1: (PhO)2P(O)N3, Et3N, 4 Angstroem molecular sieves / toluene / 2 h / 70 °C 2: 1 h / 23 °C 3: H2, Rh<(COD)-(R,R)-DIPAMP>(+)*BF4(-) / 16 h / 23 °C / 2280 Torr 4: 90 percent / diisobutylaluminum hydride / CH2Cl2 / 1 h / -78 °C 5: 61 percent / HOAc / 18 h / 23 °C 6: 87 percent / Cs2CO3 / dimethylformamide / 1 h / 23 °C 7: diisobutylaluminum hydride / toluene / 5 h / -78 °C 8: KF*2H2O / methanol / 0.33 h / 23 °C 9: CH3SO3H, 3 Angstroem molecular sieves / CH2Cl2 / 5 h / 23 °C 10: 72 percent / Et3N, DMAP / CH2Cl2 / 6 h / 23 °C 11: 89 percent / DMAP / CH2Cl2 / 13 h / 23 °C 12: 92 percent / i-Pr2NEt / CH2Cl2 / 0.33 h / 23 °C 13: 1.) Bu3SnH, PdCl2(PPh3)2, HOAc, 2.) NaBH3CN, HOAc / 1.) CH2Cl2, 23 deg C, 15 min, 2.) CH3CN, 23 deg C, 30 min 14: 83 percent / PdCl2(PPh3)2, LiCl / dimethylformamide / 2 h / 80 °C 15: (PhSeO)2O / CH2Cl2 / 0.25 h / 23 °C 16: Bu4NF / tetrahydrofuran / 0.17 h / 23 °C 17: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 18: 0.5 h / -40 °C 19: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 20: 23 °C 21: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 22: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 23: 82 percent / silica gel / ethanol / 23 °C 24: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 25: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: 61 percent / HOAc / 18 h / 23 °C 2: 87 percent / Cs2CO3 / dimethylformamide / 1 h / 23 °C 3: diisobutylaluminum hydride / toluene / 5 h / -78 °C 4: KF*2H2O / methanol / 0.33 h / 23 °C 5: CH3SO3H, 3 Angstroem molecular sieves / CH2Cl2 / 5 h / 23 °C 6: 72 percent / Et3N, DMAP / CH2Cl2 / 6 h / 23 °C 7: 89 percent / DMAP / CH2Cl2 / 13 h / 23 °C 8: 92 percent / i-Pr2NEt / CH2Cl2 / 0.33 h / 23 °C 9: 1.) Bu3SnH, PdCl2(PPh3)2, HOAc, 2.) NaBH3CN, HOAc / 1.) CH2Cl2, 23 deg C, 15 min, 2.) CH3CN, 23 deg C, 30 min 10: 83 percent / PdCl2(PPh3)2, LiCl / dimethylformamide / 2 h / 80 °C 11: (PhSeO)2O / CH2Cl2 / 0.25 h / 23 °C 12: Bu4NF / tetrahydrofuran / 0.17 h / 23 °C 13: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 14: 0.5 h / -40 °C 15: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 16: 23 °C 17: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 18: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 19: 82 percent / silica gel / ethanol / 23 °C 20: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 21: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: 90 percent / diisobutylaluminum hydride / CH2Cl2 / 1 h / -78 °C 2: 61 percent / HOAc / 18 h / 23 °C 3: 87 percent / Cs2CO3 / dimethylformamide / 1 h / 23 °C 4: diisobutylaluminum hydride / toluene / 5 h / -78 °C 5: KF*2H2O / methanol / 0.33 h / 23 °C 6: CH3SO3H, 3 Angstroem molecular sieves / CH2Cl2 / 5 h / 23 °C 7: 72 percent / Et3N, DMAP / CH2Cl2 / 6 h / 23 °C 8: 89 percent / DMAP / CH2Cl2 / 13 h / 23 °C 9: 92 percent / i-Pr2NEt / CH2Cl2 / 0.33 h / 23 °C 10: 1.) Bu3SnH, PdCl2(PPh3)2, HOAc, 2.) NaBH3CN, HOAc / 1.) CH2Cl2, 23 deg C, 15 min, 2.) CH3CN, 23 deg C, 30 min 11: 83 percent / PdCl2(PPh3)2, LiCl / dimethylformamide / 2 h / 80 °C 12: (PhSeO)2O / CH2Cl2 / 0.25 h / 23 °C 13: Bu4NF / tetrahydrofuran / 0.17 h / 23 °C 14: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 15: 0.5 h / -40 °C 16: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 17: 23 °C 18: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 19: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 20: 82 percent / silica gel / ethanol / 23 °C 21: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 22: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 2: 0.5 h / -40 °C 3: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 4: 23 °C 5: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 6: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 7: 82 percent / silica gel / ethanol / 23 °C 8: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 