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

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Abstract
The solvolysis rates and products of the 6endo‐R‐substituted 2endo‐norbornyl toluenesulfonates 6a–6i have been determined. The rates of 6a–6g correlate with the inductive constants σ the 6endo‐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 6exo‐R‐norbornyl cations when the substituent is an electron donor and from unrearranged 6endo‐R‐substituted cations when the substituent is an electron acceptor.