Collect. Czech. Chem. Commun. 2000, 65, 1173-1182

Synthesis of 8,14-Secosteroids from (S)-(+)-Carvone

Anna I. Kotyatkinaa, Vladimir N. Zhabinskiia, Vladimir A. Khripacha,* and Aede de Grootb

a Institute of Bioorganic Chemistry, National Academy of Sciences, Kuprevich str. 5/2, 220141 Minsk, Belarus
b Wageningen University and Research Center, Dreijenplein 8, 6703 HB Wageningen, The Netherlands


A total synthesis of functionalised 8,14-seco steroids with five- and six-membered D rings is described. The synthesis is based on the transformation of (S)-carvone into a steroidal AB ring moiety with a side chain at C-9 that allowed the creation of a nitrile oxide at this position. The nitrile oxides were coupled with cyclic enones or enol derivatives of 1,3-diketones, and reductive cleavage of the obtained cycloadducts gave the desired products. The formation of a twelve-membered ring compound was observed in cycloaddition of one of the nitrile oxides with cyclopentenone as the result of an intramolecular ene-reaction followed by retroaldol reaction.

Keywords: Steroids; Secosteroids; Isoxazoles; Isoxazolines; Nitrile oxides; Carvone; Terpenoids; Total synthesis.

References: 21 live references.