Preparative TLC developed by 60 EtOAc in hexane to afford the preferred item 9 (one hundred mg, 83 ) as a pale pink gel. 1H NMR (300 MHz, CDCl3) 14.72 (d, 1H, J = three.three Hz), 8.39 (s, 1H), six.19 (s, 1H), 5.60 (s, 1H), 5.29 (d, 1H, J = 12.0 Hz), four.90 (s, 1H), four.30 (dd, 1H, J = 1.2 Hz, 9.9 Hz), 4.09 (dd, 1H, J = 0.9 Hz, 9.9 Hz), 3.92 (m, 1H), 3.09 (d, 1H, J = 9.6 Hz), two.55 (m, 1H), 2.29 (d, 1H, J = 15.0 Hz), two.05 (m, 3H), 1.84 (m, 1H), 1.67 (s, 3H), 1.60 (m, 2H), 1.37 (s, 3H), 1.29 (s, 3H), 1.04 (s, 3H); 13C NMR (75 MHz, CDCl3) 204.six, 185.4, 184.eight, 150.four, 120.7, 109.two, 101.two, 95.7, 71.6, 70.0, 64.4, 58.1, 56.0, 48.3, 43.7, 40.1, 39.9, 33.2, 30.five, 30.3, 30.0, 25.3, 20.six, 19.eight; HRMS Calcd for C24H31O7: [M + H]+ 431.2064; discovered 431.2063. Synthesis of (3S,3aR,3a1R,6aR,7S,7aR,11aS,11bS)-7-hydroxy-5,5,8,8-tetramethyl-15methylene-11,14-dioxo-2,3,3a,7,7a,8,11,11b-octahydro-1H-6a,11a-(epoxymethano)-3,3a1ethanophenanthro[1,10-de][1,3]dioxine-10-carbaldehyde (10) To a stirring remedy of phenylselenyl chloride (33.6 mg, 0.175 mmol) in CH2Cl2 (3 mL) at 0 was added pyridine (0.017 mL, 0.208 mmol). The remedy was stirred for 45 min, and then a remedy of -keto aldehyde 9 (60 mg, 0.139 mmol) in CH2Cl2 (2 mL) was added. The mixture was stirred at 0 for 15 min and at rt for 45 min. It was then extracted twice with 1 N HCl (aq.). The organic phase was dried over MgSO4, filtered, and concentrated below reduced stress. The crude item was further purified employing the preparative TLC created by hexane/EtOAc (1:1) to afford the selenide as a yellow gel (60.0 mg, 74 ). To a stirring resolution on the above selenide (60.0 mg, 0.102 mmol) in CH2Cl2 (5.8 mL) was added 35 H2O2 (aq.) resolution (0.10 mL, 1.2 mmol). The mixture was vigorously stirred forNIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptJ Med Chem. Author manuscript; offered in PMC 2014 November 14.Ding et al.Page5 min, followed by the addition of an additional portion of 35 H2O2 (aq.) solution (0.10 mL, 1.two mmol) with vigorous stirring for an additional 5 min. The reaction mixture was then extracted twice with water.3,3′-Diindolylmethane The extract was dried more than MgSO4, filtered, and concentrated beneath decreased stress.Methazolamide The crude product was additional purified working with the preparative TLC developed by hexane/EtOAc (1:1) to afford ten (43 mg, 97 ) as a pale yellow gel.PMID:24211511 []25D -102 (c 0.10, CH2Cl2); HPLC purity 98.1 (tR = 18.33 min); 1H NMR (600 MHz, CDCl3) 9.83 (s, 1H), 7.59 (s, 1H), 6.18 (s, 1H), five.61 (s, 1H), five.42 (d, 1H, J = 12.6 Hz), four.89 (s, 1H), four.33 (dd, 1H, J = 1.2 Hz, ten.two Hz), 4.09 (m, 2H), 3.10 (d, 1H, J = 9.0 Hz), 2.56 (m, 1H), two.06 (m, 2H), 2.00 (d, 1H, J = eight.four Hz), 1.67 (s, 3H), 1.56 (m, 3H), 1.52 (s, 3H), 1.36 (s, 3H), 1.32 (s, 3H); 13C NMR (150 MHz, CDCl3) 204.five, 195.2, 188.0, 168.four, 150.0, 133.0, 121.three, 101.5, 95.8, 71.three, 69.8, 64.9, 56.1, 55.7, 47.0, 46.five, 40.0, 36.2, 30.0, 29.7, 25.3, 24.2, 19.0; HRMS Calcd for C24H29O7: [M + H]+ 429.1908; discovered 429.1897. Synthesis of (3S,4aR,5S,6aR,9S,11aS,11bS,14R,E)-5,14-dihydroxy-2(methoxymethylene)-4,4-dimethyl-8-methyleneoctahydro-1H-3,11b-(epoxymethano)-6a,9methanocyclohepta[a]naphthalene-1,6,7(2H,8H)-trione (13) To a solution of ten (5 mg, 0.011 mmol) within a mixture of MeOH (2 mL) and CH2Cl2 (0.five mL) was added 5 HCl aqueous answer (0.2 mL) at rt. The resulting mixture was stirred at rt for 2 h. The reaction mixture was then diluted with water and extracted with dichloromethane. The extract was washed with saturated NaHCO3 (aq.) remedy and brine,.
