Denitrogenative Ring-Contraction of Pyridines to a Cyclopentadienyl Skeleton at a Dititanium Hydride Framework

Abstract

Selective removal of the nitrogen atom from an aromatic N-heterocycle, such as pyridine, is of significant interest and importance, yet it remains highly challenging. Here, we report an unprecedented denitrogenative ring-contraction reaction of pyridines at a dititanium hydride framework, yielding cyclopentadienyl and nitride species under mild conditions. The reaction of pyridine with a dititanium tetrahydride complex (1) bearing rigid acridane-based PNP-pincer ligands at room temperature produced a cyclopentadienyl/nitride complex (2), in which the two Ti atoms are bridged by a nitride atom and one Ti atom is bonded to a cyclopentadienyl group formed by pyridine denitrogenation and ring-contraction. The reactions of 2-, 3-, and 4-methylpyridines with 1 under similar conditions yielded the same product (3), a methylcyclopentadienyl-ligated analog of 2. When 2,4- or 3,5-dimethylpyridine reacted with 1 at 60 °C, the 1,3-dimethylcyclopentadienyl-ligated analog (5) formed almost quantitatively. The mechanistic details have been elucidated by isolation of key intermediates and density functional theory calculations. It was revealed that the reaction proceeded via coordination of the N atom of a pyridine unit to a Ti atom in 1 followed by H₂ release, C═N reduction, two C–N bond cleavage (ring-opening and denitrogenation), and C–C coupling (ring closing). The involvement of C–H activation in an isopropyl group of a PNP ligand at the later stages of the reaction significantly contributed to the stabilization of the denitrogenative ring-contraction product. This work not only provides unprecedented mechanistic insights into denitrogenation of aromatic N-heterocycles but also represents a novel example of skeletal editing of aromatic N-heterocycles.