Synthesis of potential pregnenolone and progesterone spin probes for biomembranes and immunoassays

Synthesis and Evaluation of Osteogenic Oxysterols as Hedgehog Pathway Activators

“…The first series of asymmetric Grignarda ttempts used Ti(OiPr) 4 ,c hiral BINOL, and ac helating agent (BDMAEE, bis [2-(N,N-dimethylamino)ethyl] ether). [16] After multiple alterations to the procedure with no success, we thought the Grignard reagent may be too deactivated with the use of the chelating BDMAEE, makingt he reaction unsuccessful even with heating due to the deactivated nature of the alkyl-aldehydes tarting material. Severalo ther attempts were taken without the use of BDMAEEf ollowing as econd procedure.…”

“…The solution was concentrated and directly purified by flash chromatography (SiO 2 ,1 0% EtOAc in hexanes) to yield 10 as aw hite solid (0.195 g, 64 %). 1 (2S,4S)-2-((3S,10R,13R,17R)-10,13-dimethyl-3-((tetrahydro-2Hpyran-2-yl)oxy)-2, 3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl)-6-methylheptan-4-ol (11) and (2S,4R)-2-((3S,10R,13R,17R)-10,13-dimethyl-3-((tetrahydro-2H-pyran-2-yl)oxy)-2, 3,4,7,8,9,10,11,12,13,14,15,16,17- 1h exanes/EtOAc] were as previously described. [11] 23(S)-hydroxycholesterol (4).O HC 11 (0.050 g, 0.103 mmol) was dissolved in 5:1M eOH/THF (6 mL), to which 2 n HCl (2 mL) was added dropwise.…”

Synthesis of 3β,6α-dihydroxy-5α-cholan-23-one

“…22-Hydroxy-23,24-dinorchol-4-en-3-one (7) 5,6 was obtained in 68% yield by reduction of the commercially available 3-oxo-23,24-dinorchol-4-en-22-al (6) using one hydride equivalent of NaBH 4 at rt.…”

Total assignment of1H and13C NMR spectra of pregnenolone and progesterone haptens using 2D NMR spectroscopy

“…15 Allylated pregnenolone was treated with AD mixˇto obtain the hydroxylated derivative 19. 14 The 1 H and 13 C NMR spectra were recorded on Bruker AM 500 and Varian VXR 300S spectrometers (with digital resolution 0.16 Hz). The spectra were referenced with tetramethylsilane as 0.0 ppm for 1 H NMR and the central line of CDCl 3 was set to 77.0 ppm for 13 C NMR.…”