85689-16-3Relevant academic research and scientific papers
Nitrenium and Carbenium Ions in Rearrangements of 2-Azabicyclic Systems
Heesing, Albert,Herdering, Wilhelm
, p. 1081 - 1096 (2007/10/02)
An ionic mechanism proceeding in intimate ion pairs is suggested for the rearrangement of N-sulfonyloxy derivatives of 2-azabicycloheptane and -hept-5-ene (e. g. 9, 11 -> 10, 12). 1.Experiments with 18O labelled educts show partial scrambling dependend both on structure of educt and solvent. 2.In methanol the intermediate carbenium ions (19, 23) react to give methoxy compounds. 3.MINDO/3-calculations are in agreement with the experiments: a) In the saturated systems the nitrenium ion 20 is a stable intermediate. b) The optimized geometries of the rearranged carbenium ions (21, 23) are consistent with the products obtained in methanol.
