Us Na2SO4, filtered, and evaporated to provide an oily residue. The residue was additional purified utilizing preparative TLC developed by 60 EtOAc in hexane to afford the desired solution 9 (one hundred mg, 83 ) as a pale pink gel. 1H NMR (300 MHz, CDCl3) 14.72 (d, 1H, J = three.3 Hz), eight.39 (s, 1H), six.19 (s, 1H), five.60 (s, 1H), 5.29 (d, 1H, J = 12.0 Hz), 4.90 (s, 1H), 4.30 (dd, 1H, J = 1.two Hz, 9.9 Hz), 4.09 (dd, 1H, J = 0.9 Hz, 9.9 Hz), 3.92 (m, 1H), three.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.four, 184.8, 150.four, 120.7, 109.two, 101.two, 95.7, 71.six, 70.0, 64.4, 58.1, 56.0, 48.three, 43.7, 40.1, 39.9, 33.2, 30.5, 30.3, 30.0, 25.3, 20.6, 19.8; HRMS Calcd for C24H31O7: [M + H]+ 431.2064; identified 431.2063. Synthesis of (3S,3aR,3a1R,6aR,7S,7aR,11aS,11bS)-7-hydroxy-5,five,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 (ten) To a stirring option of phenylselenyl chloride (33.six mg, 0.175 mmol) in CH2Cl2 (three mL) at 0 was added pyridine (0.017 mL, 0.208 mmol). The option was stirred for 45 min, and then a option 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 product was additional purified utilizing the preparative TLC created by hexane/EtOAc (1:1) to afford the selenide as a yellow gel (60.0 mg, 74 ). To a stirring option from 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 another portion of 35 H2O2 (aq.Buy334951-61-0 ) answer (0.n-(2-Methoxyethyl)aniline Order 10 mL, 1.PMID:23756629 2 mmol) with vigorous stirring for another five min. The reaction mixture was then extracted twice with water. The extract was dried more than MgSO4, filtered, and concentrated below reduced pressure. The crude product was further purified working with the preparative TLC created by hexane/EtOAc (1:1) to afford ten (43 mg, 97 ) as a pale yellow gel. []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), six.18 (s, 1H), five.61 (s, 1H), five.42 (d, 1H, J = 12.six Hz), 4.89 (s, 1H), four.33 (dd, 1H, J = 1.2 Hz, ten.two Hz), 4.09 (m, 2H), three.10 (d, 1H, J = 9.0 Hz), 2.56 (m, 1H), 2.06 (m, 2H), two.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) 204.5, 195.2, 188.0, 168.four, 150.0, 133.0, 121.3, 101.five, 95.eight, 71.three, 69.8, 64.9, 56.1, 55.7, 47.0, 46.5, 40.0, 36.two, 30.0, 29.7, 25.three, 24.2, 19.0; HRMS Calcd for C24H29O7: [M + H]+ 429.1908; identified 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 remedy of ten (five mg, 0.011 mmol) within a mixture of MeOH (2 mL) and CH2Cl2 (0.5 mL) was added five HCl aqueous option (0.two mL) at rt. The resulting mixture was stirred at rt for two h. The reaction mixture was then diluted with water and extr.
