Celite; silver carbonate in toluene T=95°C; 2 h;

boron tribromide in dichloromethane T=-23°C; 5 h;

toluene-4-sulfonic acid in benzene 1.08333 h; Ambient temperature;

1: 32 g / acetic acid / 1 h / 25 °C 2: 88 percent / 4percent KOH / methanol; diethyl ether / 2 h / 25 °C 3: 30percent H2O2 / tetrahydrofuran; H2O / 2.5 h / 25 °C 4: tetrahydrofuran; H2O / 2 h / 55 °C 5: 20.6 g / Jones reagent / tetrahydrofuran; H2O; acetone / 0.25 h 6: 1.) THF, -20 deg C, 30 min, 2.) -78 deg C 7: 38 g / Et3N / CH2Cl2 / 0.5 h / -5 °C 8: 28.09 g / DBU / benzene / 1 h / 25 °C 9: 78 percent / H2 / 10percent Pd/C / benzene; pyridine / 0.67 h / 25 °C 10: Et3N, Na2SO4 / ethanol / 7 h / 25 °C 11: 5.3 g / LDA / tetrahydrofuran; hexane / -78 deg C -> 0 deg C, 1 h; 0 deg C, 4 h 12: 100 percent / Li, NH3 liq. / tetrahydrofuran / 0.5 h 13: 1 mg / 4-(dimethylamino)pyridine / pyridine / 16 h / 25 °C 14: 2.8 g / pyridine / 8 h / 0 °C 15: 1.8 g / DBU / pyridine / 3 h / Heating 16: 1.44 g / acetic acid; tetrahydrofuran; H2O / 8 h / 25 °C 17: 65 percent / pyridinium chlorochromate / CH2Cl2 / 4 h / 25 °C 18: 1.) NaH, 2.) n-BuLi / 1.) THF, 0 deg C, 10 min, 2.) THF-hexane, 0 deg C, 10 min, 3.) 0 deg C, 15 min 19: 34 mg / Zn(BH4)2 / diethyl ether / 1 h / 25 °C 20: 32 mg / p-toluenesulfonic acid monohydrate / benzene / 0.25 h / 25 °C View Scheme

1: 1.) THF, -20 deg C, 30 min, 2.) -78 deg C 2: 38 g / Et3N / CH2Cl2 / 0.5 h / -5 °C 3: 28.09 g / DBU / benzene / 1 h / 25 °C 4: 78 percent / H2 / 10percent Pd/C / benzene; pyridine / 0.67 h / 25 °C 5: Et3N, Na2SO4 / ethanol / 7 h / 25 °C 6: 5.3 g / LDA / tetrahydrofuran; hexane / -78 deg C -> 0 deg C, 1 h; 0 deg C, 4 h 7: 100 percent / Li, NH3 liq. / tetrahydrofuran / 0.5 h 8: 1 mg / 4-(dimethylamino)pyridine / pyridine / 16 h / 25 °C 9: 2.8 g / pyridine / 8 h / 0 °C 10: 1.8 g / DBU / pyridine / 3 h / Heating 11: 1.44 g / acetic acid; tetrahydrofuran; H2O / 8 h / 25 °C 12: 65 percent / pyridinium chlorochromate / CH2Cl2 / 4 h / 25 °C 13: 1.) NaH, 2.) n-BuLi / 1.) THF, 0 deg C, 10 min, 2.) THF-hexane, 0 deg C, 10 min, 3.) 0 deg C, 15 min 14: 34 mg / Zn(BH4)2 / diethyl ether / 1 h / 25 °C 15: 32 mg / p-toluenesulfonic acid monohydrate / benzene / 0.25 h / 25 °C View Scheme

