C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C–H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C–H activation until summer 2018.

3d Transition Metals for C-H Activation.

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.

Good Partnership between Sulfur and Fluorine: Sulfur-Based Fluorination and Fluoroalkylation Reagents for Organic Synthesis

Carbon trifluoromethylation reactions of hydrocarbon derivatives and heteroarenes.

Transformations of aromatic compounds into the corresponding amines, amides, and imides through carbon–hydrogen (C–H) bond functionalization represent one of the most step- and atom-economical methods for the synthesis of arylamine compounds. Because arylamines are privileged structures in materials- and biology-oriented functional molecules, the development of novel and efficient synthetic methods for aromatic C–H amination has received significant attention from a wide range of research fields including materials and pharmaceuticals. This review covers recent advances in catalytic aromatic C–H amination reactions. An array of recently developed new reactions are categorized by the nature of aromatic substrates: (1) 5-membered heteroarenes, (2) arenes having a nitrogen moiety in the molecule (intramolecular C–H amination), (3) arenes having a directing group, (4) simple arenes with excess amounts, and (5) simple arenes as the limiting reagents.

Catalytic Methods for Aromatic C–H Amination: An Ideal Strategy for Nitrogen-Based Functional Molecules

Synthesis of Oxindoles through Silver‐Catalyzed Trifluoromethylation–, Difluoromethylation– and Arylsulfonylation–Cyclization Reaction of N‐Arylacrylamides

Shaobo Zhuang

Papers

Synthesis of Oxindoles through Silver‐Catalyzed Trifluoromethylation–, Difluoromethylation– and Arylsulfonylation–Cyclization Reaction of N‐Arylacrylamides

Copper-mediated ortho C-H sulfonylation of benzoic acid derivatives with sodium sulfinates.

Copper-Mediated ortho-Nitration of Arene and Heteroarene CH Bonds Assisted by an 8-Aminoquinoline Directing Group

Synthesis of oxindoles via Cu-mediated reactions between N-phenylacrylamides and ethyl 2-bromo-2-methylpropionate

Copper-Mediated ortho-Nitration of Arene and Heteroarene C—H Bonds Assisted by an 8-Aminoquinoline Directing Group.