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Die Cyclopropylcarbinyl‐Cyclobutyl‐Homoallyl‐Umlagerung. I. Teil. Synthese von Tricyclo[3.2.1.0 2,7 ]octan‐3‐ol, endo ‐ und exo ‐Tricyclo[3.2.1.0 3,6 ]octan‐4‐ol und exo ‐Bicyclo[3.2.1]‐oct‐2‐en‐7‐ol
Author(s) -
Geisel Manfred,
Grob Cyril A.,
Santi Werner,
Tschudi Werner
Publication year - 1973
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19730560322
Subject(s) - chemistry , ketone , bicyclic molecule , yield (engineering) , medicinal chemistry , alcohol , aqueous solution , hydroboration , hydrate , stereochemistry , organic chemistry , catalysis , materials science , metallurgy
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 .