13,14-seco-steroids: A new type of modified steroids containing a nine-membered ring
(1999) Helvetica Chimica Acta — Vol. 82, n° 5, p. 707-721 (1999)
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- Oxidations of 14 alpha-hydroxy-5 alpha-cholestan-3 beta-yl acetate (5) with lead tetraacetate under thermal or photolytic conditions or in the presence of iodine proceed mainly by fragmentation of the C(13)-C(14) bond to give as the primary products the 13,18-didehydro-13,14-seco derivative 6 and the (E)-Delta(12)-13,14-seco ketone 11, respectively. Further transformations of these compounds under conditions of their formation afforded, in addition, the acetoxy derivatives 7-9 (from 6), and the D-homo-C-nor compound 12 and (12R,13R)-epoxide 13 (from 11). Unexpectedly, the photolytic lead-tetraacetate oxidation of 5 resulted partly (to ca. 20%) in a reversible fragmentation involving scission and recombination of the C(8)-C(14) bond followed by formation of rite 14 beta,22-ether 10. Possible mechanisms for the observed transformations are discussed.
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Bjelakovic, M., Declercq, J.-P., Lorenc, L., Pavlovic, V., Mihailovic, ML., Tinant, B., & Kalvoda, J. (1999). 13,14-seco-steroids: A new type of modified steroids containing a nine-membered ring. Helvetica Chimica Acta, 82(5), 707-721. https://doi.org/10.1002/(SICI)1522-2675(19990505)82:5<707::AID-HLCA707>3.0.CO;2-O (Original work published 1999)