Journal of the Chemical Society. Perkin transactions II p. 1369 - 1376 (1984)
Update date:2022-08-05
Topics:
Maskill, H.
Wilson, Alan A.
Bicyclo<3.2.1>octan-3-ylamines have been deaminated in acetic acid by nitrous acid and via their N-phenyltriazines; their ethyl N-nitrosocarbabamates have also been solvolysed in ethanol.The exo-isomers give mainly unrearranged substitution, some elimination, and very little rearrangement.The unrearranged substitution is derived from both the solvent (the external nucleophile, either acetic acid or ethanol) and internal nucleophile liberated in the deaminative fragmentation step (water from the nitrous acid reaction, aniline from the triazene, and ethyl carbonate from the nitrosocarbamate).It is of predominantly retained configuration i n all three reactions with the solvents, and, as demonstrated in the solvolysis, with the internal nucleophile.The endo-isomers give mainly elimination, some unrearranged substitution, and appereciable rearrangement.The solvent-derived unrearranged substitution is with predominant inversion of configuration in all three reactions whereas that from the internal nucleophile, established by the nitrosocarbamate solvolysis, is predominantly with retention.Rearangement from both endo- and exo-compounds is best explained in terms of hydride shift from the first formed carbonium ions (in nitrogen-separated complex ion-pairs with hydrogen-bonded anions) produced in the deaminative fragmentation.This gives rearranged classical bicyclo<3.2.1>octan-2-yl carbonium ions which, in competition with nucleophilic capture and proton loss, undergo further stepwise rearrangement to a common unsymmetrical non-classical carbonium ion.The non-classical cation and its classical precursors (which, from exo-and endo-substrates, differ in the location of the counter-anion) give rise to substitution products derived from solvent and the internal nucleophile.The non-classical carbonium ion also gives some tricyclo<3.2.1.02,7>octane.The high yields of internal substitution products from both endo- and exo-compounds rule out long lived intermediates such as diazonium ions.
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