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Umlagerungen von Tricyclo[3.2.1.1 2,4 ]non‐6‐yl‐, Tricyclo[4.2.1.1 2,5 ]dec‐3‐yl‐ und Tricyclo[4.2.2.1 2,5 ]undec‐3‐yl‐Kationen
Author(s) -
Kirmse Wolfgang,
Mönch Dietmar,
Müller Katja,
Gomann Klaus
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250542
Subject(s) - chemistry , carbocation , bicyclic molecule , reactivity (psychology) , stereochemistry , tricyclic , deuterium , medicinal chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
Rearrangements of Tricyclo[3.2.1.1 2,4 ]non‐6‐yl, Tricyclo[4.2.1.1 2,5 ]dec‐3‐yl, and Tricyclo[4.2.2.1 2,5 ]undec‐3‐yl Cations The tricyclic ketones 5, 9, 13 , and 24 were prepared by modified or novel routes. The corresponding tosylhydrazones 10, 11, 14 , and 25 were photolyzed in 0.5 N NaOH (NaOD) to generate the title cations 2, 15–17 , and 28 , respectively, by way of diazonium precursors. The distribution of deuterium labels revealed rapid degenerate Wagner‐Meerwein rearrangements of 2 and 28 contrasting the unsymmetrical behavior of the parent bicyclo[3.2.1]oct‐6‐yl cation ( 1 ). The virtually irreversible rearrangement of 17 to 15 , on the other hand, mirrors the preferred chair conformation of 1 . The results with tricyclic carbocations support our previous explanation for the exceptional reactivity of 1 .