5-alpha-Hydroxy- Laxogenin

5α-hydroxy Laxogenin is a brassinosteroid analog and a derivative of diosgenin.Topical administration of 5α-hydroxy laxogenin (4, 8, and 12 ppm), in combination with a commercial fertilizer, increases the yield and fresh weight of endives (C. endivia).It also inhibits sodium chloride-induced decreases in the fresh weight of lettuce shoots and roots when applied topically at concentrations of 0.1 and 1 μM, as well as inhibits increases in ethylene emission at a concentration of 1 μM.

Five grams (10.2 mmol) of Compound 8 were dissolved in 390 mL of methanol. Subsequently, a solution of 4.6 g of NaHCO3 in 60 mL of water was added while refluxing for 3 h. After allowing thereaction mixture to settle at room temperature, it was poured in water, to obtain 4.35 g of Compound S9(95percent), mp 272 °C (methanol). IR (KBr): νmax 3396 (ν OH), 2953 (ν CH), 1703 (ν C=O), 1449 and 1380(δ CH), 1055 (ν C=O), 977 (spiroketal); 1H-NMR (δ, ppm): 1.97/1.30 (m, 2H, H-1), 1.80/1.45 (m, 2H, H-2), 3.93 (m, 1H, H-3), 1.84/1.69 (m, 2H, H-4), 2.82/2.04 (m, 2H, H-7), 1.94 (m, 1H, H-8), 1.99 (m, 1H, H-9), 1.51/1.36 (m, 2H, H-11), 1.81/1.28 (m, 2H, H-12), 1.47 (m, 1H, H-14), 1.96/1.29 (m, 2H, H-15), 4.44 (m, 1H, H-16), 1.83 (m, 1H, H-17), 0.82 (s, 3H, CH3-18), 0.83 (s, 3H, H-19), 1.90 (m, 1H, H-20), 0.99(d, 3H, CH3-21), 1.70/1.60 (m, 2H, H-23), 1.65/1.46 (m, 2H, H-24), 1.64 (m, 1H, H-25), 3.48/3.40 (m, 2H, H-26), 0.82 (d, CH3-27). 13C-NMR (δ, ppm: 30.4 (C-1), 29.8 (C-2), 67.2 (C-3), 36.5 (C-4), 80.7 (C-5), 211.7(C-6), 41.9 (C-7), 36.7 (C-8), 44.6 (C-9), 42.4 (C-10), 21.3 (C-11), 39.5 (C-12), 41.1 (C-13), 56.1 (C-14), 31.6(C-15), 80.5 (C-16), 62.0 (C-17), 16.4 (C-18), 14.2 (C-19), 41.6 (C-20), 14.5 (C-21), 109.3 (C-22), 31.3 (C-23), 28.8 (C-24), 30.3 (C-25), 66.9 (C-26), 17.1 (C-27).After dissolving 4 g (9 mmol) of Compound S9 in 500 mL of acetone, 4 mL of Jones reagent(8 N-CrO3:5.33 g of CrO3 were dissolved in 4.4 mL of concentrate H2SO4, then water was addedto obtain a 20-mL solution) were included drop-wise at room temperature. When the reaction wasconcluded, isopropanol was added until the mixture lost the orange color. After the solution wasfiltered by gravity, it was poured in water. The solid product was purified by column chromatography(1:1 hexane'EtOAc) affording 3.1 g of S15 (81.5percent), mp 283 °C (methanol). IR (KBr): numax 3345 (nu OH), 2953 (nu CH), 1713 (nu C=O), 1456 and 1376 (delta CH), 1057 (nu C-O), 980 and 899 (spiroketal); 1H-NMR(delta, ppm): 2.10/1.86 (m, 2H, H-1), 2.40 (m, 2H, H-2), 2.78/2.25 (m, 2H, H-4), 2.96/2.34 (m, 2H, H-7), 1.99 (m, 1H, H-8), 1.90 (m, 1H, H-9), 1.50 (m, 2H, H-11), 1.81/1.31 (m, 2H, H-12), 1.46 (m, 1H, H-14), 1.99/1.32 (m, 2H, H-15), 4.47 (m, 1H, H-16), 1.85 (m, 1H, H-17), 0.83 (s, 3H, CH3-18), 1.04 (s, 3H, CH3-19), 1.90 (m, 1H, H-20), 1.01 (d, 3H, CH3-21), 1.69 (m, 2H, H-23), 1.50 (m, 2H, H-24), 1.66 (m, 1H, H-25), 3.5/3.38 (m, 2H, H-26), 0.82 (d, 3H, CH3-27). 