Collect. Czech. Chem. Commun. 1986, 51, 1462-1475

Solvolysis of Westphalen-type compounds

Alexander Kasal and Jaroslav Zajíček

Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6


Action of some nucleophilic reagents (CH3COOAg, CH3COOK, LiAlH4) on 6β-chloro- and 6β-methanesulfonyloxy-5-methyl-19-nor-5β-cholest-9-enes VIII - XII affords predominantly A-homo-B,19-dinor-5β-cholest-9-ene derivatives, arising by rearrangement and substitution (XIII, XXIV) or rearrangement and elimination (e.g. XX). Hydrogenolysis of compounds of the type VIII with lithium aluminium hydride gives, in addition, a product of rearrangement, fragmentation and further reduction (XXVI), and 5-methyl-6α,10-cyclo-19-nor-5β,9β,10α-cholestan-3β-ol (XXX).