1: 1.) EtMgBr, 2.) CuI 2: 83 percent / Ph3P, Br2 / CCl4 / 3 h 3: 1.) Mg / 1.) THF, from 45 deg C to 50 deg C, 2.) THF, RT, 0.5 h 4: tetrahydrofuran / 1 h / Ambient temperature 5: O3 / cyclohexane; acetic acid / 5 °C 6: aq. H2CrO4 / cyclohexane; acetic acid / 4 h / 20 °C 7: 94 percent / K2CO3 / methanol / 2 h / 50 °C 8: 93 percent / NaBH4, NaOH, Ni(OAc)2*4H2O, ethylene diamine, H2 / ethanol / 2 h / 20 °C View Scheme

1: 1.) LiNH2, liq. NH3, HMPA / 1.) -33 deg C, 2 h, 2.) THF, -33 deg C, 6 h 2: 90 percent / PTSA / methanol; H2O / 12 h / Ambient temperature View Scheme

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 View Scheme

(i) Li, liq. NH3, (ii) /BRN= 1239238/, (iii) aq. H2SO4, CrO3; Multistep reaction;

1: 1.) MeLi / 1.) THF, ether, -20 deg C, 10 min; 2.) rt, 2 h 2: 1.) DIBAH; 2.) I2 / 1.) THF, hexane, 35 deg C 4 h; 2.) -78 deg C, then 0 deg C, 30 min 3: NaOH / methanol / 4 h / 40 °C 4: acetic acid / Ambient temperature 5: 1.) ZnBr2 / 2.) Pd(PPh3)4 / 1.) THF, -40 deg C; 2.) 10 deg C, 1 h View Scheme

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 View Scheme