ISSN:
0009-2940
Keywords:
2-Norbornyl cations, 5,5,6,6-tetramethyl-
;
Tetracyclo[4.2.2.12,5.01,6]undec-3-yl cations
;
Wagner-Meerwein rearrangements
;
Alkyl-bridged ions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Rearrangements of 5,5,6,6-Tetraalkyl-2-norbornyl CationsWhen the 6,6-dimethyl-2-norbornyl cation (9) is generated from the tosylhydrazone 5 by way of the diazonium ion 8, a 2H label is distributed equally between positions 1 and 2 of the exo-alcohol 10. The degeneracy of 9, previously derived from solvolytic studies, is thus confirmed for the deaminative route. 5,5,6,6-Tetramethyl-2-norbornanone (25) and tetracyclo[4.2.2.12,5.01,6]undecan-3-one (31) are prepared by using Diels-Alder methodology. The corresponding tosylhydrazones 26 and 32 are employed as precursors for the 5,5,6,6-tetramethyl-2-norbornyl and tetracyclo[4.2.2.12,5.01,6]undec-3-yl cations (11 and 12). Again, the distributions of 2H labels are close to 1 : 1. The angular distortions expected from repulsive interactions of the methyl groups in 11 and from cyclobutane annulation in 12 do not affect the relative energies of the bridged ions.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240137
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