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The Aluminum‐Bromide‐Catalyzed Adamantane Rearrangement of syn ‐ and anti ‐Tricyclo[4.2.1.1 2,5 ]decane
Author(s) -
Brossi Marco,
Ganter Camille
Publication year - 1987
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.19870700731
Subject(s) - carbocation , chemistry , decane , adamantane , bromide , medicinal chemistry , allylic rearrangement , stereochemistry , hydride , catalysis , photochemistry , organic chemistry , hydrogen
In the presence of AlBr 3 in CS 2 at temperatures below 0°, syn ‐tricyclo[4.2.1.1 2,5 ]decane ( 1 ) isomerizes exclusively to anti ‐tricyclo[4.2.1.1 2,5 ]decane ( 2 ) at a higher rate than the latter rearranges to 2‐ exo ,3‐ exo ‐trimethylene‐8,9,10‐trinorbornane ( 4 ). However, at temperature above 0°, the anti ‐isomer 2 isomerizes to 4 faster than 1 to 2 and 4 . As a consequence, hydride abstraction occurs at C(3) (→carbocation a , which rearranges to carbocation b ( anti ‐skeleton)) in the syn ‐isomer 1 , and more readily at C(9) (→carbocation c ) than at C(3) (→carbocation b ) in the anti ‐isomer 2 .