A colorless amorphous gel (264 mg, 80 ). 1H NMR (600 MHz, CDCl3) six.16 (s, 1H), five.82 (d, 1H, J = 12.0 Hz), five.58 (s, 1H), four.76 (dd, 1H, J = six.0 Hz, 12.0 Hz), four.14 (d, 1H, J = 4.2 Hz), three.92 (m, 1H), three.07 (d, 1H, J = 9.0 Hz), two.99 (s, 3H), two.51 (m, 1H), two.05 (m, 1H), 1.89 (m, 2H), 1.77 (m, 3H), 1.63 (s, 3H), 1.52 (m, 1H), 1.38 (d, 1H, J = 7.two Hz), 1.33 (s, 3H), 1.19 (s, 3H), 1.18 (s, 3H), 1.16 (d, 1H, J = 7.two Hz); 13C NMR (150 MHz, CDCl3) 205.1, 150.4, 120.5, 101.0, 94.6, 84.7, 72.9, 69.9, 62.3, 59.five, 55.9, 50.0, 40.six, 40.1, 38.2, 33.two, 33.0, 31.five, 30.1 (2C), 26.four, 25.four, 22.four, 18.8; HRMS Calcd for C24H36O8S: [M+H]+ 483.2047; identified 483.2052. Synthesis of (3S,3aR,3a1R,6aR,7S,7aR,11aR,11bS)-7-hydroxy-5,5,8,8-tetramethyl-15methylene-2,three,3a,7,7a,eight,9,11b-octahydro-1H-6a,11a-(epoxymethano)-3,3a1ethanophenanthro[1,10-de][1,3]dioxin-14-one (17) To a answer of 16 (34 mg, 0.07 mmol) in DMF (five mL) was added LiBr (18 mg, 0.21 mmol) and Li2CO3 (15 mg, 0.21 mmol) at rt. The resulting mixture was stirred at 115 for 2 h. The reaction mixture was then diluted with water and extracted with EtOAc. The organic extract was washed with saturated NaHCO3 (aq.) option and brine, dried more than anhydrous Na2SO4, filtered, and evaporated to provide an oily residue. The crude residue was further purified by silica gel column; elution with 25 EtOAc in hexane afforded the desired product 17 as a colorless powder (25 mg, 84 ).2-Bromo-N,N-diphenylaniline manufacturer HPLC purity 99.eight (tR = 18.2387561-40-0 Price 30 min).PMID:23291014 1H NMR (600 MHz, CDCl3) six.16 (s, 1H), 5.77 (m, 1H), 5.56 (s, 1H), 5.41 (d, 1H, J = 12.0 Hz), five.19 (dd, 1H, J = three.0 Hz, ten.2 Hz), four.82 (s, 1H), 3.99 (d, 1H, J = ten.two Hz), 3.90 (dd, 1H, J = 8.4 Hz, 12.0 Hz), 3.81 (d, 1H, J = 9.six Hz), 3.06 (d, 1H, J = 9.0 Hz), 2.53 (m, 1H), 1.95 (d, 1H, J = 17.four Hz), 1.76 (m, 4H), 1.65 (s, 3H), 1.56 (m, 1H), 1.50 (d, 1H, J = eight.four Hz), 1.35 (s, 3H), 1.18 (s, 3H), 1.05 (s, 3H); 13C NMR (150 MHz, CDCl3) 204.5, 150.5, 130.3, 124.1, 120.four, 101.2, 95.4, 72.0, 70.1, 64.8, 57.9, 56.3, 49.1, 41.1, 40.three, 38.1, 32.2, 31.1, 30.3, 30.1, 25.5, 22.1, 17.3; HRMS Calcd for C23H31O5: [M + H]+ 387.2166; located 387.2169. Synthesis of (3S,3aR,3a1R,6aR,7S,7aS,9S,11aR,11bS)-7,9-dihydroxy-5,five,8,8-tetramethyl-15methylene-2,3,3a,7,7a,8,9,11b-octahydro-1H-6a,11a-(epoxymethano)-3,3a1ethanophenanthro[1,10-de][1,3]dioxin-14-one (18) A mixture of 17 (20 mg, 0.05 mmol) and SeO2 (16 mg, 0.15 mmol) in 1,4-dioxane (4 mL) was stirred at one hundred for 16 h. The reaction mixture was then filtered, plus the filtrate was diluted with water and extracted with dichloromethane. The extract was washed with brine, dried more than anhydrous Na2SO4, filtered, and evaporated to offer an oily residue. The residue was purified working with preparative TLC created by 50 EtOAc in hexane to afford the preferred product 18 as a colorless amorphous gel (16 mg, 76 ). HPLC purity 99.7 (tR =NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptJ Med Chem. Author manuscript; readily available in PMC 2014 November 14.Ding et al.Page17.31 min); 1H NMR (600 MHz, CDCl3) 6.16 (s, 1H), six.00 (dd, 1H, J = six.0 Hz, 10.2 Hz), five.56 (s, 1H), five.42 (m, 2H), four.82 (s, 1H), three.94 (m, 2H), 3.84 (d, 1H, J = 9.six Hz), 3.06 (d, 1H, J = 9.six Hz), 2.53 (m, 1H), 1.87 (d, 1H, J = 9.0 Hz), 1.82 (m, 2H), 1.71 (m, 2H), 1.65 (s, 3H), 1.57 (m, 1H), 1.35 (s, 1H), 1.24 (s, 3H), 1.01 (s, 3H); 13C NMR (150 MHz, CDCl3) 204.1, 150.three, 130.9, 128.6, 120.6, 101.two, 95.5, 72.6, 71.five, 70.0, 64.five, 56.1, 51.0, 48.8, 40.3, 38.two, 36.7, 30.two, 30.1, 25.9, 25.four, 21.9, 17.3; HRMS Calcd for C23.