Polar versus steric effects in the solvolysis of 6 endo ‐substituted 2 endo ‐norbornyl p ‐toluenesulfonates. Norbornanes , Part 8

The solvolysis rates and products of the 6 endo ‐R‐substituted 2 endo ‐norbornyl toluenesulfonates 6a – 6i have been determined. The rates of 6a – 6g correlate with the inductive constants σ   I qthe 6 endo ‐substituents and are not related to the size of the latter. It is therefore concluded that polar rather than steric effects control the exo / endo ‐rate ratios of norbornyl sulfonates. Products are derived mainly from rearranged 6 exo ‐R‐norbornyl cations when the substituent is an electron donor and from unrearranged 6 endo ‐R‐substituted cations when the substituent is an electron acceptor.