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Deamination Reactions, 57. Bicyclo[3.2.0]hept‐3‐yl→7‐Norbornyl Rearrangements
Author(s) -
Kirmse Wolfgang,
Siegfried Rainer
Publication year - 1996
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199619960402
Subject(s) - chemistry , 2 norbornyl cation , bicyclic molecule , medicinal chemistry , heptane , nucleophile , protonation , deamination , photodissociation , solvolysis , alkyl , deuterium , ion , stereochemistry , photochemistry , organic chemistry , hydrolysis , catalysis , physics , quantum mechanics , enzyme
Bicyclo[3.2.0]heptane‐ endo ‐ and ‐ exo ‐3‐diazonium ions ( 15 , 17 ) were generated by diazotization of the analogous amines ( 12 , 14 ) as well as by photolysis of bicyclo[3.2.0]‐heptan‐3‐one tosylhydrazone ( 13 ). In contrast to solvolyses of the corresponding tosylates ( 8 , 11 ), the dediazoniation reactions afforded 16–30% of 7‐norbornanol. By means of deuterium labels, the rearrangement was found to proceed by way of sequential 2,3‐H and 1,2‐alkyl shifts; a protonated spirocyclopentane 5 [7] is not involved in this process. While the 2,3‐H shift is but moderately exo ‐selective, nucleophilic capture of the 7‐norbornyl cation (3‐D‐ 2 ) occurs stereospecifically within the limits of detection.