Quantum calculations on the acid catalyzed rearrangements of norborn-5-en-2-one, 7-oxanorborn-5-en-2-one and 7-azanorborn-5-en-2-one - The electron-releasing effect of homoconjugated carbonyl group

Protonation of norbom-5-en-2-one gives 6-oxo-2-norbomyl cation (2) as most stable C7H9O+ cation. Quantum calculations at B3LYP/6-31G(d) level (gas phase, 1 atm, 25 degrees C) predict a C-s-structure for 2 that can be represented as an intramolecular pi-complex (Dewar pi-complex model) of an acetylium ion with an alkene (cyclopent-3-enyl moiety). Isomeric 5-oxo-2-norbornyl (1) cation is calculated to be 16.7 kcal/mol less stable than 2. Part of the relatively high stability of 2 arises from the electron-releasing carbonyl group through n(C=O) sigma 2p(C+) hyperconjugation. This effect is also present in more stable 6-oxo-3-oxa (14) and 6-oxo-3-aza-2-norbornyl cation (19) as these ions are calculated to be 7.4 and 3.3 kcal/ mol, respectively, more stable than their 5-oxo isomers. (c) 2007 Elsevier B.V. All rights reserved.