Memory Effects and Stereochemistry in Multiple Carbonium Ion Rearrangements

The stereochemical configuration at the initial site of heterolysis in a carbonium ion process in solution controls the specificity of migration two steps later in many sequential multiple rearrangements. These “memory effects” are attributable to the presence on the potential energy surface of small, hitherto undetectable minima. A variety of structural, stereochemical, and isotopic marking techniques are used to demonstrate that memory effects are a general feature of the ring‐expansion route to bicyclic carbonium ions. The intermediates formed in these reactions, although necessarily symmetrical or quasi‐symmetrical at equilibrium, act unsymmetrically. The memory effect uses the rate of an intramolecular carbonium ion rearrangement as a calibration with which to compare the rate of symmetrization. In this way, the system functions as a sensor of sub‐species.