Chemical F/J‐Interconversion in the Prostaglandin Family: From Cloprostenol to Its Δ12‐J2 and 15‐Deoxy‐Δ12,14‐J2 Derivatives

Racemic cloprostenol methyl ester was converted via cyclic 9,11‐phenylboronate esters to 9α,11α‐dihydroxy‐15α‐siloxy (OTBDPS, OTBDMS) derivatives. TES‐Morf selectively reacts with last compounds to exclusively give 11‐TES derivative. In the course of further transformations, the J‐type PG was obtained. The optimal conditions for the 13,14‐double bond shift in the latter were determined and ▵12 derivatives were obtained. 15‐TBDMS derivative PGJ2 was converted to the target ω‐aryloxy derivatives ▵12‐PGJ2, its 13Z isomer, and ▵12,14‐PGJ2 by hydrolysis of the TBDMS protective group. The anticancer activity of some of the synthesized compounds was studied. Racemic cloprostenol was converted to cyPG analogues via the differentiation of the alcohol groups, oxidation and migration of the double bond. The cytotoxicity of a number of synthesized compounds was studied. The 15‐deoxy‐Δ12,14‐PGJ2 derivative of cloprostenol showed the highest anti‐cancer activity in the studied cancer cell lines.