The nature and role of 8-deltacyclyl and 7-isodeltacyclyl cations in solvolytic reactions of parent brosylates.

摘要: Solvolysis of exo-8-deltacyclyl brosylate proceeds directly through a C2 delocalized cation to acetate. The solvolysis the endo epimer presents more complex picture, reacting via classical deltacyclyl cation, nonclassical and isodeltacyclyl cation. exo-7-isodeltacyclyl generates 7-isodeltacyclyl ion subsequently forming 8-deltacyclyl acetate cationic intermediates in these three related reaction manifolds are characterized using density functional methods at B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) BPW91/6-311+G(3df, 2p)//BPW91/6-31G(d) levels.