Chromic acid oxidation of polycyclic alcohols

The rates of oxidation by chromic acid in acetic acid of a series of bicyclo[2,2,1]heptan-2-ols with symmetrical exo-5,6-substituents (1,2-benzene and 1,8-naphthalene) have been measured. Rates of oxidation were found to be determined largely by the degree of nonbonded interactions in the ground state of the molecules except in the case of endo-norbornan-2-ol with an endo-naphthalene 5,6-substituent. The α-deuterium isotope effect for oxidation of this substrate (3.7) indicated that both chromate ester formation and elimination were involved in the rate limited step but that in other cases ester elimination alone was rate controlling.