pyridinium chlorochromate in dichloromethane 2 h; Ambient temperature;

borane-THF in tetrahydrofuran T=0°C; 3.5 h;

pyridine T=-20°C; 12 h;

1: iPr2NEt / CH2Cl2 / 0.5 h / -78 °C 2: 1) mCPBA, KHCO3, 2) citric acid / 1) CH2Cl2, -30 to -20 deg C, 1 h, 2) MeOH, 0 deg C to RT 3: NaIO4 / methanol; H2O / 0 deg C, 12 h; RT, 3 h 4: CHCl3 / Ambient temperature 5: 71 percent / LTBA / tetrahydrofuran / -78 to -40 deg C; -35 deg C, 4 h 6: 89 percent / nBu3P / tetrahydrofuran / 1 h / 0 - 20 °C 7: 85 percent / 30percent H2O2 / tetrahydrofuran / 18 h / 0 - 20 °C 8: I2, NaHCO3 / CH2Cl2 / 48 h / Ambient temperature 9: 90 percent / methanol / 4 h / 0 - 20 °C 10: LTBA / tetrahydrofuran / 3 h / 0 °C 11: pyridine / 2 h / 0 - 20 °C 12: 56 percent / CSA, dihydroquinone / benzene / 3 h / Heating 13: 1) mCPBA, 2) 2N HCl / 1) CH2Cl2, -30 to -25 deg C, 20 h, 2) THF, RT, 16 h 14: Me4NBH(OAc)3 / acetic acid; acetonitrile / 2 h / 0 °C 15: DDQ / dioxane / 4 h / 80 °C 16: 94 percent / Ag2O / acetonitrile / 24 h / Ambient temperature 17: 92 percent / MsCl, Et3N / CH2Cl2 / Ambient temperature 18: 47 percent / OsO4, DABCO / tetrahydrofuran / 24 h / -40 °C 19: 92 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 16 h / Ambient temperature 20: CH(NMe2)3 / 1 h / 100 °C 21: 2N HCl / tetrahydrofuran / 20 h / Ambient temperature 22: PCC / CH2Cl2 / 5 h / Ambient temperature 23: CH2Cl2 / 0.33 h / Ambient temperature 24: DBN / CH2Cl2 / 6 h / Ambient temperature 25: K2CO3, MeOH / 5 h / Ambient temperature 26: 1N HCl / tetrahydrofuran / 12 h / Ambient temperature 27: 49 percent / pyridine / 12 h / -20 °C View Scheme

1: p-TsOH / benzene / 24 h / Heating 2: 80 percent / mCPBA / CH2Cl2 / 24 h / -20 - 0 °C 3: iPr2NEt / CH2Cl2 / 0.5 h / -78 °C 4: 1) mCPBA, KHCO3, 2) citric acid / 1) CH2Cl2, -30 to -20 deg C, 1 h, 2) MeOH, 0 deg C to RT 5: NaIO4 / methanol; H2O / 0 deg C, 12 h; RT, 3 h 6: CHCl3 / Ambient temperature 7: 71 percent / LTBA / tetrahydrofuran / -78 to -40 deg C; -35 deg C, 4 h 8: 89 percent / nBu3P / tetrahydrofuran / 1 h / 0 - 20 °C 9: 85 percent / 30percent H2O2 / tetrahydrofuran / 18 h / 0 - 20 °C 10: I2, NaHCO3 / CH2Cl2 / 48 h / Ambient temperature 11: 90 percent / methanol / 4 h / 0 - 20 °C 12: LTBA / tetrahydrofuran / 3 h / 0 °C 13: pyridine / 2 h / 0 - 20 °C 14: 56 percent / CSA, dihydroquinone / benzene / 3 h / Heating 15: 1) mCPBA, 2) 2N HCl / 1) CH2Cl2, -30 to -25 deg C, 20 h, 2) THF, RT, 16 h 16: Me4NBH(OAc)3 / acetic acid; acetonitrile / 2 h / 0 °C 17: DDQ / dioxane / 4 h / 80 °C 18: 94 percent / Ag2O / acetonitrile / 24 h / Ambient temperature 19: 92 percent / MsCl, Et3N / CH2Cl2 / Ambient temperature 20: 47 percent / OsO4, DABCO / tetrahydrofuran / 24 h / -40 °C 21: 92 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 16 h / Ambient temperature 22: CH(NMe2)3 / 1 h / 100 °C 23: 2N HCl / tetrahydrofuran / 20 h / Ambient temperature 24: PCC / CH2Cl2 / 5 h / Ambient temperature 25: CH2Cl2 / 0.33 h / Ambient temperature 26: DBN / CH2Cl2 / 6 h / Ambient temperature 27: K2CO3, MeOH / 5 h / Ambient temperature 28: 1N HCl / tetrahydrofuran / 12 h / Ambient temperature 29: 49 percent / pyridine / 12 h / -20 °C View Scheme