1: 18.67 g / Aureobasidium pullulans NRRL Y-12610 / H2O / 72 °C 2: 99 percent / 1.) NaH / dimethylsulfoxide / 1.) RT, 30 min, 2.) RT, 3 h 3: 32 g / acetic acid / 1 h / 25 °C 4: 88 percent / 4percent KOH / methanol; diethyl ether / 2 h / 25 °C 5: 30percent H2O2 / tetrahydrofuran; H2O / 2.5 h / 25 °C 6: tetrahydrofuran; H2O / 2 h / 55 °C 7: 20.6 g / Jones reagent / tetrahydrofuran; H2O; acetone / 0.25 h 8: 1.) THF, -20 deg C, 30 min, 2.) -78 deg C 9: 38 g / Et3N / CH2Cl2 / 0.5 h / -5 °C 10: 28.09 g / DBU / benzene / 1 h / 25 °C 11: 78 percent / H2 / 10percent Pd/C / benzene; pyridine / 0.67 h / 25 °C 12: Et3N, Na2SO4 / ethanol / 7 h / 25 °C 13: 5.3 g / LDA / tetrahydrofuran; hexane / -78 deg C -> 0 deg C, 1 h; 0 deg C, 4 h 14: 100 percent / Li, NH3 liq. / tetrahydrofuran / 0.5 h 15: 1 mg / 4-(dimethylamino)pyridine / pyridine / 16 h / 25 °C 16: 2.8 g / pyridine / 8 h / 0 °C 17: 1.8 g / DBU / pyridine / 3 h / Heating 18: 1.44 g / acetic acid; tetrahydrofuran; H2O / 8 h / 25 °C 19: 65 percent / pyridinium chlorochromate / CH2Cl2 / 4 h / 25 °C 20: 1.) NaH, 2.) n-BuLi / 1.) THF, 0 deg C, 10 min, 2.) THF-hexane, 0 deg C, 10 min, 3.) 0 deg C, 15 min 21: 34 mg / Zn(BH4)2 / diethyl ether / 1 h / 25 °C 22: 32 mg / p-toluenesulfonic acid monohydrate / benzene / 0.25 h / 25 °C View Scheme

1: 99 percent / 1.) NaH / dimethylsulfoxide / 1.) RT, 30 min, 2.) RT, 3 h 2: 32 g / acetic acid / 1 h / 25 °C 3: 88 percent / 4percent KOH / methanol; diethyl ether / 2 h / 25 °C 4: 30percent H2O2 / tetrahydrofuran; H2O / 2.5 h / 25 °C 5: tetrahydrofuran; H2O / 2 h / 55 °C 6: 20.6 g / Jones reagent / tetrahydrofuran; H2O; acetone / 0.25 h 7: 1.) THF, -20 deg C, 30 min, 2.) -78 deg C 8: 38 g / Et3N / CH2Cl2 / 0.5 h / -5 °C 9: 28.09 g / DBU / benzene / 1 h / 25 °C 10: 78 percent / H2 / 10percent Pd/C / benzene; pyridine / 0.67 h / 25 °C 11: Et3N, Na2SO4 / ethanol / 7 h / 25 °C 12: 5.3 g / LDA / tetrahydrofuran; hexane / -78 deg C -> 0 deg C, 1 h; 0 deg C, 4 h 13: 100 percent / Li, NH3 liq. / tetrahydrofuran / 0.5 h 14: 1 mg / 4-(dimethylamino)pyridine / pyridine / 16 h / 25 °C 15: 2.8 g / pyridine / 8 h / 0 °C 16: 1.8 g / DBU / pyridine / 3 h / Heating 17: 1.44 g / acetic acid; tetrahydrofuran; H2O / 8 h / 25 °C 18: 65 percent / pyridinium chlorochromate / CH2Cl2 / 4 h / 25 °C 19: 1.) NaH, 2.) n-BuLi / 1.) THF, 0 deg C, 10 min, 2.) THF-hexane, 0 deg C, 10 min, 3.) 0 deg C, 15 min 20: 34 mg / Zn(BH4)2 / diethyl ether / 1 h / 25 °C 21: 32 mg / p-toluenesulfonic acid monohydrate / benzene / 0.25 h / 25 °C View Scheme

