Transition‐Metal‐Free and DBU Promoted Strong Si–F Bond Activation: Catalytic Si–F/Si–H Cross Coupling Reaction under Mild Condition

Comprehensive Summary Developing method for strong Si–F σ bond activation is a very important tool in organosilicon transformation chemistry, only few examples of Si–F bond activation are precedent in the literature. Herein, we developed a new and efficient method to activate strong Si–F bond by transition‐metal‐free Si–F/Si–H cross coupling reaction catalyzed with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) catalytic system under mild conditions. Various disiloxanes bearing tolerated functional groups were successfully synthesized in moderate to excellent yields from fluorosilanes and hydrosilanes. Moreover, H 2 O was found to be the oxygen donor in this catalytic system. Density functional theory calculations were performed to verify the mechanism of DBU promoted Si–F/Si–H cross‐coupling reactions.