An efficient route to steroidal 6α- and 6β-Malonates and acetates by alkylation of π-Allylpalladium complexes

Abstract

Reaction of the π-allylpalladium compounds derived from some 3-oxo 4- ene steroids with malonate ion gives dialkyl (3-oxo-steroid-4-en-6β- yl)malonates in high yield and with complete stereo-specificity. The 6β-malonates can be epimerized to give the more stable 6α-epimers or decarboalkoxylated to give the corresponding acetic acid derivatives.