Ruthenium-Mediated Phospha-Buchner Ring Expansion: Phosphorus Insertion into a Pendant Arene

Abstract

A ruthenium metalloligand platform enables formal phosphorus-atom insertion from NaOCP into a pendant electron-rich arene, affording a Ru-bound phosphepine without prior arene functionalization. X-ray diffraction confirms a puckered, bond-localized seven-membered P-heterocycle formed without arene prefunctionalization. DFT supports dearomatizative [2+1] cycloaddition followed by facile electrocyclic ring opening.