13C-NMR (delta, ppm): 31.8 (C-1), 37.3 (C-2), 210.2(C-3), 41.9 (C-4), 82.7 (C-5), 210.4 (C-6), 44.8 (C-7), 36.8 (C-8), 44.7 (C-9), 43.1 (C-10), 21.3 (C-11), 39.5(C-12), 41.0 (C-13), 56.0 (C-14), 31.6 (C-15), 80.4 (C-16), 62.0 (C-17), 16.4 (C-18), 13.9 (C-19), 41.6 (C-20), 14.5 (C-21), 109.3 (C-22), 31.3 (C-23), 28.8 (C-24), 30.3 (C-25), 66.9 (C-26), 17.1 (C-27).Five grams (10.2 mmol) of Compound 8 were dissolved in 390 mL of methanol. Subsequently, a solution of 4.6 g of NaHCO3 in 60 mL of water was added while refluxing for 3 h. After allowing thereaction mixture to settle at room temperature, it was poured in water, to obtain 4.35 g of Compound S9(95percent), mp 272 °C (methanol). IR (KBr): numax 3396 (nu OH), 2953 (nu CH), 1703 (nu C=O), 1449 and 1380(delta CH), 1055 (nu C=O), 977 (spiroketal); 1H-NMR (delta, ppm): 1.97/1.30 (m, 2H, H-1), 1.80/1.45 (m, 2H, H-2), 3.93 (m, 1H, H-3), 1.84/1.69 (m, 2H, H-4), 2.82/2.04 (m, 2H, H-7), 1.94 (m, 1H, H-8), 1.99 (m, 1H, H-9), 1.51/1.36 (m, 2H, H-11), 1.81/1.28 (m, 2H, H-12), 1.47 (m, 1H, H-14), 1.96/1.29 (m, 2H, H-15), 4.44 (m, 1H, H-16), 1.83 (m, 1H, H-17), 0.82 (s, 3H, CH3-18), 0.83 (s, 3H, H-19), 1.90 (m, 1H, H-20), 0.99(d, 3H, CH3-21), 1.70/1.60 (m, 2H, H-23), 1.65/1.46 (m, 2H, H-24), 1.64 (m, 1H, H-25), 3.48/3.40 (m, 2H, H-26), 0.82 (d, CH3-27). 13C-NMR (delta, ppm: 30.4 (C-1), 29.8 (C-2), 67.2 (C-3), 36.5 (C-4), 80.7 (C-5), 211.7(C-6), 41.9 (C-7), 36.7 (C-8), 44.6 (C-9), 42.4 (C-10), 21.3 (C-11), 39.5 (C-12), 41.1 (C-13), 56.1 (C-14), 31.6(C-15), 80.5 (C-16), 62.0 (C-17), 16.4 (C-18), 14.2 (C-19), 41.6 (C-20), 14.5 (C-21), 109.3 (C-22), 31.3 (C-23), 28.8 (C-24), 30.3 (C-25), 66.9 (C-26), 17.1 (C-27).General procedure: The glucosyl donor 5 (1.29 g, 1.75 mmol), hecogenin 3 (579 mg, 1.34 mmol) and 4 A molecular sieves were suspended in dry CH2Cl2 (25 mL) and the mixture was stirred at room temperature under nitrogen atmosphere for 15 min. A solution of TMSOTf (12 muL, 0.067 mmol) in CH2Cl2 (2.4 mL) was added and the reaction mixture was stirred for 1 h. The reaction was quenched by addition of Et3N and then filtered. The filtrate was evaporated to dryness and the crude product was purified by flash column chromatography (n-hexane/EtOAc 4:1) to afford 6 (1.23 g, 91percent) as a white solid.

5α-Hydroxy laxogenin is a synthetic derivative of a naturally occurring spirostane-type steroid, laxogenin. It is a synthetic spirostane-type steroid, which is contained in dietary supplements and advertised as anabolic agent.