Palladium‐Catalyzed Benzylic Silylation of Diarylmethyl Carbonates with Silylboranes under Base‐Free Conditions

A palladium‐catalyzed benzylic silylation of diarylmethyl carbonates with silylboranes has been developed. The reaction proceeds smoothly even under external base‐free conditions, and the corresponding benzylic silanes are formed in good to high yields. The obtained benzyl silane derivatives can work as the benzylic nucleophiles by the action of a suitable fluoride source and react with some carbon electrophiles to deliver the corresponding benzylic C−C cross‐coupled products. Additionally, while still preliminary, the allylic silylation of the isoelectronic allylic carbonates is also achieved. A palladium‐catalyzed benzylic silylation reaction of diarylmethyl carbonates with silylboranes has been developed. By taking advantage of in‐situ generated alkoxide ligand arising from the carbonate substrate, the reaction proceeds smoothly even under external base‐free conditions. The resulting benzyl silane moiety can undergo the post functionalizations to deliver the more complex diarylmethane derivatives. Additionally, the related base‐free allylic silylation reaction is also demonstrated.