https://pubs.rsc.org/en/content/articlepdf/2019/NP/C8NP00092A

Marine natural products.

The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century 1 organic chemists have sought to develop new and more efficient aryl -aryl bond-forming methods. Although there exist a variety of routes for the construction of aryl -aryl bonds, arguably the most common method is through the use of transition-metalmediated reactions. 2-4 While earlier reports focused on the use of stoichiometric quantities of a transition metal to carry out the desired transformation, modern methods of transitionmetal-catalyzed aryl -aryl coupling have focused on the development of high-yielding reactions achieved with excellent selectivity and high functional group tolerance under mild reaction conditions. Typically, these reactions involve either the coupling of an aryl halide or pseudohalide with an organometallic reagent (Scheme 1), or the homocoupling of two aryl halides or two organometallic reagents. Although a number of improvements have developed the former process into an industrially very useful and attractive method for the construction of aryl -aryl bonds, the need still exists for more efficient routes whereby the same outcome is accomplished, but with reduced waste and in fewer steps. In particular, the obligation to use coupling partners that are both activated is wasteful since it necessitates the installation and then subsequent disposal of stoichiometric activating agents. Furthermore, preparation of preactivated aryl substrates often requires several steps, which in itself can be a time-consuming and economically inefficient process.

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck-Type-lautens.pdf

Aryl-aryl bond formation by transition-metal-catalyzed direct arylation.

Microwave assisted organic synthesis-a review

The direct functionalization of C-H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon-carbon and carbon-heteroatom bonds. This Review provides an overview of C-H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.

C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals

The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications i...

http://pubs.acs.org/doi/pdfplus/10.1021/acs.chemrev.5b00482

Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis.

Palladium and copper-catalysed arylation of amines, alcohols and thiols, powerful tools for the construction of C–N, C–O and C–S bonds, are typically carried out in organic (and often toxic) solvents. Therefore the use of such a sustainable, benign solvent as water in this context has gained growing attention. This tutorial review presents the most recent advances dealing with palladium and copper-catalysed carbon–heteroatom bond formation performed in total or partial aqueous media. The particular and distinctive features of water which are apparently responsible for the acceleration and greater chemoselectivity of the aqueous protocols will also be discussed.

Palladium and copper-catalysed arylation reactions in the presence of water, with a focus on carbon-heteroatom bond formation.

A novel protocol for the copper-catalysed S-arylation of thiophenol derivatives with aryl halides leading to diaryl sulfides is reported. The reactions were catalysed by a combination of a copper salt and a 1,2-diamine derivative (acting both as the ligand and as the base) using exclusively water as the solvent. The recovery and successful reutilisation of the aqueous medium containing the active catalyst is described. Furthermore, one example of a "one-pot" process involving Br/I exchange of an aryl bromide and further S-arylation is presented.

Simple and efficient recyclable catalytic system for performing copper-catalysed S-arylation reactions in the presence of water.

On-Water Chemistry: Copper-Catalyzed Straightforward Synthesis of Benzo[b]furan Derivatives in Neat Water§

Suzuki-Miyaura biaryl and diarylmethane syntheses via the coupling of arylboronic acids with aryl and arylmethyl bromides are performed in water by means of two new CNC-type palladium pincer complexes. Good to excellent results (including high TON values and extended recycling procedures) are obtained in most cases for a range of electronically dissimilar halides and boronic acids. On the basis of a series of kinetics studies, transmission electron microscopy (TEM), mercury drop tests, and quantitative poisoning experiments, the real role of the latter palladacycles, closely linked to the formation and active participation of palladium nanoparticles, is discussed.

Esther Domínguez

Papers

Palladium and copper-catalysed arylation reactions in the presence of water, with a focus on carbon-heteroatom bond formation.

Simple and efficient recyclable catalytic system for performing copper-catalysed S-arylation reactions in the presence of water.

On-Water Chemistry: Copper-Catalyzed Straightforward Synthesis of Benzo[b]furan Derivatives in Neat Water§

Insights into the Role of New Palladium Pincer Complexes as Robust and Recyclable Precatalysts for Suzuki–Miyaura Couplings in Neat Water

A Nonsymmetric Pincer-Type Palladium Catalyst In Suzuki, Sonogashira, and Hiyama Couplings in Neat Water