RESUMO
This work reports an intramolecular C(sp3)-H annulation of functionalized 2,6-lutidines catalyzed by an organocalcium hydride [{(DIPPnacnac)CaH(thf)}2] (DIPPnacnac = CH{(CMe)(2,6-iPr2-C6H3N)}2). This reaction constitutes a streamlined approach for producing a new family of tetrahydro-1,5-naphthyridines and hexahydropyrido[3,2-b]azocines derivatives in good to excellent yields with high atom efficiency and broad substrates scope. A calcium alkyl complex was isolated from the stoichiometric reaction between calcium hydride and the substrate through deprotonation, which was structurally characterized and confirmed as the catalytic intermediate.
RESUMO
This work describes the chemo- and stereoselective benzylic C(sp3)-H alkenylation of tertiary ortho-methyl anilines with internal alkynes using a simple ß-diketiminato scandium catalyst. This protocol offers an efficient method for the synthesis of a new family of tertiary ortho-allylanilines in high yields. The resultant alkenylation products facilely underwent further chemical transformation to other valuable anilines. A cationic scandium benzyl species was isolated from a stoichiometric reaction and confirmed to be the catalytic intermediate.
RESUMO
The intrinsic electrophilic feature for the terminal nitrogen of α-diazo-ß-ketoesters/ketones has been elucidated by the intermolecular nucleophilic addition of two molecules of a dimethylsulfonium ylide. This methodology allows for access to highly functionalized hydrazones with a broad scope and good functional group tolerance. The reaction operates under simple and mild conditions without using a catalyst.