2842-85-5Relevant academic research and scientific papers
ELIMINATION OF 14β-HYDROXY-12-MESYLOXY-5β-STEROIDS
Habermehl, Gerhard G.,Hammann, Peter E.
, p. 4345 - 4348 (1985)
Elimination of a 12α-methanesulfoxy group in 3β-acetoxy-14β-hydroxy-12α-mesyloxy-5β-androstane-17β-carboxylic-acid-14β-lactone under preventing Wagner-Meerwein rearrangements by steric fixation, is reported.Furthermore, the synthesis of this compound and the different elimination behaviors in the 12α- and the 12β-isomers are described.
Elimination Reactions and Rearrangement of 14β-Hydroxy-12-sulfonyloxy Steroids.
Hammann, Peter E.,Habermehl, Gerhard G.
, p. 149 - 156 (2007/10/02)
Elimination of 12α- or 12β-(methylsulfonyloxy)-14β-hydroxy steroids proceeds under rearrangement of the steroid nucleus.From the 12α-sulfonyloxy compounds of 19 the (12βH)-14(13->12)abeo-13(18)-ene steroid 21 is obtained, whereas the 14β-hydroxy-(12βH)-17(13->12)abeo-13(18)ene compounds 14, 20 result from the 12β-methylsulfonyloxy derivatives of the steroids 13, 18.Structures were determined by means of 2D-NMR analyses and decoupling experiments.The theoretical explanation of this rearrangement leads to the possibility of an elimination of the 12α-methylsulfonyloxy group to yield the Δ11-alkene (28).This is possible by steric fixation of the migrating C-atoms at positions 14 and 17 in the 20,14β-lactone (26, 27).
