We report a uniquely high-yielding, general, and practical ortho bromination and iodination reaction of different classes of aromatic compounds. This reaction occurs by Rh(III)-catalyzed C-H bond activation methodology and is therefore the first example of the application of this cationic catalyst for C-Br and C-I bond formation.

rhodium (RhCp*)-catalyzed C À H transformations have emerged as a prosperous field in C À H bond activation. Recent advances in this area have significantly focused on the development of new strategies for C À C and C À heteroatom bond formation that are characterized by the novel reactivity of the RhCp* catalyst to undergo formal S N-type reactions with electrophilic substrates. This review is intended to give an overview on this rather new class of RhCp*-catalyzed C À H transformations, covering recent C À C and C À heteroatom bond-forming reactions. The nature of the reaction partner in these C À H functionalization reactions serves as a guideline throughout this article and, combined with selected descriptions of mechanistic proposals, should emphasize general characteristics of transformations within this novel reaction class.

All(yl) possible! A rhodium(III)‐catalyzed intermolecular direct CH allylation reaction utilizing readily accessible allyl carbonates was developed. This method allows the allylation of electron‐neutral arenes, providing complete γ‐selectivity, high isomeric ratio, good substrate scope, and excellent functional group compatibility.

The Rh(III)-catalyzed selective bromination and iodination of electron-rich heterocycles is reported. Kinetic investigations show that Rh plays a dual role in the bromination, catalyzing the directed halogenation and preventing the inherent halogenation of these substrates. As a result, this method gives highly selective access to valuable halogenated heterocycles with regiochemistry complementary to those obtained using uncatalyzed approaches, which rely on the inherent reactivity of these classes of substrates. Furans, thiophenes, benzothiophenes, pyrazoles, quinolones, and chromones can be applied.

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