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Deamination Reactions, 57. Bicyclo[3.2.0]hept-3-yl→7-Norbornyl Rearrangements

✍ Scribed by Kirmse, Wolfgang ;Siegfried, Rainer

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
316 KB
Volume
1996
Category
Article
ISSN
0947-3440

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✦ Synopsis

Abstract

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.

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