New bisfuran derivative from sarsasapogenin: An X-ray and NMR analysis

The new bisfuran derivative, (22S,23S)-22,23-dihydroxy-23,26-epoxyfurostane (5), was obtained from the known oxidation of sarsasapogenin acetate with NaNO2/BF3 in 5% aqueous acetic acid. The structure of 5 was established using one and two-dimensional 1H, 13C experiments (DEPT, COSY, HETCOR and HMBC) and the configurations at the newly formed stereogenic centers were established as 22S,23S by an X-ray diffraction analysis. Addition of TiCl4 to bisfuran 5 confirmed that this compound is an intermediate in the rearrangement to 22-oxo-23-spiroketals since it was transformed quantitatively into the latter product. The 23-nitroimino intermediate 2 was isolated from the same reaction and its structure established also by an X-ray diffraction analysis; this compound was further transformed into the 23-nitramine 7 which could find application in functionalization of position 24.