Rhodium(III)-catalyzed direct functionalization of C-H bonds under oxidative conditions leading to C-C, C-N, and C-O bond formation is reviewed. Various arene substrates bearing nitrogen and oxygen directing groups are covered in their coupling with unsaturated partners such as alkenes and alkynes. The facile construction of C-E (E = C, N, S, or O) bonds makes Rh(III) catalysis an attractive step-economic approach to value-added molecules from readily available starting materials. Comparisons and contrasts between rhodium(III) and palladium(II)-catalyzed oxidative coupling are made. The remarkable diversity of structures accessible is demonstrated with various recent examples, with a proposed mechanism for each transformation being briefly summarized (critical review, 138 references).

C–C, C–O and C–N bond formation via rhodium(III)-catalyzed oxidative C–H activation

Aromatic substrates with oxygen- and nitrogen-containing substituents undergo oxidative coupling with alkynes and alkenes under rhodium catalysis through regioselective C-H bond cleavage. Coordination of the substituents to the rhodium center is the key to activate the C-H bonds effectively. Various fused-ring systems can be constructed through these reactions.

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Oxidative Coupling of Aromatic Substrates with Alkynes and Alkenes under Rhodium Catalysis

The potential of palladacycles: more than just precatalysts

Light-Emitting Self-Assembled Materials Based on d(8) and d(10) Transition Metal Complexes.

Intermolecular dehydrogenative Heck reactions.

Ortho vinylation of aromatic amides via cyclopalladation complexes

Reaction of norbornenes with phenylpalladium chloride

(±)-Pterocarpin (8) and other chromanocoumarans were synthesized in one step by the reaction of 2H-chromens with o-chloromercuriphenols in the presence of lithium chloropalladite.

A new route to chromanocoumarans. Synthesis of (±)-pterocarpin

The reaction of 1,2-dihydronaphthalene, indene, and acenaphthylene with phenylpalladium chloride prepared in situ from phenylmercuric chloride and lithium chloropalladate in aqueous acetone afforded 2-phenyltetrarol, 2-phenylindanol, and 2-phenylacenaphthenol respectively, accompanying by the corresponding phenylated olefins. Acetoxyphenylation products were also obtained in the reactions in acetic acid. The configurations of these oxyphenylated compounds were determined to be trans.

Naoto Inoue

Papers

Ortho vinylation of aromatic amides via cyclopalladation complexes

Reaction of norbornenes with phenylpalladium chloride

A new route to chromanocoumarans. Synthesis of (±)-pterocarpin

The Oxyphenylation of Cyclic Olefins Conjugated to the Benzene Ring by Means of Palladium Chloride

Ortho vinylation of anilines via cyclopalladation: a new route to nitrogen heterocycles