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The Homoallyl-Cyclopropylcarbinyl Cation Rearrangement in the Solvolyses of exo- and endo-5-Norbornen-2-yl p-Bromobenzenesulfonates. Application of 2H-NMR. Spectroscopy

✍ Scribed by Ulrich Burger; Jean-Marie Sonney; Pierre Vogel

Publisher
John Wiley and Sons
Year
1980
Tongue
German
Weight
524 KB
Volume
63
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The buffered trifluoroethanolyses and acetolyses of exo‐(2‐D)‐ (6) and endo‐(2‐D)‐5‐norbornen‐2‐yl brosylates (7) yielded exo‐5‐norbornen‐2‐yl and 3‐nortricyclyl derivatives. The deuterium distribution in these products was determined unambiguously by ^2^H‐NMR. and MS. In contrast to previous reports, each hydrogen and, consequently, each deuterium atom could be identified. Product ratio and label distribution in the solvolysis of 6 make unnecessary the intervention of asymmetrical homoallylic cation intermediates. The results are most economically rationalized by invoking symmetrical 3‐nortricyclyl ion‐pair intermediates.

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In the preceding letter we have reported on the apparently complex solvolyses of the norbornen-2-yl brosylates 1 and 2. In order to understand nore about the behaviour of hawallylic systems we have studied the acetolysis of the title cca-qzounds 2 and 4. In principle, both pair: of substrates (l/3 a