Die Cyclopropylcarbinyl-Cyclobutyl-Homoallyl-Umlagerung. I. Teil. Synthese von Tricyclo[3.2.1.02,7]octan-3-ol, endo- und exo-Tricyclo[3.2.1.03,6]octan-4-ol und exo-Bicyclo[3.2.1]-oct-2-en-7-ol

✍ Scribed by Manfred Geisel; Cyril A. Grob; Werner Santi; Werner Tschudi

• Publisher: John Wiley and Sons
• Year: 1973
• Tongue: German
• Weight: 737 KB
• Volume: 56
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19730560322

✦ Synopsis

Abstract

Tricyclo[3.2.1.0^2,7^]octan‐3‐ol (1) and its 4‐isomer 7 were obtained by hydroboration of tricyclo[3.2.1.0^2,7^]oct‐3‐ene (5). The former alcohol 1 is quantitatively converted to the isomeric alcohol exo‐bicyclo[3.2.1]oct‐2‐en‐7‐ol (3) by treatment with aqueous acid.

Photolysis of 1‐diazo‐3‐(cyclopent‐3‐enyl)‐propan‐2‐one (12c) gave a high yield of tricyclo[3.2.1.0^3,6^]octan‐4‐one (10a). Reduction of the latter ketone produced a mixture of endo‐ and exo‐tricyclo[3.2.1.0^3,6^]octan‐4‐ol 2 and 9, respectively. Oxidation of these secondary alcohols with silver carbonate in benzene furnished a mixture of the ketone 10a and the lactone 14 of 6‐hydroxy‐bicyclo[2.1.1]heptane‐2‐carboxylic acid. The latter is thought to be formed by oxydation of the hydrate of the strained ketone 10a.