tris-(2-chloro-ethyl)-amine; triphenylphosphine; diethylazodicarboxylate in tetrahydrofuran; benzene a) -10 deg C, 30 min, b) 0 deg C, 2 h, c) RT, overnight;

4-(N,N-dimethlyamino)pyridine; triethylamine in dichloromethane T=20°C; 20 h;

1: 1.) NaH / 1.) THF, DMF, RT, 1h, 2.) RT, 20h 2: 1.) lithium diisopropylamide / 1.) THF, hexane, -78 deg C, 40 min, 2.) THF, -78 deg C, 5 min 3: 81 percent / 30percent H2O2 / ethyl acetate / 0.5 h / 15 - 20 °C 4: 11 percent / OsO4, N-methylmorpholine N-oxide*H2O / acetone; H2O / 14 h / Ambient temperature 5: 90 percent / p-TsOH / acetone / 2 h / Ambient temperature 6: 86 percent / H2 / Pd black / ethanol / 13 h / 760 Torr / Ambient temperature 7: 72 percent / borane-Me2S complex / tetrahydrofuran / 1 h / 70 °C 8: 1.) DMSO, oxalyl chloride, 2.) NEt3 / 1.) CH2Cl2, -20 deg C, 2.) -20 deg C 9: 1.) CuI, THF-Me2S / 1.) THF, -78 deg C, 2.) -78 deg C 10: 1.) NaH / 1.) THF, DMF, RT, 2.) RT 11: 1.) borane-THF complex, 2.) 30percent H2O2, 3N NaOH / 1.) THF, 45 deg C, 2.) 60 deg C 12: 1.) NEt3, 2.) H2, HCl / 2.) 10percent Pd/C / 1.) CH2Cl2, RT, 16h, 2.) EtOH, MeOH, 1 atm, RT, 6h View Scheme

1: 99 percent / DMAP; Et3N / CH2Cl2 / 20 °C 2: 86 percent / DMAP; Et3N / CH2Cl2 / 20 °C 3: 75 percent Chromat. / TBAF*3H2O / tetrahydrofuran / 0.08 h / 20 °C View Scheme

carbon tetrabromide; triphenylphosphine in acetonitrile T=25°C; 70 h;

1: 12 g / potassium hydroxide; tetra-n-butylammonium hydrogen sulfate / CHCl3 / 18 h 2: 75 percent / tributyltin hydride; NaI; AIBN / 1,2-dimethoxy-ethane / 12 h / Heating 3: 61 percent / TMSCl / 2 h / 50 °C View Scheme

1: 86 percent / TosOH / toluene / 9 h / Heating 2: 1.) LDA, / 1.) THF, -78 deg C, 30 min, 2.) THF, -20 deg C, 20 min 3: 100 percent / LAH / tetrahydrofuran / 1 h / Heating 4: 65 percent / H2 / 10percentPd/C / ethyl acetate; acetic acid / 2 h / 2327.2 Torr 5: 77.9 g / aq.K2CO3 / tetrahydrofuran / 0.25 h / 0 °C 6: 78.4 g / aq.(CrO3/H2SO4) / acetone / 3 h / -5 °C 7: 86.3 percent / H2 / 10percentPd/C / methanol / 2 h / 760 Torr / Ambient temperature View Scheme

toluene-4-sulfonic acid

1.1: toluene-4-sulfonic acid / toluene / |Reflux; |Dean-Stark 2.1: lithium hexamethyldisilazane / tetrahydrofuran / 2 h / -50 - -40 °C 2.2: 0.5 h / -55 - -45 °C 3.1: potassium hydrogencarbonate / methanol; water / 10 - 50 °C 4.1: potassium tert-butylate / tetrahydrofuran / 1 h / 10 - 60 °C 4.2: 10 - 60 °C 5.1: lithium aluminium tetrahydride / tetrahydrofuran / 1.5 h / 50 - 60 °C 6.1: palladium 10 on activated carbon; ammonium formate / methanol; water / 10 - 50 °C / |Inert atmosphere 7.1: dichloromethane / 20 - 45 °C 7.2: 20 °C 8.1: Jone's reagent / acetone / 2 h / 0 - 37 °C View Scheme

hydrogenchloride; oxygen; sodium hydrogencarbonate; platinum 1.) H2O, 2.) reflux, 6 h; Yield given. Multistep reaction;