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The solvolysis rate constants k for the 6-endo-substituted 2-exo-norbornyl toluenesulfonates 7 have been determined. Values of log k correlate well with the respective inductive constants of the substituents except when the latter are nucleophilic and therefore lead to endo-cyclization, or when they are n-electron donors and cause concerted fragmentation. In general 6-endo-substituted tosylates 7 react somewhat more slowly than their 6-exo-epimers.Identical or different mixtures were obtained from the C(6)-epimers 7 and 1 depending on whether the substituent was an electron donor or acceptor. It is concluded that donor substituents at C (6) enhance 1,3-bridging in the intermediate epimeric cations and lead to their rapid and complete equilibration, and that electron acceptors reduce bridging and hence their equilibration rates.Corresponding author. 2,Norbornanes, Part 5: [l].

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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 Iq 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.

The Synthesis and Hydrolysis of 6endo‐Substituted 2endo‐Norbornyl p‐Toluenesulfonates The hydrolysis products of the p‐toluenesulfonates of several hitherto unknown 6endo‐substituted 2endo‐norbornanols have been determined.