potassium hydroxide in ethanol 3 h; Heating;

1: NaBH4 2: DMAP 3: K2CO3 / methanol 4: MnO2 / (COCl)2, DMSO and Et3N 5: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 6: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 7: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 8: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 9: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 10: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 11: MeOH / PPTS / 0.08 h / Heating 12: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 13: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 14: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 15: PCC, sodium acetate / CH2Cl2 / 2.5 h 16: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 17: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 18: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: 1.) sodium hydride / 1.) DME, RT, 10 min; 2.) DME, RT, overnight 2: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 3: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 4: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 5: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 6: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 7: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 8: MeOH / PPTS / 0.08 h / Heating 9: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 10: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 11: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 12: PCC, sodium acetate / CH2Cl2 / 2.5 h 13: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 14: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 15: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: DMAP 2: K2CO3 / methanol 3: MnO2 / (COCl)2, DMSO and Et3N 4: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 5: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 6: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 7: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 8: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 9: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 10: MeOH / PPTS / 0.08 h / Heating 11: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 12: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 13: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 14: PCC, sodium acetate / CH2Cl2 / 2.5 h 15: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 16: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 17: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: 86 percent / DIBAH / CH2Cl2; hexane / 0.17 h / -78 °C 2: 1.) sodium hydride / 1.) DME, RT, 10 min; 2.) DME, RT, overnight 3: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 4: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 5: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 6: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 7: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 8: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 9: MeOH / PPTS / 0.08 h / Heating 10: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 11: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 12: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 13: PCC, sodium acetate / CH2Cl2 / 2.5 h 14: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 15: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 16: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: 2.) acetyl chloride / 1.) THF, -10 deg C, 30 min; 2.) -10 deg C, 5 min. 2: 86 percent / DIBAH / CH2Cl2; hexane / 0.17 h / -78 °C 3: 1.) sodium hydride / 1.) DME, RT, 10 min; 2.) DME, RT, overnight 4: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 5: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 6: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 7: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 8: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 9: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 10: MeOH / PPTS / 0.08 h / Heating 11: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 12: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 13: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 14: PCC, sodium acetate / CH2Cl2 / 2.5 h 15: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 16: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 17: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 2: 2.) acetyl chloride / 1.) THF, -10 deg C, 30 min; 2.) -10 deg C, 5 min. 3: 86 percent / DIBAH / CH2Cl2; hexane / 0.17 h / -78 °C 4: 1.) sodium hydride / 1.) DME, RT, 10 min; 2.) DME, RT, overnight 5: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 6: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 7: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 8: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 9: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 10: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 11: MeOH / PPTS / 0.08 h / Heating 12: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 13: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 14: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 15: PCC, sodium acetate / CH2Cl2 / 2.5 h 16: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 17: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 18: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: 100 percent / K2CO3 / methanol / -20 °C 2: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 3: 2.) acetyl chloride / 1.) THF, -10 deg C, 30 min; 2.) -10 deg C, 5 min. 4: 86 percent / DIBAH / CH2Cl2; hexane / 0.17 h / -78 °C 5: 1.) sodium hydride / 1.) DME, RT, 10 min; 2.) DME, RT, overnight 6: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 7: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 8: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 9: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 10: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 11: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 12: MeOH / PPTS / 0.08 h / Heating 13: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 14: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 15: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 16: PCC, sodium acetate / CH2Cl2 / 2.5 h 17: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 18: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 19: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: 1.) TMEDA, n-BuLi 2.) ClTi(O-iPr)3 / 1.) ether, hexane, -78 deg C, 1 h 2.) ether, hexane, -78 deg C, 2 h then -10 deg C, 1.5 h 2: LiAlH4 / tetrahydrofuran / 0.5 h / 0 °C / Heating 3: PPTS / CH2Cl2 / 0.08 h / Ambient temperature 4: 1.) B2H6, 2-methyl-2-butene 3.) 3M NaOH, 30percent aq. H2O2 / 1.) THF, -10 deg C, 2 h 2.) THF, 0 deg C, 30 min; 3.) THF, RT, 30 min. 5: 90 percent / triphenylphosphine, imidazole, I2 / tetrahydrofuran; acetonitrile / 0.5 h / -10 °C 6: 1.) NaH / 1.) DMSO, RT, 30 min; 2.) DMSO, overnight 7: MeOH / PPTS / 0.08 h / Heating 8: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 9: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 10: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 11: PCC, sodium acetate / CH2Cl2 / 2.5 h 12: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 13: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 14: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme

1: 1.) DMSO, (COCl)2 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min; 2.) CH2Cl2, -78 to 0 deg C 2: 35 percent / K2CO3, 18-crown-6 / toluene / 80 °C 3: H2O / PPTS / tetrahydrofuran / 1.5 h / Heating 4: PCC, sodium acetate / CH2Cl2 / 2.5 h 5: 1.) LDA, 1,10-phenanthroline / 1.) THF, -78 deg C, 15 min; 2.) THF, -20 deg C, 5 min. 6: 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulphonate / copper(II) iodide / acetonitrile / 4 h / 55 - 58 °C 7: 90 percent / KOH / aq. ethanol / 3 h / Heating View Scheme