A palladium-catalyzed cross-coupling reaction of diarylmethanol derivatives with diborylmethane has been developed. The reaction proceeds chemoselectively to deliver the corresponding homobenzylic boronates in good yields.

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.

Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP-or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.