About the participation of σ, π and n orbitals in the solvolysis of 2- and 3-oxo-1-norbornyl triflates

Article abstract of DOI:10.1016/0040-4020(96)00845-9

The solvolysis of 3,3-dimethyl-2-oxo- and 2,2-dimethyl-3-oxo-1-norbornyltriflates (6 and 8) takes place with formation of ring contracted and fragmented products respectively. The effect of the substituents on the solvolysis rates is explained taking into account n- and σ-participation. This n,σ-participation causes changes in the structure and stability of the intermediate carbocations, which can be detected by the AM1 method.