77452-55-2Relevant academic research and scientific papers
Intramolecular Reactions Involving Positions C(2), C(6) and C(2), C(7) in the Bicyclononane Ring System
Bishop, Roger,Parker, William,Stevenson, James Ronald
, p. 565 - 573 (1981)
Reactions likely to involve C(2)-C(6) and C(2)-C(7) intramolecular reactions in bicyclononane derivatives are discussed in terms of the conformations available to the ring system.While endo-6-hydroxybicyclononan-2-one (11) incorporated three deuterium atoms (excluding the hydroxy-group) on heating with NaOD, the exo-isomer (17) exchanged the six hydrogens adjacent to the oxygenation functions but not the carbinyl proton.Evidence is presented favouring a stereospecific base-induced 2,6-hydride migration, most probably proceeding via a twin-twist boat transition state.Treatment of 6,6-ethylenedioxy-2-methoxymethylenebicyclononane (36) with aqueous HCl in acetone produced 2-hydroxyprotoadamantan-10-one (38) in high yield.This process resulted from hydrolysis of the oxygenated groups thereby liberating the endo-keto-aldehyde intermediate (37) which underwent subsequent intramolecular aldol condensation between the C(2) aldehyde and C(7).
