1: 1) lithium diisopropylamide / 1) THF, -78 deg C, 45 min, 2a) THF, -78 deg C, 45 min, 2b) r.t., 5 h 2: 1) MeI, 2) 5 percent aq. NaHCO3 / 1a) MeOH, 4 deg C, overnight, 1b) r.t., 5 h, 2) CH2Cl2, r.t., 16 h 3: 95 percent / CeCl3*6H2O, NaBH4 / methanol / 0 °C / 5 to 10 min 4: 1a) MS 3 Angstroem, diisopropyl (-)-tartrate, 1b) Ti(O-i-Pr)4, 2) cumene hydroperoxide / 1a) CH2Cl2, r.t., 1b) -5 deg C, 20 min, 2a) -5 deg C, 8 h, 2b) 4 deg C, overnight 5: 51 percent / Ti(O-i-Pr)4 / benzene / 0.33 h 6: 98 percent / camphorsulfonic acid / CH2Cl2 / 5 h 7: 90 percent / LiAlH4 / diethyl ether / 1 h / Heating 8: 67 percent / pyridinium dichromate / dimethylformamide / 30 h / Ambient temperature 9: 99 percent / diethyl ether 10: 93 percent / Ti(OEt)4 / 60 h / 100 °C 11: 1) O3, 2) Me2S / 1) CH2Cl2, -78 deg C, 45 min, 2) to r.t., 7 h 12: 67 percent / NaIO4, 2 percent RuCl3*3H2O / acetonitrile; CCl4 / 0.33 h / Ambient temperature; phosphate buffer, pH 7 13: 96 percent / HOAc / H2O / 8 h / 75 °C 14: 74 percent / 2-chloro-1-methylpyridinium iodide, 4-(dimethylamino)pyridine / acetonitrile / a) 0 deg C, 3 h, b) r.t., 10 h 15: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 16: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 17: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 18: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 19: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 20: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 21: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 70 percent / pyridinium chlorochromate, NaOAc / CH2Cl2 / 2 h 2: 1) lithium diisopropylamide / 1) THF, -78 deg C, 45 min, 2a) THF, -78 deg C, 45 min, 2b) r.t., 5 h 3: 1) MeI, 2) 5 percent aq. NaHCO3 / 1a) MeOH, 4 deg C, overnight, 1b) r.t., 5 h, 2) CH2Cl2, r.t., 16 h 4: 95 percent / CeCl3*6H2O, NaBH4 / methanol / 0 °C / 5 to 10 min 5: 1a) MS 3 Angstroem, diisopropyl (-)-tartrate, 1b) Ti(O-i-Pr)4, 2) cumene hydroperoxide / 1a) CH2Cl2, r.t., 1b) -5 deg C, 20 min, 2a) -5 deg C, 8 h, 2b) 4 deg C, overnight 6: 51 percent / Ti(O-i-Pr)4 / benzene / 0.33 h 7: 98 percent / camphorsulfonic acid / CH2Cl2 / 5 h 8: 90 percent / LiAlH4 / diethyl ether / 1 h / Heating 9: 67 percent / pyridinium dichromate / dimethylformamide / 30 h / Ambient temperature 10: 99 percent / diethyl ether 11: 93 percent / Ti(OEt)4 / 60 h / 100 °C 12: 1) O3, 2) Me2S / 1) CH2Cl2, -78 deg C, 45 min, 2) to r.t., 7 h 13: 67 percent / NaIO4, 2 percent RuCl3*3H2O / acetonitrile; CCl4 / 0.33 h / Ambient temperature; phosphate buffer, pH 7 14: 96 percent / HOAc / H2O / 8 h / 75 °C 15: 74 percent / 2-chloro-1-methylpyridinium iodide, 4-(dimethylamino)pyridine / acetonitrile / a) 0 deg C, 3 h, b) r.t., 10 h 16: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 17: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 18: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 19: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 20: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 21: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 22: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 97 percent / LiAlH4 / diethyl ether / 0 °C 2: 70 percent / pyridinium chlorochromate, NaOAc / CH2Cl2 / 2 h 3: 1) lithium diisopropylamide / 1) THF, -78 deg C, 45 min, 2a) THF, -78 deg C, 45 min, 2b) r.t., 5 h 4: 1) MeI, 2) 5 percent aq. NaHCO3 / 1a) MeOH, 4 deg C, overnight, 1b) r.t., 5 h, 2) CH2Cl2, r.t., 16 h 5: 95 percent / CeCl3*6H2O, NaBH4 / methanol / 0 °C / 5 to 10 min 6: 1a) MS 3 Angstroem, diisopropyl (-)-tartrate, 1b) Ti(O-i-Pr)4, 2) cumene hydroperoxide / 1a) CH2Cl2, r.t., 1b) -5 deg C, 20 min, 2a) -5 deg C, 8 h, 2b) 4 deg C, overnight 7: 51 percent / Ti(O-i-Pr)4 / benzene / 0.33 h 8: 98 percent / camphorsulfonic acid / CH2Cl2 / 5 h 9: 90 percent / LiAlH4 / diethyl ether / 1 h / Heating 10: 67 percent / pyridinium dichromate / dimethylformamide / 30 h / Ambient temperature 11: 99 percent / diethyl ether 12: 93 percent / Ti(OEt)4 / 60 h / 100 °C 13: 1) O3, 2) Me2S / 1) CH2Cl2, -78 deg C, 45 min, 2) to r.t., 7 h 14: 67 percent / NaIO4, 2 percent RuCl3*3H2O / acetonitrile; CCl4 / 0.33 h / Ambient temperature; phosphate buffer, pH 7 15: 96 percent / HOAc / H2O / 8 h / 75 °C 16: 74 percent / 2-chloro-1-methylpyridinium iodide, 4-(dimethylamino)pyridine / acetonitrile / a) 0 deg C, 3 h, b) r.t., 10 h 17: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 18: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 19: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 20: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 21: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 22: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 23: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 95 percent / CeCl3*6H2O, NaBH4 / methanol / 0 °C / 5 to 