Baeyer–Villiger oxidation of 19-substituted steroidal ketones: structure of rearranged products involving participation of the 19-substituent

Abstract

Baeyer–Villiger reactions of 19-hydroxy-4β,5-epoxy-5β-androstane-3,17-dione (2), 19-hydroxy-4α,5-epoxy-5α-androstane-3,17-dione (13), 17β,19-dihydroxy-5β-androstan-3-one (18), and 19-hydroxyandrost-4-ene-3,17-dione (1) are reported. When carbonyl functions are present at C-3 and C-17, Baeyer–Villiger rearrangement occurs preferentially at C-17. The rearrangement product obtained from the Δ⁴-3-ketone (1) was found to be 5β-formyl-5,19-dihydroxy-17-oxo-A-nor-3,5-seco-5β-androstane-3-carboxylic acid 5,19(R) lactol 3,5-lactone (27).