The present review is devoted to summarizing the recent advances (2015-2017) in the field of metal-catalysed group-directed C-H functionalisation In order to clearly showcase the molecular diversity that can now be accessed by means of directed C-H functionalisation, the whole is organized following the directing groups installed on a substrate Its aim is to be a comprehensive reference work, where a specific directing group can be easily found, together with the transformations which have been carried out with it Hence, the primary format of this review is schemes accompanied with a concise explanatory text, in which the directing groups are ordered in sections according to their chemical structure The schemes feature typical substrates used, the products obtained as well as the required reaction conditions Importantly, each example is commented on with respect to the most important positive features and drawbacks, on aspects such as selectivity, substrate scope, reaction conditions, directing group removal, and greenness The targeted readership are both experts in the field of C-H functionalisation chemistry (to provide a comprehensive overview of the progress made in the last years) and, even more so, all organic chemists who want to introduce the C-H functionalisation way of thinking for a design of straightforward, efficient and step-economic synthetic routes towards molecules of interest to them Accordingly, this review should be of particular interest also for scientists from industrial R&D sector Hence, the overall goal of this review is to promote the application of C-H functionalisation reactions outside the research groups dedicated to method development and establishing it as a valuable reaction archetype in contemporary R&D, comparable to the role cross-coupling reactions play to date

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A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.

Supramolecular catalysis is a rapidly expanding discipline which has benefited from the development of both homogeneous catalysis and supramolecular chemistry. The properties of classical metal and organic catalysts can now be carefully tailored by means of several suitable approaches and the choice of reversible interactions such as hydrogen bond, metal–ligand, electrostatic and hydrophobic interactions. The first part of these two subsequent reviews will be dedicated to catalytic systems for which non-covalent interactions between the partners of the reaction have been designed although mimicking enzyme properties has not been intended. Ligand, metal, organocatalyst, substrate, additive, and metal counterion are reaction partners that can be held together by non-covalent interactions. The resulting catalysts possess unique properties compared to analogues lacking the assembling properties. Depending on the nature of the reaction partners involved in the interactions, distinct applications have been accomplished, mainly (i) the building of bidentate ligand libraries (intra ligand–ligand), (ii) the building of di- or oligonuclear complexes (inter ligand–ligand), (iii) the alteration of the coordination spheres of a metal catalyst (ligand–ligand additive), and (iv) the control of the substrate reactivity (catalyst–substrate). More complex systems that involve the cooperative action of three reaction partners have also been disclosed. In this review, special attention will be given to supramolecular catalysts for which the observed catalytic activity and/or selectivity have been imputed to non-covalent interaction between the reaction partners. Additional features of these catalysts are the easy modulation of the catalytic performance by modifying one of their building blocks and the development of new catalytic pathways/reactions not achievable with classical covalent catalysts.

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Supramolecular catalysis. Part 1: non-covalent interactions as a tool for building and modifying homogeneous catalysts.

Over the last decade molecular containers have been increasingly studied within the context of complex chemical systems. Herein we discuss selected examples from the literature concerning three aspects of this field: complex host–guest behaviour, adaptive transformations of molecular containers and reactivity modulation within them.

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Molecular containers in complex chemical systems

As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis and C–H bond functionalization is well foreseeable, and the joint force along this line has been demonstrated to be a powerful approach in making inert C–H bond functionalization more viable, predictable, and selective. In this review, we provide a comprehensive summary of organocatalysis in inert C–H bond functionalization over the past two decades. The review is arranged by types of inert C–H bonds including alkane C–H, arene C–H, and vinyl C–H as well as those activated benzylic C–H, allylic C–H, and C–H bonds alpha to the heteroatom such as nitrogen and oxygen. In each section, the discussion is classified by the explicit organocatalytic mode involved.

Organocatalysis in Inert C–H Bond Functionalization

The area of direct asymmetric functionalization of inert C–H bonds has attracted considerable attention in recent years. To realize this type of challenging but promising transformations, a lot of strategies have emerged including asymmetric C–H bond insertion by metal carbenoids or analogs, cross dehydrogenative coupling, [1,5]-hydride transfer, C–H bond functionalization involving a transient metal–carbon species and other miscellaneous methods. This review is intended to summarize and discuss the most recent developments (contributions mainly after 2009) within this area.

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Recent development of direct asymmetric functionalization of inert C–H bonds

The combination of transition metal catalysis and organocatalysis as a new and exciting research area has attracted increasing attention as it can enable the development of unprecedented transformations that is not possible by use of either of the catalytic systems alone, and can improve the reactivity, efficiency and stereocontrol of existing chemical transformations. In this review, we summarize recent remarkable progress in the field of combined transition metal catalysis and organocatalysis, further highlighting the potential of this new and exciting research area and the many challenges that still remain for the future.

Combining transition metal catalysis and organocatalysis--an update.

The [Ni(IMes)2]-catalyzed transformation of fluoroarenes into arylboronic acid pinacol esters via C–F bond activation and transmetalation with bis(pinacolato)diboron (B2pin2) is reported. Various partially fluorinated arenes with different degrees of fluorination were converted into their corresponding boronate esters.

Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C–F Bond Cleavage

Rhenium-catalyzed oxyalkylation of alkenes is described, where hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were used as, for the first time, not only an oxygenation source but also an alkylation source via decarboxylation. The reaction also features a wide substrate scope, totally regiospecific difunctionalization, mild reaction conditions, and ready availability of both substrates. Mechanistic studies revealed a decarboxylation/radical-addition/cation-trapping cascade operating in the reaction.

Zhen-Ting Du

Papers

Combining transition metal catalysis and organocatalysis--an update.

Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C–F Bond Cleavage

Alkene Oxyalkylation Enabled by Merging Rhenium Catalysis with Hypervalent Iodine(III) Reagents via Decarboxylation

Rhenium-catalyzed regiodivergent addition of indoles to terminal alkynes.

Diastereoconvergent Synthesis of trans-5-Hydroxy-6-Substituted-2-Piperidinones by Addition–Cyclization–Deprotection Process