Synthesis of estrone via a thallium(III)-mediated fragmentation of a 19-hydroxy-androst-5-ene precursor

Article abstract of DOI:10.1016/S0040-4039(00)61750-1

Estrone (6) has been synthesized from 1, an industrial precursor of androstane steroids, in seven steps. Key features of the strategy include the functionalization of C-19 (1 → 2) and a stereoelectronically controlled, Tl(III)-mediated degradation (2 → 3). Oppenauer oxidation of diol 4 then gave the unsaturated hydroxyketone 5, acid treatment of which induced aromatization affording 6.