potassium hydroxide; platinum Hydrogenation;

1: pig liver esterase 2: oxalyl chloride, DMF / CH2Cl2 / 0.33 h / Ambient temperature 3: Et3N / tetrahydrofuran / 1 h / 0 - 20 °C 4: 1.) aq. LiOH*H2O, 2.) TFA / 1.) THF, 50 deg C, 5 h, 2.) CHCl3, RT, 14 h 5: 57 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / benzene / 2 h / 140 °C 6: 1.) HCl, 2.) K2CO3, 3.) POCl3, 4.) NaBH4 View Scheme

1: oxalyl chloride, DMF / CH2Cl2 / 0.33 h / Ambient temperature 2: Et3N / tetrahydrofuran / 1 h / 0 - 20 °C 3: 1.) aq. LiOH*H2O, 2.) TFA / 1.) THF, 50 deg C, 5 h, 2.) CHCl3, RT, 14 h 4: 57 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / benzene / 2 h / 140 °C 5: 1.) HCl, 2.) K2CO3, 3.) POCl3, 4.) NaBH4 View Scheme

1: Aluminium hydride / diethyl ether / -60 °C 2: t-BuCOOH / 140 °C 3: PPTS / ethanol / Heating 4: LDA / tetrahydrofuran / -78 °C 5: 1.) DIBAL / 1.) CH2Cl2, -78 deg C 2.) glyme, room temp. 6: imidazole / dimethylformamide / Ambient temperature 7: pyridinium chlorochromate / CH2Cl2 / Ambient temperature 8: p-TsOH / methanol / Heating 9: 72 h / 170 °C 10: 1.) 1N HCl 2.) 5percent H2SO4 / 1.) Et2O, room temp. 2.) reflux 11: osmium tetroxide / pyridine / 0 °C / epimers ratio 8:7 12: lead tetracetate / tetrahydrofuran / 0 °C 13: CrO3, H2SO4 / acetone / 0 °C 14: OsO4, NaIO4 / tetrahydrofuran; H2O / 0 °C 15: diethyl ether / Ambient temperature 16: 1.) NaBCNH3 / 1.) MeOH, room temp. 2.) toluene, reflux 17: 1.) POCl3 2.) NaBH4 / 1.) benzene, reflux 2.) MeOH, 0 deg C View Scheme

1: t-BuCOOH / 140 °C 2: PPTS / ethanol / Heating 3: LDA / tetrahydrofuran / -78 °C 4: 1.) DIBAL / 1.) CH2Cl2, -78 deg C 2.) glyme, room temp. 5: imidazole / dimethylformamide / Ambient temperature 6: pyridinium chlorochromate / CH2Cl2 / Ambient temperature 7: p-TsOH / methanol / Heating 8: 72 h / 170 °C 9: 1.) 1N HCl 2.) 5percent H2SO4 / 1.) Et2O, room temp. 2.) reflux 10: osmium tetroxide / pyridine / 0 °C / epimers ratio 8:7 11: lead tetracetate / tetrahydrofuran / 0 °C 12: CrO3, H2SO4 / acetone / 0 °C 13: OsO4, NaIO4 / tetrahydrofuran; H2O / 0 °C 14: diethyl ether / Ambient temperature 15: 1.) NaBCNH3 / 1.) MeOH, room temp. 2.) toluene, reflux 16: 1.) POCl3 2.) NaBH4 / 1.) benzene, reflux 2.) MeOH, 0 deg C View Scheme

hydrogenchloride; sodium tetrahydroborate; potassium carbonate; trichlorophosphate Yield given. Multistep reaction;

acetic acid T=140°C;

1: pyridine / 12 h 2: TFA / tetrahydrofuran / 1 h / Heating 3: NaOMe / methanol / 12 h 4: β-glucosidase / H2O / 72 h / 37 °C / pH 5.0 5: 85 percent / NaCNBH3 / methanol / 48 h 6: 75 percent / aq. HCl / acetone / 2 h / Heating 7: glacial acetic acid / Heating View Scheme

1: β-glucosidase / H2O / 72 h / 37 °C / pH 5.0 2: 85 percent / NaCNBH3 / methanol / 48 h 3: 75 percent / aq. HCl / acetone / 2 h / Heating 4: glacial acetic acid / Heating View Scheme

1: 85 percent / NaCNBH3 / methanol / 48 h 2: 75 percent / aq. HCl / acetone / 2 h / Heating 3: glacial acetic acid / Heating View Scheme