1: 80 percent / mCPBA / CH2Cl2 / 24 h / -20 - 0 °C 2: iPr2NEt / CH2Cl2 / 0.5 h / -78 °C 3: 1) mCPBA, KHCO3, 2) citric acid / 1) CH2Cl2, -30 to -20 deg C, 1 h, 2) MeOH, 0 deg C to RT 4: NaIO4 / methanol; H2O / 0 deg C, 12 h; RT, 3 h 5: CHCl3 / Ambient temperature 6: 71 percent / LTBA / tetrahydrofuran / -78 to -40 deg C; -35 deg C, 4 h 7: 89 percent / nBu3P / tetrahydrofuran / 1 h / 0 - 20 °C 8: 85 percent / 30percent H2O2 / tetrahydrofuran / 18 h / 0 - 20 °C 9: I2, NaHCO3 / CH2Cl2 / 48 h / Ambient temperature 10: 90 percent / methanol / 4 h / 0 - 20 °C 11: LTBA / tetrahydrofuran / 3 h / 0 °C 12: pyridine / 2 h / 0 - 20 °C 13: 56 percent / CSA, dihydroquinone / benzene / 3 h / Heating 14: 1) mCPBA, 2) 2N HCl / 1) CH2Cl2, -30 to -25 deg C, 20 h, 2) THF, RT, 16 h 15: Me4NBH(OAc)3 / acetic acid; acetonitrile / 2 h / 0 °C 16: DDQ / dioxane / 4 h / 80 °C 17: 94 percent / Ag2O / acetonitrile / 24 h / Ambient temperature 18: 92 percent / MsCl, Et3N / CH2Cl2 / Ambient temperature 19: 47 percent / OsO4, DABCO / tetrahydrofuran / 24 h / -40 °C 20: 92 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 16 h / Ambient temperature 21: CH(NMe2)3 / 1 h / 100 °C 22: 2N HCl / tetrahydrofuran / 20 h / Ambient temperature 23: PCC / CH2Cl2 / 5 h / Ambient temperature 24: CH2Cl2 / 0.33 h / Ambient temperature 25: DBN / CH2Cl2 / 6 h / Ambient temperature 26: K2CO3, MeOH / 5 h / Ambient temperature 27: 1N HCl / tetrahydrofuran / 12 h / Ambient temperature 28: 49 percent / pyridine / 12 h / -20 °C View Scheme

1: NaIO4 / 24 h / Ambient temperature 2: p-TsOH / benzene / 24 h / Heating 3: 80 percent / mCPBA / CH2Cl2 / 24 h / -20 - 0 °C 4: iPr2NEt / CH2Cl2 / 0.5 h / -78 °C 5: 1) mCPBA, KHCO3, 2) citric acid / 1) CH2Cl2, -30 to -20 deg C, 1 h, 2) MeOH, 0 deg C to RT 6: NaIO4 / methanol; H2O / 0 deg C, 12 h; RT, 3 h 7: CHCl3 / Ambient temperature 8: 71 percent / LTBA / tetrahydrofuran / -78 to -40 deg C; -35 deg C, 4 h 9: 89 percent / nBu3P / tetrahydrofuran / 1 h / 0 - 20 °C 10: 85 percent / 30percent H2O2 / tetrahydrofuran / 18 h / 0 - 20 °C 11: I2, NaHCO3 / CH2Cl2 / 48 h / Ambient temperature 12: 90 percent / methanol / 4 h / 0 - 20 °C 13: LTBA / tetrahydrofuran / 3 h / 0 °C 14: pyridine / 2 h / 0 - 20 °C 15: 56 percent / CSA, dihydroquinone / benzene / 3 h / Heating 16: 1) mCPBA, 2) 2N HCl / 1) CH2Cl2, -30 to -25 deg C, 20 h, 2) THF, RT, 16 h 17: Me4NBH(OAc)3 / acetic acid; acetonitrile / 2 h / 0 °C 18: DDQ / dioxane / 4 h / 80 °C 19: 94 percent / Ag2O / acetonitrile / 24 h / Ambient temperature 20: 92 percent / MsCl, Et3N / CH2Cl2 / Ambient temperature 21: 47 percent / OsO4, DABCO / tetrahydrofuran / 24 h / -40 °C 22: 92 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 16 h / Ambient temperature 23: CH(NMe2)3 / 1 h / 100 °C 24: 2N HCl / tetrahydrofuran / 20 h / Ambient temperature 25: PCC / CH2Cl2 / 5 h / Ambient temperature 26: CH2Cl2 / 0.33 h / Ambient temperature 27: DBN / CH2Cl2 / 6 h / Ambient temperature 28: K2CO3, MeOH / 5 h / Ambient temperature 29: 1N HCl / tetrahydrofuran / 12 h / Ambient temperature 30: 49 percent / pyridine / 12 h / -20 °C View Scheme

