Synthesis of Disilanes, Dihydrosiloles, and 1,4‐Disilacyclohexa‐2,5‐dienes by Transition‐Metal‐Free Transfer of Diphenylsilylene and Dimethylsilylene from Silylboronic Esters
Ikuo Sasaki, Asahi Maebashi, Jiaying Li, Toshimichi Ohmura, Michinori Suginome
Abstract
Abstract We found that the transfer of diphenylsilylene (Ph 2 Si:) from Ph 2 (Et 2 N)Si−B(pin) ( 1 a ) takes place in toluene or p ‐xylene at 110–135 °C under transition‐metal‐free conditions. The reaction of alkoxysilanes with 1 a affords alkoxydisilanes through the insertion of diphenylsilylene into the Si−O bond. Dihydrosiloles and a 1,4‐disilacyclohexa‐2,5‐diene are synthesized by the reaction of 1 a with 1,3‐dienes and an alkyne, respectively, through cycloaddition of the carbon‐carbon unsaturated bonds with diphenylsilylene. Me 2 (Et 2 N)Si−B(pin) ( 10 ) is applicable to the transition‐metal‐free transfer of dimethylsilylene (Me 2 Si:).
Topics & Concepts
ChemistryTransition metalCycloadditionTolueneAlkyneMetalCarbon fibersHydrocarbonMedicinal chemistryPolymer chemistryPhotochemistryCatalysisOrganic chemistryComposite materialComposite numberMaterials scienceSynthesis and characterization of novel inorganic/organometallic compoundsOrganoboron and organosilicon chemistryCatalytic Cross-Coupling Reactions