Molecular rearrangements of poststerone derivative steroid core with formation of unique D-homostructures of pregnane and androstane series

Abstract

20R-Hydroxy short-chain ecdysteroids were synthesized by chemo- and stereoselective reduction of poststerone acetonide with L-Selectride or LiAlH₄. The same reaction with the excess of L- Selectride followed by the treatment of the reaction mixture with hydrochloric acid is accompanied by (8R)-13(14 → 8)abeo- rearrangements, which resulted in the contraction/expansion of C/D pregnane rings. The reaction of 20R-hydroxy poststerone analogs with (diethylamino)sulfur trifluoride (DAST) proceeds through intramolecular rearrangements and provides D-homo- or 13,14-seco- androstane structures.

Keywords: 20-hydroxyecdysone; DAST-fluorination; Ecdysteroid; L-Selectride; Molecular rearrangement; Poststerone.