Acted with dichloromethane. The extract was washed with saturated NaHCO3 (aq.) resolution and brine, dried more than anhydrous Na2SO4, filtered, and evaporated to give an oily residue. The residue was purified working with preparative TLC developed by EtOAc to afford the desired item 13 as a colorless amorphous gel (three.five mg, 78 ). []25D -110 (c 0.10, CH2Cl2); HPLC purity 98.3 (tR = 14.58 min); 1H NMR (300 MHz, CDCl3) 7.59 (s, 1H), 6.18 (s, 1H), 5.47 (s, 1H), 4.67 (m, 2H), four.43 (d, 1H, J = 0.9 Hz), 4.33 (s, 1H), four.22 (m, 1H), three.94 (s, 3H), three.91 (m, 1H), 3.09 (m, 1H), 2.92 (m, 1H), 1.62 (m, 3H), 1.57 (m, 1H), 1.52 (s, 3H), 0.99 (s, 3H); 13C NMR (75 MHz, CDCl3) 205.five, 201.four, 196.7, 156.3, 146.0, 118.6, 115.four, 75.1, 74.two, 71.7, 66.3, 62.1, 61.5, 51.7, 51.0, 45.three, 42.0, 38.two, 30.9, 28.five, 21.8, 20.1; HRMS Calcd for C22H27O7: [M + H]+ 403.1751; discovered 403.1768. Synthesis of (3S,4aR,5S,6aR,9S,11aS,11bS,14R,Z)-5,14-dihydroxy-2(hydroxymethylene)-4,4-dimethyl-8-methyleneoctahydro-1H-3,11b-(epoxymethano)-6a,9methanocyclohepta[a]naphthalene-1,6,7(2H,8H)-trione (14) To a remedy of ten (15 mg, 0.035 mmol) in THF (two mL) was added five HCl (aq.) answer (0.three mL) at rt. The resulting mixture was stirred at rt for four h. The reaction mixture was then diluted with water and extracted with dichloromethane. The extract was washed with saturated NaHCO3 (aq.) remedy and brine, dried over anhydrous Na2SO4, filtered, and evaporated to provide an oily residue. The residue was purified employing preparative TLC developed by five methanol in dichloromethane to afford the preferred solution 14 as a pale pink amorphous gel (11 mg, 80 ). []25D -104 (c 0.1, CH2Cl2); HPLC purity 96.6 (tR = four.47 min); 1H NMR (300 MHz, CDCl3) 7.99 (br s, 1H), 7.13 (s, 1H), 6.26 (s, 1H), five.49 (s, 1H), four.61 (d, 1H, J = 6.0 Hz), 4.54 (d, 1H, J = 4.5 Hz), 4.47 (s, 1H), 3.83 (m, 4H), 3.11 (d, 1H, J = 1.2 Hz), three.05 (d, 1H, J = 3.9 Hz), 1.89 (m, 1H), 1.75 (m, 2H), 1.57 (m, 2H), 1.48 (s, 3H), 0.96 (s, 3H); 13C NMR (75 MHz, CDCl3) 205.1, 200.4, 199.four, 160.1, 144.eight, 120.three, 113.2, 71.6, 65.eight, 60.9, 51.four, 50.6, 45.6, 41.2, 38.7, 31.1, 29.six (2C), 22.five, 20.0. HRMS Calcd for C21H25O7: [M + H]+ 389.1595; found 389.1591.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptJ Med Chem. Author manuscript; accessible in PMC 2014 November 14.Ding et al.PageSynthesis of (3S,3aR,3a1R,6aR,7S,7aR,11S,11aS,11bS)-7-hydroxy-5,five,eight,8-tetramethyl-15methylene-14-oxodecahydro-1H-6a,11a-(epoxymethano)-3,3a1-ethanophenanthro[1,10-de] [1,3]dioxin-11-yl methanesulfonate (16) To a resolution of oridonin (500 mg, 1.36 mmol) in acetone (20 mL) was added p-TsOH (20 mg) and 2,2-dimethoxypropane (three.0 mL) at rt. The resulting mixture was stirred at rt for two h. The reaction mixture was then diluted with water and extracted with dichloromethane.1118786-85-8 supplier The extract was washed with saturated NaHCO3 (aq.Buy196862-45-0 ) resolution and brine, dried over anhydrous Na2SO4, filtered, and evaporated to afford compound 15 as a colorless gel (520 mg, 93 ); To a option of 15 (277 mg, 0.PMID:31085260 68 mmol) in dichloromethane was added Et3N (138 mg, 1.37 mmol) and MsCl (94 mg, 0.82 mmol) dropwise at 0 . The mixture was stirred at rt overnight, diluted with water, and extracted with dichloromethane. The organic extract was washed with saturated NaHCO3 (aq.) option and brine, dried more than anhydrous Na2SO4, filtered, and evaporated to give an oily residue. The crude residue was additional purified by silica gel column; elution with 50 EtOAc in hexane afforded the desired solution 16 as.