1: in tetrahydrofuran; dichloromethane T=20°C; 0.333333 h; Inert atmosphere; 2: With sodium tris(acetoxy)borohydride T=20°C; 4 h; Inert atmosphere;

1: 1.) NaOH, Adogen 464 / 1) CH2Cl2, water, rt, 30 min; 2) CH2Cl2, water, 0 deg C, 1 h 2: 1.) n-BuLi, 2.) I2 / 1) THF, pentane, -60 deg C, 2 h; 2) THF, pentane, -60 deg C --> rt, 1 h 3: 66 percent / copper bronze / dimethylformamide / 3 h / Heating 4: 1.) n-BuLi, 2.) I2 / 1) THF, pentane, -60 deg C, 2 h; 2) THF, pentane, -60 deg C --> rt, 1 h 5: 82 percent / tetrakis(triphenylphosphine)palladium(0) / dioxane / 14 h / Heating 6: 1.) O3, 1.) dimethyl sulfide / 1) 1,2-dichloroethane, -78 deg C; 2) 1,2-dichloroethane, -78 deg C, 1 h, 0 deg C, 1 h, rt, 1 h 7: 75 percent / sodium triacetoxyborohydride / 1,2-dichloro-ethane / 0.17 h / Ambient temperature View Scheme

1: 1.) n-BuLi, 2.) I2 / 1) THF, pentane, -60 deg C, 2 h; 2) THF, pentane, -60 deg C --> rt, 1 h 2: 66 percent / copper bronze / dimethylformamide / 3 h / Heating 3: 1.) n-BuLi, 2.) I2 / 1) THF, pentane, -60 deg C, 2 h; 2) THF, pentane, -60 deg C --> rt, 1 h 4: 82 percent / tetrakis(triphenylphosphine)palladium(0) / dioxane / 14 h / Heating 5: 1.) O3, 1.) dimethyl sulfide / 1) 1,2-dichloroethane, -78 deg C; 2) 1,2-dichloroethane, -78 deg C, 1 h, 0 deg C, 1 h, rt, 1 h 6: 75 percent / sodium triacetoxyborohydride / 1,2-dichloro-ethane / 0.17 h / Ambient temperature View Scheme

1: 66 percent / copper bronze / dimethylformamide / 3 h / Heating 2: 1.) n-BuLi, 2.) I2 / 1) THF, pentane, -60 deg C, 2 h; 2) THF, pentane, -60 deg C --> rt, 1 h 3: 82 percent / tetrakis(triphenylphosphine)palladium(0) / dioxane / 14 h / Heating 4: 1.) O3, 1.) dimethyl sulfide / 1) 1,2-dichloroethane, -78 deg C; 2) 1,2-dichloroethane, -78 deg C, 1 h, 0 deg C, 1 h, rt, 1 h 5: 75 percent / sodium triacetoxyborohydride / 1,2-dichloro-ethane / 0.17 h / Ambient temperature View Scheme

1: 82 percent / tetrakis(triphenylphosphine)palladium(0) / dioxane / 14 h / Heating 2: 1.) O3, 1.) dimethyl sulfide / 1) 1,2-dichloroethane, -78 deg C; 2) 1,2-dichloroethane, -78 deg C, 1 h, 0 deg C, 1 h, rt, 1 h 3: 75 percent / sodium triacetoxyborohydride / 1,2-dichloro-ethane / 0.17 h / Ambient temperature View Scheme

1: 1.) O3, 1.) dimethyl sulfide / 1) 1,2-dichloroethane, -78 deg C; 2) 1,2-dichloroethane, -78 deg C, 1 h, 0 deg C, 1 h, rt, 1 h 2: 75 percent / sodium triacetoxyborohydride / 1,2-dichloro-ethane / 0.17 h / Ambient temperature View Scheme

1: 1.) n-BuLi, 2.) I2 / 1) THF, pentane, -60 deg C, 2 h; 2) THF, pentane, -60 deg C --> rt, 1 h 2: 82 percent / tetrakis(triphenylphosphine)palladium(0) / dioxane / 14 h / Heating 3: 1.) O3, 1.) dimethyl sulfide / 1) 1,2-dichloroethane, -78 deg C; 2) 1,2-dichloroethane, -78 deg C, 1 h, 0 deg C, 1 h, rt, 1 h 4: 75 percent / sodium triacetoxyborohydride / 1,2-dichloro-ethane / 0.17 h / Ambient temperature View Scheme

formic acid T=100°C; Eschweiler-Clarke Methylation; 4 h;

hydrogenchloride in dichloromethane 2 h;