LAUSR

Mechanism-guided reaction development is a well-appreciated research paradigm in chemistry since the merging of mechanistic knowledge would accelerate the discovery of new synthetic methods. Low-valent transition metals such as Pd(0)- and Rh(I)-catalyzed C-H arylation with aryl (pseudo)halides is among the enabling reactions for the exclusive cross-coupling of two different aryl partners. However, different from the situation of Pd(0)-catalysis, the mechanism of Rh(I)-catalyzed C-H arylation is underexplored. The sequence of the elementary steps of aryl C-H activation and oxidative addition of aryl (pseudo)halides remains unclear. Herein, we report comprehensive experimental and computational studies toward explicit mechanistic understandings of Rh(I)-catalyzed intermolecular asymmetric C-H arylation between 2-pyridinylferrocenes and aryl bromides. The identification of each elementary step in the catalytic cycle and the structural characterization of the key intermediates and transition states allow the rational design and development of challenging intramolecular reactions. The successful realization of this reaction mode set the foundation for the facile synthesis of planar chiral [m]ferrocenophanes (m = 6-8), a class of rarely explored target molecules with strained structures and intriguing molecular topology.