Long-range olefin isomerization could lead to the remote functionalization of hydrocarbon chains, which is advantageous with regards to atom-, step-, and redox economy. However, present methodologies for long-range olefin isomerization are mainly focused on heteroatom directed remote olefin migration; studies using aryl groups as the directing group are limited. The limited examples either utilize aryl olefins with special substituted groups on a benzene ring, or use elaborately optimized ligands or co-catalysts to accelerate the isomerization. A more simple catalytic system for general aryl olefins, without the need for special ligands or co-catalysts, was to be developed. Herein, we report a Pd-catalyzed long-range olefin isomerization (up to 15 units) for general aryl olefins via a 1,2-hydrogen shift mechanism. This methodology provides a simple pathway to long-range olefin isomerization without the participation of special ligands or co-catalysts.

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Amines are widely applied in the chemical and pharmaceutical industries, and the development of synthetic methods for their preparation is driven by their importance. The amination of alkenes is a direct and efficient method for the construction of amines, of which oxidative amination is more valuable because it can give the desired products with greater functionality and flexibility. In oxidative amination, using molecular oxygen (O2) as a terminal oxidant has promising industrial application prospects. In recent years, the palladium‐catalyzed aerobic oxidation of alkenes has seen significant progress, and its related research has also been extended to the aerobic oxidative amination of alkenes. The corresponding oxidation systems have been developed from early research involving the introduction of cocatalysts to the more recent systems which utilize auxiliary ligands instead of cocatalysts. In this review, the advancements in the palladium‐catalyzed aerobic oxidative amination of monoalkenes and conjugated dienes over the last two decades are discussed, with emphasis on aerobic oxidation process and their associated mechanisms.