9: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: CH3SO3H, 3 Angstroem molecular sieves / CH2Cl2 / 5 h / 23 °C 2: 72 percent / Et3N, DMAP / CH2Cl2 / 6 h / 23 °C 3: 89 percent / DMAP / CH2Cl2 / 13 h / 23 °C 4: 92 percent / i-Pr2NEt / CH2Cl2 / 0.33 h / 23 °C 5: 1.) Bu3SnH, PdCl2(PPh3)2, HOAc, 2.) NaBH3CN, HOAc / 1.) CH2Cl2, 23 deg C, 15 min, 2.) CH3CN, 23 deg C, 30 min 6: 83 percent / PdCl2(PPh3)2, LiCl / dimethylformamide / 2 h / 80 °C 7: (PhSeO)2O / CH2Cl2 / 0.25 h / 23 °C 8: Bu4NF / tetrahydrofuran / 0.17 h / 23 °C 9: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 10: 0.5 h / -40 °C 11: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 12: 23 °C 13: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 14: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 15: 82 percent / silica gel / ethanol / 23 °C 16: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 17: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: 72 percent / Et3N, DMAP / CH2Cl2 / 6 h / 23 °C 2: 89 percent / DMAP / CH2Cl2 / 13 h / 23 °C 3: 92 percent / i-Pr2NEt / CH2Cl2 / 0.33 h / 23 °C 4: 1.) Bu3SnH, PdCl2(PPh3)2, HOAc, 2.) NaBH3CN, HOAc / 1.) CH2Cl2, 23 deg C, 15 min, 2.) CH3CN, 23 deg C, 30 min 5: 83 percent / PdCl2(PPh3)2, LiCl / dimethylformamide / 2 h / 80 °C 6: (PhSeO)2O / CH2Cl2 / 0.25 h / 23 °C 7: Bu4NF / tetrahydrofuran / 0.17 h / 23 °C 8: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 9: 0.5 h / -40 °C 10: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 11: 23 °C 12: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 13: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 14: 82 percent / silica gel / ethanol / 23 °C 15: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 16: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: 82 percent / silica gel / ethanol / 23 °C 2: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 3: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 2: 82 percent / silica gel / ethanol / 23 °C 3: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 4: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: 87 percent / Cs2CO3 / dimethylformamide / 1 h / 23 °C 2: diisobutylaluminum hydride / toluene / 5 h / -78 °C 3: KF*2H2O / methanol / 0.33 h / 23 °C 4: CH3SO3H, 3 Angstroem molecular sieves / CH2Cl2 / 5 h / 23 °C 5: 72 percent / Et3N, DMAP / CH2Cl2 / 6 h / 23 °C 6: 89 percent / DMAP / CH2Cl2 / 13 h / 23 °C 7: 92 percent / i-Pr2NEt / CH2Cl2 / 0.33 h / 23 °C 8: 1.) Bu3SnH, PdCl2(PPh3)2, HOAc, 2.) NaBH3CN, HOAc / 1.) CH2Cl2, 23 deg C, 15 min, 2.) CH3CN, 23 deg C, 30 min 9: 83 percent / PdCl2(PPh3)2, LiCl / dimethylformamide / 2 h / 80 °C 10: (PhSeO)2O / CH2Cl2 / 0.25 h / 23 °C 11: Bu4NF / tetrahydrofuran / 0.17 h / 23 °C 12: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 13: 0.5 h / -40 °C 14: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 15: 23 °C 16: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 17: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 18: 82 percent / silica gel / ethanol / 23 °C 19: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 20: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme

1: (PhSeO)2O / CH2Cl2 / 0.25 h / 23 °C 2: Bu4NF / tetrahydrofuran / 0.17 h / 23 °C 3: 91 percent / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, DMAP / CH2Cl2 / 0.5 h / 23 °C 4: 0.5 h / -40 °C 5: 1.) i-Pr2NEt, 2.) tert-butyl alcohol, N-tert-butyl-N',N',N'',N''-tetramethylguanidine / 1.) 0 deg C, 30 min, 2.) 23 deg C 6: 23 °C 7: 84 percent / PdCl2(PPh3)2, Bu3SnH, HOAc / CH2Cl2 / 0.08 h / 23 °C 8: 70 percent / <N-methylpyridinium-4-carboxaldehyde>iodide, 1,8-diazabicyclo<6.4.0>undec-7-ene, DMF / CH2Cl2 / 0.67 h / 23 °C 9: 82 percent / silica gel / ethanol / 23 °C 10: aq. CF3COOH / tetrahydrofuran / 9 h / 23 °C 11: aq. AgNO3 / acetonitrile / 11 h / 23 °C View Scheme