lithium hexamethyldisilazane in tetrahydrofuran T=-68°C;

1: 72 percent / diethyl ether / 30 °C / Irradiation 2: 63 percent / diethyl ether / -78 °C 3: KH, 18-Cr-6 / tetrahydrofuran / 0.42 h / 60 °C 4: 77 percent / toluene / 20 h / 175 °C 5: 82 percent / benzene / Irradiation 6: LiN(SiMe3)2 / tetrahydrofuran / -68 °C View Scheme

1: 1.) NaH / 1.) dioxane, MeOH, reflux; 2.) reflux, 90 min 2: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 3: LiAlH4 / diethyl ether / 1 h / below 10 deg C 4: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 5: OsO4, NaIO4 / diethyl ether; H2O / 7 h 6: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 7: pyridine / Ambient temperature 8: 75 percent AcOH / 1 h / 30 °C 9: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 10: NaOAc / 0.67 h / 130 °C 11: 1 percent NaOMe / methanol / 1 h / Ambient temperature 12: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 13: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 14: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 15: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 16: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 17: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 18: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme

1: LiAlH4 / diethyl ether / 1 h / below 10 deg C 2: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 3: OsO4, NaIO4 / diethyl ether; H2O / 7 h 4: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 5: pyridine / Ambient temperature 6: 75 percent AcOH / 1 h / 30 °C 7: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 8: NaOAc / 0.67 h / 130 °C 9: 1 percent NaOMe / methanol / 1 h / Ambient temperature 10: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 11: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 12: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 13: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 14: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 15: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 16: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme

1: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 2: OsO4, NaIO4 / diethyl ether; H2O / 7 h 3: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 4: pyridine / Ambient temperature 5: 75 percent AcOH / 1 h / 30 °C 6: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 7: NaOAc / 0.67 h / 130 °C 8: 1 percent NaOMe / methanol / 1 h / Ambient temperature 9: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 10: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 11: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 12: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 13: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 14: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 15: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme

1: pyridine / Ambient temperature 2: 75 percent AcOH / 1 h / 30 °C 3: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 4: NaOAc / 0.67 h / 130 °C 5: 1 percent NaOMe / methanol / 1 h / Ambient temperature 6: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 7: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 8: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 9: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 10: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 11: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 12: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme

1: OsO4, NaIO4 / diethyl ether; H2O / 7 h 2: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 3: pyridine / Ambient temperature 4: 75 percent AcOH / 1 h / 30 °C 5: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 6: NaOAc / 0.67 h / 130 °C 7: 1 percent NaOMe / methanol / 1 h / Ambient temperature 8: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 9: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 10: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 11: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 12: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 13: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 14: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme

1: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 2: LiAlH4 / diethyl ether / 1 h / below 10 deg C 3: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 4: OsO4, NaIO4 / diethyl ether; H2O / 7 h 5: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 6: pyridine / Ambient temperature 7: 75 percent AcOH / 1 h / 30 °C 8: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 9: NaOAc / 0.67 h / 130 °C 10: 1 percent NaOMe / methanol / 1 h / Ambient temperature 11: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 12: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 13: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 14: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 15: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 16: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 17: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme

1: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 2: pyridine / Ambient temperature 3: 75 percent AcOH / 1 h / 30 °C 4: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 5: NaOAc / 0.67 h / 130 °C 6: 1 percent NaOMe / methanol / 1 h / Ambient temperature 7: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 8: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 9: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 10: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 11: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 12: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 13: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme

1: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 2: NaOAc / 0.67 h / 130 °C 3: 1 percent NaOMe / methanol / 1 h / Ambient temperature 4: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 5: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 6: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 7: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 8: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 9: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 10: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min View Scheme