Palladium(II)-Catalyzed [2+2+1] Annulation of Alkynes and Hydroxylamines: A Rodox-Neutral Approach to Fully Substituted Pyrroles.

A palladium-catalyzed [2+2+1] annulation of alkynes and hydroxylamines has been developed for the rapid construction of fully substituted pyrroles. This transformation involves sequential nucleophilic-addition of hydroxylamine to alkyne, alkyne migratory insertion, and synergistic demetallization cyclization, which provides a redox-neutral annulation approach to pyrrole derivatives. Moreover, the strategy enabled alteration of the photophysical properties of pyrrole products by varying the aryl substituents, thus leading to the development of N-functionalized tetraarylpyrroles as new fluorophores.

Construction of Structurally Rigid Azulen-6-ones via Migratory Rearrangement of Spirocycles and Their Photophysical Studies.

We report the synthesis of polysubstituted 1,1,2,3-tetraarylazulen-6-ones through the ring opening and scaffold rearrangement of spirocycles in the presence of ferric chloride under ambient conditions. Control experiments shown that this reaction may proceeded through a radical cation mechanism and futher theoretical calculation revealed that the electronic distribution of the radical cation intermediate dominated this oxidative rearrangement instead of dehydrogenation. It is noteworthy that some interesting photophysical properties, including aggregation-induced emission, halochromism, and two-photon fluorescence, were discovered for the azulen-6-one 2a, making them to work as promising functional materials in optical-related fields.