1.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 3 h / 25 °C 1.2: 59 percent / DMAP / tetrahydrofuran; toluene / 12 h / 25 °C 2.1: hydroquinone; nBu3SnH / Mo(CO)3(tBuNC)3 / tetrahydrofuran / 12 h / 55 °C 2.2: 54 percent / I2 / CH2Cl2 / 25 °C 3.1: 90 percent / CuI / Pd(PPh3)4 / toluene / 8 h / 80 °C 4.1: 69 percent / Me2BBr / CH2Cl2 / 2 h / -78 °C 5.1: 85 percent / TEMPO; TCCA / CH2Cl2 / 1 h / 25 °C 6.1: NaClO2; NaH2PO4; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 0.5 h / 25 °C 7.1: NaBH4; CeCl3*7H2O / methanol / 1 h / 0 °C View Scheme

1: 90 percent / CuI / Pd(PPh3)4 / toluene / 8 h / 80 °C 2: 69 percent / Me2BBr / CH2Cl2 / 2 h / -78 °C 3: 85 percent / TEMPO; TCCA / CH2Cl2 / 1 h / 25 °C 4: NaClO2; NaH2PO4; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 0.5 h / 25 °C 5: NaBH4; CeCl3*7H2O / methanol / 1 h / 0 °C View Scheme

1.1: 89 percent / DDQ / H2O; CH2Cl2 / 0.5 h / 25 °C / pH 7.0 2.1: 94 percent / TEMPO; bis(acetoxy)iodobenzene / CH2Cl2 / 2 h / 25 °C 3.1: BF3*OEt2 / tetrahydrofuran / 1 h / -78 °C 4.1: 86 percent / iPr2NEt / CH2Cl2 / 12 h / 25 °C 5.1: 88 percent / HF*pyridine / tetrahydrofuran / 12 h / 25 °C 6.1: 83 percent / CF3COOH / CH2Cl2 / 3 h / 0 °C 7.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 3 h / 25 °C 7.2: 59 percent / DMAP / tetrahydrofuran; toluene / 12 h / 25 °C 8.1: hydroquinone; nBu3SnH / Mo(CO)3(tBuNC)3 / tetrahydrofuran / 12 h / 55 °C 8.2: 54 percent / I2 / CH2Cl2 / 25 °C 9.1: 90 percent / CuI / Pd(PPh3)4 / toluene / 8 h / 80 °C 10.1: 69 percent / Me2BBr / CH2Cl2 / 2 h / -78 °C 11.1: 85 percent / TEMPO; TCCA / CH2Cl2 / 1 h / 25 °C 12.1: NaClO2; NaH2PO4; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 0.5 h / 25 °C 13.1: NaBH4; CeCl3*7H2O / methanol / 1 h / 0 °C View Scheme

1.1: 83 percent / CF3COOH / CH2Cl2 / 3 h / 0 °C 2.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 3 h / 25 °C 2.2: 59 percent / DMAP / tetrahydrofuran; toluene / 12 h / 25 °C 3.1: hydroquinone; nBu3SnH / Mo(CO)3(tBuNC)3 / tetrahydrofuran / 12 h / 55 °C 3.2: 54 percent / I2 / CH2Cl2 / 25 °C 4.1: 90 percent / CuI / Pd(PPh3)4 / toluene / 8 h / 80 °C 5.1: 69 percent / Me2BBr / CH2Cl2 / 2 h / -78 °C 6.1: 85 percent / TEMPO; TCCA / CH2Cl2 / 1 h / 25 °C 7.1: NaClO2; NaH2PO4; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 0.5 h / 25 °C 8.1: NaBH4; CeCl3*7H2O / methanol / 1 h / 0 °C View Scheme

1.1: 86 percent / iPr2NEt / CH2Cl2 / 12 h / 25 °C 2.1: 88 percent / HF*pyridine / tetrahydrofuran / 12 h / 25 °C 3.1: 83 percent / CF3COOH / CH2Cl2 / 3 h / 0 °C 4.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 3 h / 25 °C 4.2: 59 percent / DMAP / tetrahydrofuran; toluene / 12 h / 25 °C 5.1: hydroquinone; nBu3SnH / Mo(CO)3(tBuNC)3 / tetrahydrofuran / 12 h / 55 °C 5.2: 54 percent / I2 / CH2Cl2 / 25 °C 6.1: 90 percent / CuI / Pd(PPh3)4 / toluene / 8 h / 80 °C 7.1: 69 percent / Me2BBr / CH2Cl2 / 2 h / -78 °C 8.1: 85 percent / TEMPO; TCCA / CH2Cl2 / 1 h / 25 °C 9.1: NaClO2; NaH2PO4; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 0.5 h / 25 °C 10.1: NaBH4; CeCl3*7H2O / methanol / 1 h / 0 °C View Scheme

