Nuclear magnetic resonance studies on the conformation of five-membered ring phosphites and related compounds

1972 ◽  
Vol 94 (12) ◽  
pp. 4212-4217 ◽  
Author(s):  
Richard H. Cox ◽  
M. Gary Newton
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Membered Ring ◽  
Magnetic Resonance Studies ◽  
Related Compounds ◽  
Nuclear Magnetic

Nuclear magnetic resonance studies. XL. Tricyclooctanone rearrangement, [3.2.1.0] → [3.3.0.0], via γ-enolization and a 2Hmr study of H/D exchange in tricyclic ketones

1984 ◽  
Vol 62 (7) ◽  
pp. 1385-1391 ◽  
Author(s):  
A. K. Cheng ◽  
Ashim K. Ghosh ◽  
J. B. Stothers
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Membered Ring ◽  
Deuterium Incorporation ◽  
Magnetic Resonance Studies ◽  
Endo Isomer ◽  
Exchange Processes ◽  
Initial Transformation ◽  
Nuclear Magnetic

The effect of strongly basic conditions (t-BuO−/t-BuOH/185 °C) on the exo and endo isomers of 7,7-dimethyltri-cyclo[3.2.1.02.4]octan-6-one has been examined. While the exo isomer is stable, the endo isomer readily rearranges to 4,4-dimethyltricyclo[3.3.0.02.8]octan-3-one (6) which subsequently undergoes reduction of the three-membered ring. The initial transformation is one of very few examples of γ-enolate rearrangement. Experiments in tert-buiyl alcohol-O-d1 were carried out to establish the several sites of deuterium incorporation in the initial ketones and in 6 using 2Hmr. These results reveal the stereochemistry of γ-enolate formation and cleavage as well as the stereoselectivities and relative rates of the exchange processes.

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