ISSN:
1572-8854
Keywords:
Cycloalkyne intermediates
;
base-induced rearrangements
;
ring expansion
;
molecular mechanics
;
Gaussian RHF/6-31G
Source:
Springer Online Journal Archives 1860-2000
Topics:
Geosciences
,
Physics
Notes:
Abstract The base-catalyzed rearrangement reactions of 2-bromomethylenebenzonorbornene8 and 2,2-dibromomethylenebenzonorbornene9 were studied. Reaction of8 with potassiumtert-butoxide in THF gave only the enol ether11 whose formation is rationalized via a carbene-cycloalkyne mechanism. However, treatment of9 with phenyllithium in THF at −40°C gave the ringenlarged dibromide13 whose structure is reported herein. The ring-enlarged product13 is rationalized in terms of carbanionic rearrangement. Quantum mechanical calculations are consistent with these observations.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01665821
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