Iridium‐Catalyzed Intramolecular C–H Silylation of Siloxane‐Tethered Arene and Hydrosilane: Facile and Catalytic Synthesis of Cyclic Siloxanes

Catalytic C–H silylation is an increasingly important topic in the field of organosilicon chemistry and homogenous catalysis as well as organic synthesis, but such syntheses and transformations are usually challenging and often incompatible with some functional groups. In this manuscript, a new type of silanol‐directed intramolecular dehydrogenative silylation under iridium catalysis has been developed. The described silylative cyclization has good functional group compatibility, providing a general and efficient route to unsymmetrical cyclic siloxanes with multiple potentially modifiable silicon atoms in high site‐selectivities. The resulting organosilicon compounds exhibit diverse synthetic applications owing to their unique structures.