1: 1.) HF; 2.) 2-methoxypropene / 2.) pyridinium p-toluenesulfonate / 1.) H2O, MeCN, r.t., 1.75 h; 2.) CH2Cl2, 0 deg C, 40 min 2: 1.) (COCl)2; 2.Et3N / 1.) DMSO, CH2Cl2, -78 deg C, 15 min; 2.) -78 deg C, 5 min 3: 80 percent / L-Selectride / tetrahydrofuran / -78 deg C, 1 h; -43 deg C, 12 h 4: 99 percent / Et3N / DMAP / CH2Cl2 / 68 h / Ambient temperature 5: 92 percent / Bu4NF / tetrahydrofuran / 1.75 h / Ambient temperature 6: 1.) (COCl)2; 2.) Et3N / 1.) DMSO,CH2Cl2, -78 deg C, 20 min; 2.) -78 deg C, 10 min, -78 deg C -> r.t., 30 min 7: 88 percent / 1.3N HCl / tetrahydrofuran / 2 h / Ambient temperature 8: 61 percent / Ag2CO3/Celite / toluene / 2 h / 95 °C View Scheme

1: 85 percent / C8K, TiCl3 / 1,2-dimethoxy-ethane / r.t., 5 h; reflux, 3 h 2: 1.) HF; 2.) 2-methoxypropene / 2.) pyridinium p-toluenesulfonate / 1.) H2O, MeCN, r.t., 1.75 h; 2.) CH2Cl2, 0 deg C, 40 min 3: 1.) (COCl)2; 2.Et3N / 1.) DMSO, CH2Cl2, -78 deg C, 15 min; 2.) -78 deg C, 5 min 4: 80 percent / L-Selectride / tetrahydrofuran / -78 deg C, 1 h; -43 deg C, 12 h 5: 99 percent / Et3N / DMAP / CH2Cl2 / 68 h / Ambient temperature 6: 92 percent / Bu4NF / tetrahydrofuran / 1.75 h / Ambient temperature 7: 1.) (COCl)2; 2.) Et3N / 1.) DMSO,CH2Cl2, -78 deg C, 20 min; 2.) -78 deg C, 10 min, -78 deg C -> r.t., 30 min 8: 88 percent / 1.3N HCl / tetrahydrofuran / 2 h / Ambient temperature 9: 61 percent / Ag2CO3/Celite / toluene / 2 h / 95 °C View Scheme

1: 50 percent / (Ph3P)3RhCl / toluene; acetonitrile / 2.5 h / Heating 2: 1.) LDA / 1.) Et2O, -78 deg C, 1 h; 2.) -78 deg C, 10 min 3: 96 percent / i-Pr2NH / DMAP / diethyl ether / 36 h / Ambient temperature 4: 1.) O3; 2.) Ph3P / 1.) CH2Cl2, -78 deg C; 2.) -78 deg C, 20 min, r.t., 8 h 5: 85 percent / C8K, TiCl3 / 1,2-dimethoxy-ethane / r.t., 5 h; reflux, 3 h 6: 1.) HF; 2.) 2-methoxypropene / 2.) pyridinium p-toluenesulfonate / 1.) H2O, MeCN, r.t., 1.75 h; 2.) CH2Cl2, 0 deg C, 40 min 7: 1.) (COCl)2; 2.Et3N / 1.) DMSO, CH2Cl2, -78 deg C, 15 min; 2.) -78 deg C, 5 min 8: 80 percent / L-Selectride / tetrahydrofuran / -78 deg C, 1 h; -43 deg C, 12 h 9: 99 percent / Et3N / DMAP / CH2Cl2 / 68 h / Ambient temperature 10: 92 percent / Bu4NF / tetrahydrofuran / 1.75 h / Ambient temperature 11: 1.) (COCl)2; 2.) Et3N / 1.) DMSO,CH2Cl2, -78 deg C, 20 min; 2.) -78 deg C, 10 min, -78 deg C -> r.t., 30 min 12: 88 percent / 1.3N HCl / tetrahydrofuran / 2 h / Ambient temperature 13: 61 percent / Ag2CO3/Celite / toluene / 2 h / 95 °C View Scheme