Chiral crystallization: freezing a rapid Cope rearrangement in the solid state.

Homotropylidene and its derivatives undergo a fast Cope rearrangement. A homotropylidene system (cyclooctatetraene dimer) is reported that racemizes rapidly by such a valence isomerization in solution at room temperature. In the solid state, however, this rearrangement is frozen, and the single crystals precipitating from the racemic solution contain only one enantiomer.