Themed collection C-H Functionalization

Significant progress has been accomplished in direct olefinations through twofold C–H bond functionalization of arenes and heteroarenes employing readily accessible, selective and inexpensive ruthenium(II) catalysts.

We present a review highlighting advancements in the field of asymmetric cycloisomerization reactions which, due to significant improvements occurring in the last twenty years, efficiently produce diverse polycyclic compounds with excellent selectivity.

Towards “Oxidative-Ullmann–Goldberg” and “Oxidative-Buchwald–Hartwig” type amination reactions.

This review gathers metal-catalysed sp² C–H bond activation reactions in water for C–C bond cross-couplings and shows the partnership of water to increase the catalyst activity.

The activation and catalytic functionalization of methane are reviewed showing that this area requires further and urgent development in the incoming years.

Ligand cyclometalative C–H bond activation in rare earth and actinide complexes is discussed. The scope is intended to outline routine cases, while also highlighting exceptional cyclometalation reactions that lead to unusual bonding modes.

Our recent developments in transition metal-catalyzed oxidative coupling via C–H functionalization of aromatic, benzylic and allylic C–H bonds is summarized.

This tutorial review aims to highlight the current achievements in the field of A³-couplings and related transformations.

Ligand chemistry has given a significant impetus to produce functionalized indoles by assisting novel powerful palladium-catalysed intra- and intermolecular cyclizations.

Rh(III) catalysts readily catalyze the oxidative C–H activation of arenes under chelation assistance, leading to C–C, C–N, and C–O bond formation.

C–H amination has become a viable method for the efficient installation of nitrogen atoms en route to allyl amines and α-amino carbonyl compounds.

A room temperature decarboxylation/C–H functionalization cascade has been developed for concise construction of quaternary oxindoles by means of visible-light photoredox catalysis.

A palladium-catalyzed decarboxylative acylation of phenylacetamides with α-oxocarboxylic acids via C–H bond activation is described.

An efficient synthesis of fluorenones from diaryl ketones by Pd-catalyzed oxidative cyclization is described. A possible mechanism involving a carbonyl group assisted ortho-C–H activation and cyclometalation followed by a second C–H activation to form a six-membered palladacycle and reductive elimination is proposed.

An I₂ promoted iodination, Kornblum oxidation, and annulation domino protocol was developed to construct 2-acylbenzothiazoles from aromatic ketones and o-aminobenzenethiols.

Using CuBr₂ as an additive, the Pd-catalyzed intermolecular C–H–C–H cross-coupling between benzoxazoles and unactivated simple arenes has been developed.

A one-step efficient synthesis of 3-acyloxindole derivatives was developed with extremely good substrate scope and significant opportunities for structural diversification.

A direct synthesis of iron–NHC complexes by C–H activation of the corresponding imidazolium salts with commercially available Fe₃(CO)₁₂.

A cobalt–N-heterocyclic carbene catalyst promotes a chelation-assisted aromatic C–H functionalization reaction via addition to an aromatic aldimine.

A highly chemo-, regio-selective, and efficient palladium-catalyzed deamidative arylation of azoles with arylamides was developed via a tandem decarbonylation–C–H activation.

Iron served as the catalyst for the direct C–H functionalization/C–S bond formation to afford benzothiazoles under mild conditions.

Selective hydroxylation of 3° and benzylic C–H bonds is made possible using a non-metal-based catalyst system, Oxone as the terminal oxidant, and an aqueous fluoroalcohol solvent mixture.

A Rh(III)-catalyzed C–H activation–desymmetrization of diazabicycles with arenes as an expedient approach to functionalized cyclopentenes is reported.

An unprecedented Rh(III)-catalyzed cyclization of benzamides and methylenecyclopropanes for the divergent synthesis of privileged heterocycles is reported.

A family of iridium(III)-bis(oxazolinyl)phenyl complexes has been developed to catalyze enantioselective C-H functionalization reactions. DFT studies provide evidence for an axially bound carbene and provide a unique model for stereoinduction in atom transfer reactions employing bis(oxazolinyl)phenyl ligands.

We report the [Y{N(SiMe₃)₂}₃] catalysed dehydrocoupling of triphenylphosphonium methylide with phenylsilane to form the silylated ylide Ph₃PCHSiH₂Ph.

The first application of visible-light-mediated synthetic photochemistry in continuous flow is described. Using an operationally simple photoreactor design, several Ru(bpy)₃²⁺-catalyzed transformations were performed with 10–50 fold rate enhancement over the corresponding batch methods.

Quinolines and tetrahydroquinolines were prepared from a common precursor through Pd(0)-catalyzed cyclopropane C–H bond functionalization.