Mechanistic criteria for cation radical reactions: Aminium salt-catalyzed cyclopropanation

Article abstract of DOI:10.1021/ja00126a007

Mechanistic studies of the cyclopropanation of a series of trans-stilbenes by ethyl diazoacetate catalyzed by two different triarylaminium salts decisively confirm a cation radical mechanism and rule out a hypothetical electrophilic mechanism. The elucidation of key aspects of these cation radical mechanisms, including kinetic vs equilibrium control of ionization and chain vs catalytic mechanisms, has also been achieved for these systems. New mechanistic criteria for the positive identification of cation radical mechanisms are proposed.