Construction of Medium-Sized Benzodisilacycles via Palladium-Catalyzed Intermolecular C(sp³)-H Silylation

Silacycles have attracted significant attention due to their broad applications in synthetic chemistry, medicinal chemistry, and materials science. However, the synthesis of silacyclesparticularly medium-sized ringsremains a formidable challenge. Herein, we report a general and efficient method for accessing a new family of nine- to eleven-membered benzodisilacycles bearing an additional heteroatom (O, S, N, or Si) on the ring scaffolds via palladium-catalyzed intermolecular silylation of primary and secondary C-(sp³)-H bonds. Readily available ortho-ether, thioether, tertiary amine, and silyl-substituted aryl iodides, as well as cyclic disilanes, serve as the building blocks, laying the foundation for diversity-oriented synthesis of these novel silacyclic scaffolds (>100 examples). Other salient features include excellent chemoselectivities, broad functional group tolerance, simple reaction conditions, low catalyst loading, and scalability. The key to the high efficiency of this disilylation reaction lies in the employment of cyclic disilanes as the silylation reagents. The synthetic practicality of the current strategy is further proven by the late-stage modification of pharmaceuticals and bioactive compounds.