An efficient and convenient palladium-catalyzed direct intermolecular silylation of C(sp2)–H bonds by using disilanes as the silicon source with the assistance of a readily removable bidentate directing group is reported. This strategy provided a regio- and stereoselective protocol for exclusive synthesis of Z-vinylsilanes with reasonable to excellent yields and good functional group compatibility. Silylation of the isolated palladacycle intermediate revealed the Z-stereoselective pathway. Moreover, the practicality and effectiveness of this method were illustrated by a gram-scale experiment and further functionalization of the silylation product.

An efficient and convenient method enabling direct amination of unactivated methylene C(sp3)–H bonds to form C–N bonds with azodiformates as amino source is described. This method highlights the emerging strategy of unactivated methylene as versatile functional groups in organic synthesis and provides a strategy to construct functionalized C–N bonds for the synthesis of complex molecules.Keywords: azodiformates; C−H amination; methylene; palladium-catalyzed; β-amino acid derivatives;

An efficient and convenient method has been developed to achieve direct silylation of unactivated remote primary or secondary C(sp3)–H bonds to form C–Si bonds with hexamethyldisilane (HMDS). This method highlights the emerging strategy to transform unactivated methyl or methylene into versatile functional groups in organic synthesis and provides a new method to construct functionalized C–Si bonds for synthetic chemistry.