tetrabutylammomium bromide; hydrogen bromide T=110°C; 0.75 h;

hydrogen; palladium on activated charcoal in methanol 0.333333 h;

bis(tri-n-butyltin)oxide in benzene 72 h; Heating;

1: 1.) n-BuLi, 2,2,6,6-tetramethylpiperidine / 1.) hexane, THF, -40 deg C, 40 min, 2.) hexane, THF, -40 deg C, 45 min 2: 54 percent / meta-chloroperbenzoic acid / CH2Cl2 / 21 h / 0 - 20 °C 3: 99 percent / Et3SiH, trifluoroacetic acid / CHCl3 / 1.5 h 4: 85 percent / Bu4NBr, 9 M aq. HBr / 0.75 h / 110 °C View Scheme

1: TiCl4 / CH2Cl2 / 36 h / Ambient temperature 2: 1.) O3, 2.) Zn-dust, HOAc / 1.) CH3OH, -78 deg C, 15 min, 2.) CH3OH, RT, 72 h 3: 1.) n-BuLi, 2,2,6,6-tetramethylpiperidine / 1.) hexane, THF, -40 deg C, 40 min, 2.) hexane, THF, -40 deg C, 45 min 4: 54 percent / meta-chloroperbenzoic acid / CH2Cl2 / 21 h / 0 - 20 °C 5: 99 percent / Et3SiH, trifluoroacetic acid / CHCl3 / 1.5 h 6: 85 percent / Bu4NBr, 9 M aq. HBr / 0.75 h / 110 °C View Scheme

1: 99 percent / Et3SiH, trifluoroacetic acid / CHCl3 / 1.5 h 2: 85 percent / Bu4NBr, 9 M aq. HBr / 0.75 h / 110 °C View Scheme

1: 54 percent / meta-chloroperbenzoic acid / CH2Cl2 / 21 h / 0 - 20 °C 2: 99 percent / Et3SiH, trifluoroacetic acid / CHCl3 / 1.5 h 3: 85 percent / Bu4NBr, 9 M aq. HBr / 0.75 h / 110 °C View Scheme

2: 96 percent / H2 / Pd/C / methanol / 0.33 h View Scheme

1: 1.) Al, HgCl2 / 1.) 40 deg C, 2.) -78 deg C 2: aq. LiOH / tetrahydrofuran / Ambient temperature 3: 60 °C 4: 65 percent / N-methyl morpholine, 1-hydroxybenzotriazole, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide / dimethylformamide / 12 h / Ambient temperature 5: PCC, molecular sieves 4 Angstroem / CH2Cl2 / 1.5 h / Ambient temperature 6: TFA, molecular sieves 4 Angstroem / CH2Cl2 / Ambient temperature 7: 1.) Bu3SnH, AIBN, 2.) TFA / 1.) PhMe, reflux, 2.) THF, r.t., 5 h 8: 1.) O3 2.) Ph3P / 1.) CH2Cl2, -78 deg C, 2.) -78 deg C to r.t. 9: Et3N / tetrahydrofuran / 2 h / 60 °C 10: 67 percent / (Bu3Sn)2O / benzene / 72 h / Heating View Scheme

1: 65 percent / N-methyl morpholine, 1-hydroxybenzotriazole, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide / dimethylformamide / 12 h / Ambient temperature 2: PCC, molecular sieves 4 Angstroem / CH2Cl2 / 1.5 h / Ambient temperature 3: TFA, molecular sieves 4 Angstroem / CH2Cl2 / Ambient temperature 4: 1.) Bu3SnH, AIBN, 2.) TFA / 1.) PhMe, reflux, 2.) THF, r.t., 5 h 5: 1.) O3 2.) Ph3P / 1.) CH2Cl2, -78 deg C, 2.) -78 deg C to r.t. 6: Et3N / tetrahydrofuran / 2 h / 60 °C 7: 67 percent / (Bu3Sn)2O / benzene / 72 h / Heating View Scheme