Transition Metal-Controlled Divergent Annulations of Azomethine Imines with Iodonium Ylides via C -Centered [1,2]-Rearrangement.

Transition metal-controlled divergent annulation reactions of azomethine imines with iodonium ylides via C -centered [1,2]-rearrangement have been developed. The azomethine imino group, as a switchable and transient directing group (DG), underwent intramolecular nucleophilic addition and in situ generated bicyclic diaziridine, which facilitated the C -centered [1,2]-rearrangement and subsequent divergent annulations in the presence of different metal complexes as the catalysts. The benzo[ c ]chromen-1-one and pyrano[ de ]isochromene scaffolds could be independently constructed with Rh(III) and Ru(II), respectively. It was worth noting that the azomethine imino group was employed first as the switchable DG through rearrangement progress.