1: I2, NaHCO3 / CH2Cl2 / 48 h / Ambient temperature 2: 90 percent / methanol / 4 h / 0 - 20 °C 3: LTBA / tetrahydrofuran / 3 h / 0 °C 4: pyridine / 2 h / 0 - 20 °C 5: 56 percent / CSA, dihydroquinone / benzene / 3 h / Heating 6: 1) mCPBA, 2) 2N HCl / 1) CH2Cl2, -30 to -25 deg C, 20 h, 2) THF, RT, 16 h 7: Me4NBH(OAc)3 / acetic acid; acetonitrile / 2 h / 0 °C 8: DDQ / dioxane / 4 h / 80 °C 9: 94 percent / Ag2O / acetonitrile / 24 h / Ambient temperature 10: 92 percent / MsCl, Et3N / CH2Cl2 / Ambient temperature 11: 47 percent / OsO4, DABCO / tetrahydrofuran / 24 h / -40 °C 12: 92 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 16 h / Ambient temperature 13: CH(NMe2)3 / 1 h / 100 °C 14: 2N HCl / tetrahydrofuran / 20 h / Ambient temperature 15: PCC / CH2Cl2 / 5 h / Ambient temperature 16: CH2Cl2 / 0.33 h / Ambient temperature 17: DBN / CH2Cl2 / 6 h / Ambient temperature 18: K2CO3, MeOH / 5 h / Ambient temperature 19: 1N HCl / tetrahydrofuran / 12 h / Ambient temperature 20: 49 percent / pyridine / 12 h / -20 °C View Scheme

1: NaIO4 / methanol; H2O / 0 deg C, 12 h; RT, 3 h 2: CHCl3 / Ambient temperature 3: 71 percent / LTBA / tetrahydrofuran / -78 to -40 deg C; -35 deg C, 4 h 4: 89 percent / nBu3P / tetrahydrofuran / 1 h / 0 - 20 °C 5: 85 percent / 30percent H2O2 / tetrahydrofuran / 18 h / 0 - 20 °C 6: I2, NaHCO3 / CH2Cl2 / 48 h / Ambient temperature 7: 90 percent / methanol / 4 h / 0 - 20 °C 8: LTBA / tetrahydrofuran / 3 h / 0 °C 9: pyridine / 2 h / 0 - 20 °C 10: 56 percent / CSA, dihydroquinone / benzene / 3 h / Heating 11: 1) mCPBA, 2) 2N HCl / 1) CH2Cl2, -30 to -25 deg C, 20 h, 2) THF, RT, 16 h 12: Me4NBH(OAc)3 / acetic acid; acetonitrile / 2 h / 0 °C 13: DDQ / dioxane / 4 h / 80 °C 14: 94 percent / Ag2O / acetonitrile / 24 h / Ambient temperature 15: 92 percent / MsCl, Et3N / CH2Cl2 / Ambient temperature 16: 47 percent / OsO4, DABCO / tetrahydrofuran / 24 h / -40 °C 17: 92 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 16 h / Ambient temperature 18: CH(NMe2)3 / 1 h / 100 °C 19: 2N HCl / tetrahydrofuran / 20 h / Ambient temperature 20: PCC / CH2Cl2 / 5 h / Ambient temperature 21: CH2Cl2 / 0.33 h / Ambient temperature 22: DBN / CH2Cl2 / 6 h / Ambient temperature 23: K2CO3, MeOH / 5 h / Ambient temperature 24: 1N HCl / tetrahydrofuran / 12 h / Ambient temperature 25: 49 percent / pyridine / 12 h / -20 °C View Scheme

1: 71 percent / LTBA / tetrahydrofuran / -78 to -40 deg C; -35 deg C, 4 h 2: 89 percent / nBu3P / tetrahydrofuran / 1 h / 0 - 20 °C 3: 85 percent / 30percent H2O2 / tetrahydrofuran / 18 h / 0 - 20 °C 4: I2, NaHCO3 / CH2Cl2 / 48 h / Ambient temperature 5: 90 percent / methanol / 4 h / 0 - 20 °C 6: LTBA / tetrahydrofuran / 3 h / 0 °C 7: pyridine / 2 h / 0 - 20 °C 8: 56 percent / CSA, dihydroquinone / benzene / 3 h / Heating 9: 1) mCPBA, 2) 2N HCl / 1) CH2Cl2, -30 to -25 deg C, 20 h, 2) THF, RT, 16 h 10: Me4NBH(OAc)3 / acetic acid; acetonitrile / 2 h / 0 °C 11: DDQ / dioxane / 4 h / 80 °C 12: 94 percent / Ag2O / acetonitrile / 24 h / Ambient temperature 13: 92 percent / MsCl, Et3N / CH2Cl2 / Ambient temperature 14: 47 percent / OsO4, DABCO / tetrahydrofuran / 24 h / -40 °C 15: 92 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 16 h / Ambient temperature 16: CH(NMe2)3 / 1 h / 100 °C 17: 2N HCl / tetrahydrofuran / 20 h / Ambient temperature 18: PCC / CH2Cl2 / 5 h / Ambient temperature 19: CH2Cl2 / 0.33 h / Ambient temperature 20: DBN / CH2Cl2 / 6 h / Ambient temperature 21: K2CO3, MeOH / 5 h / Ambient temperature 22: 1N HCl / tetrahydrofuran / 12 h / Ambient temperature 23: 49 percent / pyridine / 12 h / -20 °C View Scheme