1: trimethyl-sulfonium iodide With n-butyllithium in tetrahydrofuran T=0°C; Inert atmosphere; 2: (+/-)-2-[bis(methylthio)methylene]-7-isopropyl-8-methoxy-4a-methyl-3,4,4a,9,10,10a-hexahydrophenanthren-1(2H)-one in tetrahydrofuran T=0 - 20°C; 2.5 h; Inert atmosphere; 3: With hydrogenchloride; water in methanol Inert atmosphere;

methoxide anion in methanol T=25°C; 0.25 h;

hydrogen; palladium on activated charcoal in ethyl acetate P=2585.7 Torr; 1.5 h;

2: MCPBA / CH2Cl2 3: base View Scheme

1: 80 percent / xylene / 72 h / Heating; 4-Angstroem sieves 2: 100 percent / MCPBA / CH2Cl2 / 30 h / 25 °C 3: 1.) lithium hexamethyldisilazide, 2.) 1 M HCl / 1.) THF, 0 deg C; 25 deg C, 2 h, 2.) 10 min View Scheme

1: 85 percent / thionyl chloride, pyridine / diethyl ether / 2 h / 0 °C 2: dimethylsulfoxide / 24 h / 70 - 75 °C 3: NaOMe / methanol / 24 h / 25 °C 4: 80 percent / xylene / 72 h / Heating; 4-Angstroem sieves 5: 100 percent / MCPBA / CH2Cl2 / 30 h / 25 °C 6: 1.) lithium hexamethyldisilazide, 2.) 1 M HCl / 1.) THF, 0 deg C; 25 deg C, 2 h, 2.) 10 min View Scheme

1: dimethylsulfoxide / 24 h / 70 - 75 °C 2: NaOMe / methanol / 24 h / 25 °C 3: 80 percent / xylene / 72 h / Heating; 4-Angstroem sieves 4: 100 percent / MCPBA / CH2Cl2 / 30 h / 25 °C 5: 1.) lithium hexamethyldisilazide, 2.) 1 M HCl / 1.) THF, 0 deg C; 25 deg C, 2 h, 2.) 10 min View Scheme

1: 90 percent / NaH / tetrahydrofuran / Ambient temperature 2: 1.) n-BuLi / 1.) TMEDA, room temperature 3: 90 percent / PBr3 / diethyl ether / 0 °C 4: 99 percent / NaH / tetrahydrofuran / 0 deg C -> room temperature 5: 1.) Ba(OH)2 / 2.) H2O, Et2O, 90 deg C, 17 h 6: LAH / diethyl ether / 0 °C 7: 1.) PBr3, LiBr, collidine, 2.) ZnBr2 / 1.) Et2O, -40 - 0 deg C, 2.) 0 deg C 8: 90 percent / LiH / dimethylformamide / 75 °C 9: SnCl4 / CH2Cl2 / 1.5 h / 0 °C 10: MeSO2Cl, (C2H5)3N / CH2Cl2 / 0 °C 11: m-ClC6H4CO3H / CH2Cl2 / Ambient temperature 12: n-C4H9Li, (i-C3H7)NH / CH2Cl2 / -78 °C View Scheme

1: 1.) n-BuLi / 1.) TMEDA, room temperature 2: 90 percent / PBr3 / diethyl ether / 0 °C 3: 99 percent / NaH / tetrahydrofuran / 0 deg C -> room temperature 4: 1.) Ba(OH)2 / 2.) H2O, Et2O, 90 deg C, 17 h 5: LAH / diethyl ether / 0 °C 6: 1.) PBr3, LiBr, collidine, 2.) ZnBr2 / 1.) Et2O, -40 - 0 deg C, 2.) 0 deg C 7: 90 percent / LiH / dimethylformamide / 75 °C 8: SnCl4 / CH2Cl2 / 1.5 h / 0 °C 9: MeSO2Cl, (C2H5)3N / CH2Cl2 / 0 °C 10: m-ClC6H4CO3H / CH2Cl2 / Ambient temperature 11: n-C4H9Li, (i-C3H7)NH / CH2Cl2 / -78 °C View Scheme

1: 99 percent / NaH / tetrahydrofuran / 0 deg C -> room temperature 2: 1.) Ba(OH)2 / 2.) H2O, Et2O, 90 deg C, 17 h 3: LAH / diethyl ether / 0 °C 4: 1.) PBr3, LiBr, collidine, 2.) ZnBr2 / 1.) Et2O, -40 - 0 deg C, 2.) 0 deg C 5: 90 percent / LiH / dimethylformamide / 75 °C 6: SnCl4 / CH2Cl2 / 1.5 h / 0 °C 7: MeSO2Cl, (C2H5)3N / CH2Cl2 / 0 °C 8: m-ClC6H4CO3H / CH2Cl2 / Ambient temperature 9: n-C4H9Li, (i-C3H7)NH / CH2Cl2 / -78 °C View Scheme