titanium tetrachloride in dichloromethane T=0 - 25°C; Acetylation; 6 h;

4-(N,N-dimethlyamino)pyridine in pyridine 8 h; Ambient temperature;

1.1: zirconocene chloride hydride / benzene / 6 h / 20 °C 1.2: 71 percent / I2 / benzene 2.1: Pd(PPh3)4 / benzene / 0.25 h / 20 °C 2.2: 70 percent / benzene / 20 °C 3.1: 80 percent / PPTs / methanol / 24 h / 20 °C 4.1: 82 percent / pyridine / 12 h / 20 °C View Scheme

1: 80 percent / PPTs / methanol / 24 h / 20 °C 2: 82 percent / pyridine / 12 h / 20 °C View Scheme

1: 78 percent / Na, liq. NH3 / 2 h 2: 90 percent / DMAP / pyridine / 8 h / Ambient temperature View Scheme

1: 72.1 percent / NaNH2, 1,3-diaminopropane / 4 h / 80 °C 2: 85 percent / PTSA / CH2Cl2 / 8 h / Ambient temperature 3: 1.) LiNH2, liq. NH3, HMPA / 1.) -33 deg C, 2 h, 2.) THF, -33 deg C, 6 h 4: 90 percent / PTSA / methanol; H2O / 12 h / Ambient temperature 5: 78 percent / Na, liq. NH3 / 2 h 6: 90 percent / DMAP / pyridine / 8 h / Ambient temperature View Scheme

1: 85 percent / PTSA / CH2Cl2 / 8 h / Ambient temperature 2: 1.) LiNH2, liq. NH3, HMPA / 1.) -33 deg C, 2 h, 2.) THF, -33 deg C, 6 h 3: 90 percent / PTSA / methanol; H2O / 12 h / Ambient temperature 4: 78 percent / Na, liq. NH3 / 2 h 5: 90 percent / DMAP / pyridine / 8 h / Ambient temperature View Scheme

1: 90 percent / PTSA / methanol; H2O / 12 h / Ambient temperature 2: 78 percent / Na, liq. NH3 / 2 h 3: 90 percent / DMAP / pyridine / 8 h / Ambient temperature View Scheme

1.1: 98 percent / dimethylsulfoxide / 3 h / 20 °C 2.1: zirconocene chloride hydride / benzene / 6 h / 20 °C 2.2: 71 percent / I2 / benzene 3.1: Pd(PPh3)4 / benzene / 0.25 h / 20 °C 3.2: 70 percent / benzene / 20 °C 4.1: 80 percent / PPTs / methanol / 24 h / 20 °C 5.1: 82 percent / pyridine / 12 h / 20 °C View Scheme

1.1: 5 h / 20 °C 2.1: 98 percent / dimethylsulfoxide / 3 h / 20 °C 3.1: zirconocene chloride hydride / benzene / 6 h / 20 °C 3.2: 71 percent / I2 / benzene 4.1: Pd(PPh3)4 / benzene / 0.25 h / 20 °C 4.2: 70 percent / benzene / 20 °C 5.1: 80 percent / PPTs / methanol / 24 h / 20 °C 6.1: 82 percent / pyridine / 12 h / 20 °C View Scheme