Facile Generation and Isolation of π‑Allyl Complexes from Aliphatic Alkenes and an Electron-Deficient Rh(III) Complex: Key Intermediates of Allylic C–H Functionalization

It has been established that a strongly electrophilic η5-cyclopentadienylrhodium complex, [CpERhCl2]2, is capable of reacting with aliphatic alkenes in the presence of a silver salt and cesium acetate at room temperature to give the corresponding π-allyl complexes in high yields. The use of an alkenyltosylamide as the alkene also afforded the corresponding π-allyl complex. Treatment of the thus obtained π-allyl complex with a silver­(I) salt and copper­(II) acetate afforded the allylic amination product, which proves the intermediacy of this π-allyl complex in the rhodium­(III)-catalyzed intramolecular oxidative allylic amination.