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- Title
The adamantane rearrangement of 1,2-trimethylenenorbornanes. Part V. Rearrangements of 1,2-trimethylenenorbornanes initiated by regioselective formation of carbocation centers at C(2) and C(6).
- Authors
Klester, Alfred Michael; Ganter, Camille
- Abstract
The behaviour of the regioselectively generated carbocation centers at C(2) and C(6) in 1,2-trimethylenenorbornanes was investigated in order to study the occurrence or absence of a degenerate rearrangement E⇄M in the adamantane rearrangement of both 1,2- endo- ( 1) and 1,2- exo-trimethylenenorbornane ( 2) to 2- endo,6- endo-trimethylenenorbornane ( 3). A degenerate rearrangement E⇄M is inevitably involved inasmuch as a 1,2-trimethylenenorborn-2-yl cation E not only is formed directly as manifested by the conversions of the reactants 4 (C(2), C(3)-olefin) and 6 (C(2), C(3′)-olefin), but also indirectly ( via F→E) if the leaving group at C(6) to be ionized occupies the endo-position (6- endo-alcohol 8). No degenerate rearrangement E⇄M is operative starting from reactants that lead directly to a 2,6-trimethylenenorborn-2-yl cation G; this is the case with both the ionization of the 6- exo-alcohol 10 having the leaving OH-group in a stereoelectronically favoured configuration to undergo simultaneous C(1), C(2)-bond migration (→ G) as well as the protonation of the olefin 13 which is followed by same reaction pathway.
- Publication
Helvetica Chimica Acta, 1985, Vol 68, Issue 3, p734
- ISSN
0018-019X
- Publication type
Article
- DOI
10.1002/hlca.19850680323