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Nucleophilic Reactions at Tertiary Carbon. Part 2. σ- and π-routes to the 8-hydrindanyl cation

✍ Scribed by Konrad B. Becker; André F. Boschung; Cyril A. Grob

Publisher
John Wiley and Sons
Year
1973
Tongue
German
Weight
913 KB
Volume
56
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Stereoisomeric ion pairs are implicated as intermediates in the solvolysis of cis and trans‐8‐hydrindanyl chloride 3, whereas 4‐(cyclopenten‐1‐yl)butyl tosylate 5 appears to cyclize by way of an unsymmetrically solvated 8‐hydrindanyl cation. This follows from the solvolysis products and rates of these compounds in aqueous solvents.

The rate and equilibrium constants of the chlorides 3 show that the transition state for the trans‐isomer is more stable by 0.5 kcal than the one for the cis‐isomer. By inference the intermediates differ by a similar amount of energy.

Experimental results are not explained satisfactorily by conformationally isomeric 8‐hydrindanyl cations, as suggested in the literature.

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