110977-40-7Relevant academic research and scientific papers
EVALUATION OF THE ?-CONJUGATIVE EFFECT OF THE 2-METHYLENE AND THE 2-OXO SUBSTITUENT ON THE STABILITY OF CARBOCATIONS IN THE SOLVOLYSIS OF BICYCLIC BRIDGEHEAD DERIVATIVES
Takeuchi, Ken'ichi,Akiyama, Fumio,Ikai, Keizo,Shibata, Tadashi,Kato, Midori
, p. 873 - 876 (1988)
The incipient 2-methylenebicyclonon-1-yl cation is stabilized by allylic conjugation by 4 kcal/mol compared with the more rigid 2-methylenebicyclooct-1-yl cation.In contrast to this, no appreciable stabilization due to carbonyl ?-conjugation
Ring-Expansion of Bridgehead Aldehydes with 1-Adamantanecarbonyl Cation or Benzoyl Trifluoromethanesulfonate: A New Route to Bicyclic and Tricyclic 1,2-Diols
Takeuchi, Ken'ichi,Kitagawa, Itsuko,Akiyama, Fumio,Shibata, Tadashi,Kato, Midori,Okamoto, Kunio
, p. 612 - 615 (2007/10/02)
Acylation of bridgehead aldehydes with 1-adamantanecarbonyl cation generated from 1-adamantyl cation and carbon monoxide, or with benzoyl trifluoromethanesulfonate, in the presence of trifluoromethanesulfonic acid causes ring-expansion of the aldehydes by one carbon atom.Work-up of the reaction mixture with water affords a bridgehead alcohol containing the acyloxy group on the vicinal carbon, which on saponification gives a vicinal glycol in good overall yields.For example, bicycloheptane-1-carbaldehyde gives bicyclooctane-1,2-diol which is not easily accessible by the other methods.
