Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity

Multitasking catalysis offers a robust and sustainable strategy for achieving multiple transformations within a single catalytic system. Herein, we describe a rhodium‐catalyzed multitasking sequence that orchestrates long‐range isomerization, cycloisomerization, and hydrosilylation of 1,n‐dienes in a single operation. This work represents the first demonstration of a single catalytic system capable of performing these three distinct reactions consecutively. The transformation efficiently delivers silylated 2,3‐disubstituted dihydrobenzofuran derivatives, which are key structural motifs in bioactive and functional molecules. Systematic optimization revealed that the hydrosilylation step is highly sensitive to the steric and electronic properties of the silane reagent. Mechanistic investigations, including in situ 1 H NMR analyses, indicated that the hydrosilane strongly influences the equilibrium of long‐range isomerization by modulating the availability of catalytically active Rh–H species. In contrast to our previously developed hydroboration system, the current hydrosilylation conditions suppress alkene migration, resulting in limited product convergence. These findings uncover how the terminal functionalization reagent governs multitasking catalysis and provide valuable insight for designing next‐generation integrated catalytic systems.