The nature and role of 8-deltacyclyl and 7-isodeltacyclyl cations in solvolytic reactions of parent brosylates.
Solvolysis of exo-8-deltacyclyl brosylate proceeds directly through a C(2) delocalized cation to exo-8-deltacyclyl acetate. The solvolysis of the endo epimer presents a more complex picture, reacting via a classical deltacyclyl cation, the nonclassical C(2) delocalized cation, and the isodeltacyclyl cation. The solvolysis of exo-7-isodeltacyclyl brosylate generates the 7-isodeltacyclyl ion and subsequently the C(2) delocalized deltacyclyl cation forming 8-deltacyclyl acetate and exo-7-isodeltacyclyl acetate. The cationic intermediates in these three related reaction manifolds are characterized using density functional methods at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) and BPW91/6-311+G(3df, 2p)//BPW91/6-31G(d) levels.
Freeman
Peter K
PK
Department of Chemistry, Oregon State University, Corvallis, OR 97331, USA. peter.freeman@orst.edu
Dacres
Jelena E
JE
D000085:Acetates / Q000737:chemistry; D000473:Alkanes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D002412:Cations; D008958:Models, Molecular; D012997:Solvents
D000085:Acetates; D000473:Alkanes; D001643:Bridged Bicyclo Compounds; D002412:Cations; D012997:Solvents; C017573:nonane