A computational study on the sources of deuterium secondary kinetic isotope effects in carbocation-forming reactions

Calculations at the HF-DFT hybrid Becke3LYP level of theory have been undertaken on protonated 2-exo- and 2-endo-norbornanols as model substrates for 2-exo- and 2-endo-norbornyl brosylates to explore the source of the experimentally determined deuterium secondary kinetic isotope effects (KIEs). Calculations on protonated alcohols as models reproduce the "normal" behaviour of 2-endo substrate 5. The observed endo γ-KIE in the 7-unsubstituted …