1: 79 percent / NaH / tetrahydrofuran / 4 h / 20 °C 2: 79 percent / LiBr, H2O / dimethylformamide / 12 h / Heating 3: p-TsOH / toluene / 12 h / Heating 4: 1.) hydroquinone, 2.) 20percent AcOH / 1.) THF, 60 deg C, 2 d,2.) H2O, THF, 40 deg C, 72 h 5: 76 percent / LiOH, 30percent H2O2 / methanol / 5 h / 20 °C 6: 1.) NH2NH2*H2O, 2.) KOH, 3.) conc. HCl / 1.) diethylene glycol, 160 deg C, 1 h, 2.) 220-225 deg C, 4 h, 3.) H2O, 0 deg C, 4.) Et2O, 0 deg C 7: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 8: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 9: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 10: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 11: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 76 percent / LiOH, 30percent H2O2 / methanol / 5 h / 20 °C 2: 1.) NH2NH2*H2O, 2.) KOH, 3.) conc. HCl / 1.) diethylene glycol, 160 deg C, 1 h, 2.) 220-225 deg C, 4 h, 3.) H2O, 0 deg C, 4.) Et2O, 0 deg C 3: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 4: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 5: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 6: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 7: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 98 percent / H2 / 10percent Pd/C / acetic acid / 2.5 h / Ambient temperature 2: 75 percent / NaHCO3 / acetonitrile / 24 h / Heating 3: PhPOCl2 / 0.25 h / 165 °C 4: 96 percent / LiAlH4 / tetrahydrofuran / 1.5 h / - 70 deg C up to r.t. 5: Et3N, SO3*pyridine / dimethylsulfoxide / 1 h / 20 °C 6: 1) potassium tert-butoxide / 1) THF, 10 deg C, 10 min, 2a) -78 up to -50 deg C, 1 h, 2b) -25 deg C, 30 min 7: methanol, HCl, acetyl chloride / 4 h / Heating View Scheme

1: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 2: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 3: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 4: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 68 percent / imidazole / dimethylformamide / 12 h / 20 °C 2: 1.) NaH, imidazole / 1.) THF, 20 deg C, 30 min, 2.) 30 min, 3.) 15 min 3: 85 percent / AIBN, tri-n-butyl hydride / toluene / 2 h / Heating 4: 69 percent / NaH / tetrahydrofuran / 3 h / 20 °C 5: 77 percent / TBAF / tetrahydrofuran / 4 h / 20 °C 6: 1.) pyridinium dichromate, 3.) formic acid / 1.) DMF, 20 deg C, 12 h, 2.) CH2Cl2, Et2O, 3.) 20 deg C, 12 h 7: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 8: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 9: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 10: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 11: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 1.) pyridinium dichromate, 3.) formic acid / 1.) DMF, 20 deg C, 12 h, 2.) CH2Cl2, Et2O, 3.) 20 deg C, 12 h 2: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 3: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 4: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 5: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 6: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 69 percent / NaH / tetrahydrofuran / 3 h / 20 °C 2: 77 percent / TBAF / tetrahydrofuran / 4 h / 20 °C 3: 1.) pyridinium dichromate, 3.) formic acid / 1.) DMF, 20 deg C, 12 h, 2.) CH2Cl2, Et2O, 3.) 20 deg C, 12 h 4: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 5: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 6: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 7: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 8: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 1.) NaH, imidazole / 1.) THF, 20 deg C, 30 min, 2.) 30 min, 3.) 15 min 2: 85 percent / AIBN, tri-n-butyl hydride / toluene / 2 h / Heating 3: 69 percent / NaH / tetrahydrofuran / 3 h / 20 °C 4: 77 percent / TBAF / tetrahydrofuran / 4 h / 20 °C 5: 1.) pyridinium dichromate, 3.) formic acid / 1.) DMF, 20 deg C, 12 h, 2.) CH2Cl2, Et2O, 3.) 20 deg C, 12 h 6: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 7: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 8: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 9: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 10: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 85 percent / AIBN, tri-n-butyl hydride / toluene / 2 h / Heating 2: 69 percent / NaH / tetrahydrofuran / 3 h / 20 °C 3: 77 percent / TBAF / tetrahydrofuran / 4 h / 20 °C 4: 1.) pyridinium dichromate, 3.) formic acid / 1.) DMF, 20 deg C, 12 h, 2.) CH2Cl2, Et2O, 3.) 20 deg C, 12 h 5: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 6: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 7: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 8: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 9: 40 percent / t-BuOK / 2 h / 20 °C View Scheme

1: 77 percent / TBAF / tetrahydrofuran / 4 h / 20 °C 2: 1.) pyridinium dichromate, 3.) formic acid / 1.) DMF, 20 deg C, 12 h, 2.) CH2Cl2, Et2O, 3.) 20 deg C, 12 h 3: 1.) POCl3, 2.) 1M LiClO4, 3.) H2, 4.) 30percent ammonia / 3.) 10percent Pd/C / 1.) CH3CN, 100 deg C, 4 h, 2.) CH2Cl2, 10 min, 3.) DMF, 1 bar, 5 h 4: 70 percent / sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 2 h / 20 °C 5: 65 percent / tert-butyl nitrite, sodium bis(trimethylsilyl)amide / toluene; tetrahydrofuran / 1.5 h / 50 °C 6: p-TsOH, paraformaldehyde / acetic acid / 5 h / 100 - 105 °C 7: 40 percent / t-BuOK / 2 h / 20 °C View Scheme