Nucleophilic Reactions at Tertiary Carbon. Part 2. σ‐ and π‐routes to the 8‐hydrindanyl cation
1973; Wiley; Volume: 56; Issue: 8 Linguagem: Inglês
10.1002/hlca.19730560809
ISSN1522-2675
AutoresKonrad B. Becker, André F. Boschung, C. A. Grob,
Tópico(s)Organic Chemistry Cycloaddition Reactions
ResumoAbstract 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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