10 min 2: 1a) MS 3 Angstroem, diisopropyl (-)-tartrate, 1b) Ti(O-i-Pr)4, 2) cumene hydroperoxide / 1a) CH2Cl2, r.t., 1b) -5 deg C, 20 min, 2a) -5 deg C, 8 h, 2b) 4 deg C, overnight 3: 51 percent / Ti(O-i-Pr)4 / benzene / 0.33 h 4: 98 percent / camphorsulfonic acid / CH2Cl2 / 5 h 5: 90 percent / LiAlH4 / diethyl ether / 1 h / Heating 6: 67 percent / pyridinium dichromate / dimethylformamide / 30 h / Ambient temperature 7: 99 percent / diethyl ether 8: 93 percent / Ti(OEt)4 / 60 h / 100 °C 9: 1) O3, 2) Me2S / 1) CH2Cl2, -78 deg C, 45 min, 2) to r.t., 7 h 10: 67 percent / NaIO4, 2 percent RuCl3*3H2O / acetonitrile; CCl4 / 0.33 h / Ambient temperature; phosphate buffer, pH 7 11: 96 percent / HOAc / H2O / 8 h / 75 °C 12: 74 percent / 2-chloro-1-methylpyridinium iodide, 4-(dimethylamino)pyridine / acetonitrile / a) 0 deg C, 3 h, b) r.t., 10 h 13: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 14: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 15: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 16: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 17: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 18: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 19: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 67 percent / pyridinium dichromate / dimethylformamide / 30 h / Ambient temperature 2: 99 percent / diethyl ether 3: 93 percent / Ti(OEt)4 / 60 h / 100 °C 4: 1) O3, 2) Me2S / 1) CH2Cl2, -78 deg C, 45 min, 2) to r.t., 7 h 5: 67 percent / NaIO4, 2 percent RuCl3*3H2O / acetonitrile; CCl4 / 0.33 h / Ambient temperature; phosphate buffer, pH 7 6: 96 percent / HOAc / H2O / 8 h / 75 °C 7: 74 percent / 2-chloro-1-methylpyridinium iodide, 4-(dimethylamino)pyridine / acetonitrile / a) 0 deg C, 3 h, b) r.t., 10 h 8: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 9: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 10: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 11: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 12: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 13: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 14: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 98 percent / camphorsulfonic acid / CH2Cl2 / 5 h 2: 90 percent / LiAlH4 / diethyl ether / 1 h / Heating 3: 67 percent / pyridinium dichromate / dimethylformamide / 30 h / Ambient temperature 4: 99 percent / diethyl ether 5: 93 percent / Ti(OEt)4 / 60 h / 100 °C 6: 1) O3, 2) Me2S / 1) CH2Cl2, -78 deg C, 45 min, 2) to r.t., 7 h 7: 67 percent / NaIO4, 2 percent RuCl3*3H2O / acetonitrile; CCl4 / 0.33 h / Ambient temperature; phosphate buffer, pH 7 8: 96 percent / HOAc / H2O / 8 h / 75 °C 9: 74 percent / 2-chloro-1-methylpyridinium iodide, 4-(dimethylamino)pyridine / acetonitrile / a) 0 deg C, 3 h, b) r.t., 10 h 10: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 11: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 12: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 13: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 14: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 15: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 16: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 2: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 3: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 4: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 5: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 6: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 7: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 90 percent / LiAlH4 / diethyl ether / 1 h / Heating 2: 67 percent / pyridinium dichromate / dimethylformamide / 30 h / Ambient temperature 3: 99 percent / diethyl ether 4: 93 percent / Ti(OEt)4 / 60 h / 100 °C 5: 1) O3, 2) Me2S / 1) CH2Cl2, -78 deg C, 45 min, 2) to r.t., 7 h 6: 67 percent / NaIO4, 2 percent RuCl3*3H2O / acetonitrile; CCl4 / 0.33 h / Ambient temperature; phosphate buffer, pH 7 7: 96 percent / HOAc / H2O / 8 h / 75 °C 8: 74 percent / 2-chloro-1-methylpyridinium iodide, 4-(dimethylamino)pyridine / acetonitrile / a) 0 deg C, 3 h, b) r.t., 10 h 9: 91 percent / (i-Pr)2NEt / tetrahydrofuran / 15 h / 50 °C 10: 1) N-isopropylcyclohexylamine, n-BuLi / 1) THF, hexane, -60 to -50 deg C, 45 min, 2a) -60 deg C, 45 min, 2b) to -20 deg C, 10 min 11: Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 6 h 12: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 15 h / 4 °C 13: 90 percent / 3 M aq. HCl / tetrahydrofuran / a) r.t., 1 h, b) 35 deg C, 10 h 14: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 15: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme

1: 60 percent / RuCl3*3H2O, 30 percent aq. H2O2 / tetrahydrofuran / a) 0 deg C, 0.5 h, b) r.t., 2 h 2: 91 percent / camphorsulfonic acid / CHCl3 / 12 h / Ambient temperature View Scheme