Norbornanes. Part 10. Solvolysis of the Stereoisomeric 6-Cyano-2-norbornyl p-Toluenesulfonates. A Correction

The solvolysis products of the stereoisomeric 6‐cyano‐2‐norbornyl p‐toluene sulfonates 1‐4 (R  CN) in dioxane/water 7 : 3 have been determined. In contrast to an earlier report the 6exo‐cyano‐2exo‐norbornyl p‐toluenesulfonate (1; RCN) yields 30% of the 2endo‐alcohol 9 (RCN) beside the 2exo‐alcohol 10 and the norbornenes 12 and 13. The results confirm that ‐ I substituents at C(6) reduce 1,3‐bridging in the intermediate norbornyl cation and hence its rate of rearrangement. The relatively high rate constants for some 6‐fluoro‐ and 6‐cyano‐2exo norbornyl p‐toluenesulfonates are ascribed to C, C‐hyperconjugation assisted by the conjugative effects of the 6‐fluoro and cyano substituents.