Reactions of nitrosonium ethyl sulfate with olefins and dienes: An experimental and theoretical study

Nitrosonium ethyl sulfate (1), which is generated in situ from ethyl nitrit e and sulfur trioxide, is a convenient reagent for the one-pot transformati on of olefins and dienes into substituted aldehydes and ketones. New experi mental and theoretical aspects of this reaction are discussed. A DFT and ab initio computational study is undertaken to provide further insight into t he mechanism of electrophilic nitrosation, including the initial pi-complex es, transition states, and the intermediates involved in subsequent carbony l formation.