solid-supported reagents, and greener reaction media, namely, aqueous, ionic liquid, and solvent-free, for the synthesis of various heterocycles, coupling reactions, oxidation-reduction reactions, and some name reactions are described. Synthesis of Heterocycles. The synthetic chemistry community has been under increased pressure to produce, in an environmentally benign fashion, the myriad of heterocyclic systems required by society in a short span of time, and one of the best options to accelerate these synthetic processes is to use MW technology. The efficient use of the MW heating approach for the synthesis of various heterocyclic compounds in aqueous and solvent-free medium is discussed. Organic Named Reactions. The application of MW chemistry for various named reaction such as the Prins reaction, the Suzuki reaction, the Heck reaction, the Aza-Michael reaction, Trost's gamma-addition, and the Cannizzaro reaction are summarized. Synthesis and Application of Ionic Liquids. Ionic liquids (ILs), being polar and ionic, in character couple with MW irradiation very efficiently and are, therefore, ideal MW-absorbing candidates for expediting chemical reactions. MW-assisted solvent-free synthesis and application of ILs are discussed. Oxidation-Reduction Reactions. MW protocols using mineral oxides such as alumina, silica, and clay to immobilize reagents on such solid supports have been extensively explored under "dry" media conditions. Various solvent-free examples of oxidation reactions are discussed that involve mixing of neat substrates with clay-supported iron(III) nitrate (clayfen) or iodobenzene diacetate (IBD) as an oxidant; some interesting MW reduction protocols using borohydrides are also discussed. Protection-Deprotection Reactions. The protection and deprotection of alcohols and amines are common events in multistep organic syntheses. Various protection and deprotection protocols under MW irradiation are discussed, including tetrahydropyranylation and (benzyloxycarbonyl) (Cbz)-protection, which are the most frequently employed methods.