Novel Synthesis of Highly Functionalized 14-β-Hydroxysteroids Related to Batrachotoxin and Ouabain

Abstract
The use of anionic polycyclization was investigated in an effort to develop a versatile and convergent synthesis of advanced tetracyclic intermediates of batrachotoxin and ouabain analogues. Two new 5-(trialkylsilyl)-2-cyclohexenones as A ring precursors and a new Nazarov intermediate (D ring precursor) were prepared for this purpose. The reaction of the unsaturated β-keto aldehyde A ring precursor with the enolate of the Nazarov intermediate afforded, after subsequent transformations, a 14-β-hydroxysteroid with complete control of stereochemistry.