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Synthesis 1987; 1987(7): 612-615
DOI: 10.1055/s-1987-28022
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Ring-Expansion of Bridgehead Aldehydes with 1-Adamantanecarbonyl Cation or Benzoyl Trifluoromethanesulfonate: A New Route to Bicyclic and Tricyclic 1,2-Diols

Ken'ichi Takeuchi* , Itsuko Kitagawa, Fumio Akiyama, Tadashi Shibata, Midori Kato, Kunio Okamoto
  • *Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University, Sakyo-ku, Kyoto 606, Japan
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Publication Date:
20 August 2002 (online)

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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 acyloxyl group on the vicinal carbon, which on saponification gives a vicinal glycol in good overall yields. For example, bicyclo[2.2.1]heptane-1-carbaldehyde gives bicyclo[2.2.2]octane-1,2-diol which is not easily accessible by the other methods.