Recent Progress in Steroid C(sp)-H Functionalization.

Selective C-H functionalization methods could provide a valuable tool for synthesizing different steroid derivatives, which is essential not only in contexts of developing novel synthetic methodology but also as a direct way for gathering the analogues needed for studying the structure-activity relationships and obtaining biologically active compounds. The review discusses recent examples of steroid C-H functionalization to various C-X derivatives (C-O, C-C, C-N, C-S, and C-halogen) using available methods emphasizing their scope and limitations.

Synthesis of 25-Hydroxy-provitamin D by Direct Hydroxylation of Protected 7-Dehydrocholesterol.

A new synthetic route to 25-hydroxy-provitamin D was elaborated. The synthesis consists of direct hydroxylation at C-25 of 7-dehydrocholesterol hetero Diels-Alder adducts. The adducts were prepared by [4 + 2] cycloaddition of azadienophiles to the steroidal diene.

Montmorillonite Catalyzed Synthesis of Novel Steroid Dimers.

The reactions of sterols (androst-5-en-3β-ol-17-one, diosgenin, and cholesterol) and their tosylates with hydroquinone aimed at the synthesis of ,-1,4-phenylene-linked steroid dimers were studied. The reaction course strongly depended on the conditions used. The study has shown that the major reaction products are the elimination products and unusual steroid dimers resulting from the nucleophilic attack of the hydroquinone C2 carbon atom on the steroid C3 position, followed by an intramolecular addition to the C5-C6 double bond.