1: 81 percent / i-BuMgBr / Cp2TiCl2 / diethyl ether / 12 h / 26 - 28 °C 2: oxalic acid, 2,5-di-tert-butylhydroquinone / acetone; H2O / 2 h / Heating 3: 1) n-BuLi / 1) THF, hexane, -60 deg C, 1h, 2) 0 deg C, 1h 4: 44 percent / t-BuOOH, Ti(O-i-Pr)4, L-(+)-DIPT, molecular sieves 4 Angstroem / CH2Cl2 / 4 h / -21 °C 5: 86 percent / t-BuOOH, d-(-)-DIPT, Ti(O-i-Pr)4, molecular sieves 4 Angstroem / CH2Cl2 / 4 h / -21 °C 6: imidazole / dimethylformamide / Ambient temperature 7: 1) Bu3SnLi, 2) I2 / 1) THF, 0 deg C, 3h, 2) Et2O, 0 deg C, 0.5h 8: 1) disiamylborane, 2) LiOH / 2) Pd(PPh3)4 / 1) THF, 0 deg C, 1h, 2) 40 deg C, 18h 9: 85 percent / n-Bu4NF / tetrahydrofuran / 17 h / Ambient temperature View Scheme

1: 83 percent / quinoline; H2 / Lindlar catalyst / ethanol / 2 h 2: HCOOH / pentane / -40 - 20 °C View Scheme

1: 83 percent / hydrogen / Pd/BaSO4 / methanol / 30 h 2: 93 percent / oxalic acid / acetone; H2O / 1 h / 60 °C 3: 62 percent / n-BuLi / tetrahydrofuran / 1 h / -78 °C View Scheme

1: 81 percent / i-BuMgBr / Cp2TiCl2 / diethyl ether / 12 h / 26 - 28 °C 2: oxalic acid, 2,5-di-tert-butylhydroquinone / acetone; H2O / 2 h / Heating 3: 1) n-BuLi / 1) THF, hexane, -60 deg C, 1h, 2) 0 deg C, 1h View Scheme

1: 1-n-heptyne With n-butyllithium in tetrahydrofuran; N,N,N',N',N'',N''-hexamethylphosphoric triamide; hexane T=-78 - -45°C; Metallation; 0.75 h; 2: 2-bromoacetaldehyde diethyl acetal in tetrahydrofuran T=-78 - 20°C; Alkylation; 20 h;

camphor-10-sulfonic acid in dichloromethane T=20°C;

1: 83 percent / hydrogen / Pd/BaSO4 / methanol / 30 h 2: 93 percent / oxalic acid / acetone; H2O / 1 h / 60 °C 3: 62 percent / n-BuLi / tetrahydrofuran / 1 h / -78 °C 4: 69 percent / 7 h / Heating 5: 47 percent Chromat. / Al2O3 / benzene / 1 h / Heating View Scheme

1: 83 percent / hydrogen / Pd/BaSO4 / methanol / 30 h 2: 93 percent / oxalic acid / acetone; H2O / 1 h / 60 °C 3: 62 percent / n-BuLi / tetrahydrofuran / 1 h / -78 °C 4: 69 percent / 7 h / Heating 5: 47 percent Chromat. / Al2O3 / benzene / 1 h / Heating 6: 58 percent / LiAlH4 / diethyl ether / 1.5 h / -40 °C View Scheme

hydrogen; Pd-BaSO4 in methanol 30 h;

1: 83 percent / hydrogen / Pd/BaSO4 / methanol / 30 h 2: 93 percent / oxalic acid / acetone; H2O / 1 h / 60 °C 3: 62 percent / n-BuLi / tetrahydrofuran / 1 h / -78 °C 4: 69 percent / 7 h / Heating View Scheme