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The Homoallyl‐Cyclopropylcarbinyl Cation Rearrangement in the Solvolyses of exo ‐ and endo ‐5‐Norbornen‐2‐yl p ‐Bromobenzenesulfonates. Application of 2 H‐NMR. Spectroscopy
Author(s) -
Burger Ulrich,
Sonney JeanMarie,
Vogel Pierre
Publication year - 1980
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19800630429
Subject(s) - chemistry , solvolysis , deuterium , ion , stereochemistry , hydrogen , medicinal chemistry , hydrolysis , organic chemistry , physics , quantum mechanics
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.