1.1: 88 percent / HF*pyridine / tetrahydrofuran / 12 h / 25 °C 2.1: 83 percent / CF3COOH / CH2Cl2 / 3 h / 0 °C 3.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 3 h / 25 °C 3.2: 59 percent / DMAP / tetrahydrofuran; toluene / 12 h / 25 °C 4.1: hydroquinone; nBu3SnH / Mo(CO)3(tBuNC)3 / tetrahydrofuran / 12 h / 55 °C 4.2: 54 percent / I2 / CH2Cl2 / 25 °C 5.1: 90 percent / CuI / Pd(PPh3)4 / toluene / 8 h / 80 °C 6.1: 69 percent / Me2BBr / CH2Cl2 / 2 h / -78 °C 7.1: 85 percent / TEMPO; TCCA / CH2Cl2 / 1 h / 25 °C 8.1: NaClO2; NaH2PO4; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 0.5 h / 25 °C 9.1: NaBH4; CeCl3*7H2O / methanol / 1 h / 0 °C View Scheme

1.1: 94 percent / DIBAL-H / CH2Cl2 / 1.25 h / -78 - 0 °C 2.1: 96 percent / triphenylphosphine; iodine; imidazole / acetonitrile; diethyl ether / 20 °C 3.1: LiCl; diisopropylamine; n-butyllithium / tetrahydrofuran; petroleum ether / 1.33 h / -78 - 20 °C 3.2: 93 percent / tetrahydrofuran; various solvent(s) / 40 h / 0 °C 4.1: 93 percent / diisopropylamine; n-butyllithium; borane-ammonium complex / tetrahydrofuran; petroleum ether / 2.17 h / 0 - 20 °C 5.1: 95 percent / triphenylphosphine; imidazole; iodine / diethyl ether; acetonitrile / 0.17 h / 20 °C 6.1: tert-butyllithium; ZnCl2 / diethyl ether; petroleum ether / 1 h / 20 °C 6.2: 58 percent / Pd(PPh3)4 / diethyl ether; various solvent(s) / 16 h 7.1: 87 percent / TBAF / tetrahydrofuran / 20 h / 20 °C 8.1: 86 percent / H2 / Rh[(nbd)dppb]BF4 / CH2Cl2 / 4 h / 36201.3 Torr 9.1: 100 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 10.1: 93 percent / DDQ / CH2Cl2 / 1 h / 20 °C / pH 7 11.1: triethylamine / CH2Cl2 / 1.5 h / 20 °C 12.1: HF / acetonitrile / 3 h / 20 °C 13.1: 98 percent / potassium carbonate / methanol / 0.75 h 14.1: 92 percent / lithium perchlorate / acetonitrile / 24 h / 70 °C 15.1: 81 percent / diisopropylethylamine / CH2Cl2 / 28 h / 20 °C 16.1: DIBAL-H / CH2Cl2; petroleum ether / 1 h / -78 °C 17.1: 2-methyl-2-butene; NaH2PO4; NaClO2 / H2O; 2-methyl-propan-2-ol / 1 h / 0 °C 18.1: K2CO3 / dimethylformamide / 3.5 h / 20 °C 19.1: H2 / Pd/C / tetrahydrofuran; ethanol / 3 h / 10343.2 Torr 20.1: 89 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 21.1: 86 percent / potassium tert-butoxide / tetrahydrofuran / 18 h / -70 - 20 °C 22.1: 91 percent / c. HCl / methanol / 0.5 h / 20 °C 23.1: 94 percent / Pd(PPh3)4; CuI; triethylamine / 12 h / 20 °C 24.1: 94 percent / triethylamine; DAMP / CH2Cl2 / 2 h / 20 °C 25.1: PdCl2(PPh3)2; Bu3SnH / CH2Cl2 25.2: I2 / CH2Cl2 / 0 °C 25.3: potassium carbonate; methanol / -25 - 0 °C 26.1: 97 percent / Pd(PPh3)4; CuI / benzene / 4 h / 80 °C 27.1: 85 percent / P2O5 / 12 h / 20 °C 28.1: 77 percent / trisdimethylamino sulfonyl trimethylsilyldifluoride; water / dimethylformamide / 26 h / 0 °C 29.1: 84 percent / aq. NaOH / tetrahydrofuran / 30 h / 20 °C 30.1: 2,4,6-trichlorobenzoyl chloride; triethylamine; DMAP / tetrahydrofuran; toluene / 25.5 h / 0 - 20 °C 31.1: Me2BBr / CH2Cl2 / 1 h / -78 °C View Scheme

1.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1.5 h / 20 °C 2.1: 94 percent / triphenylphosphine / CH2Cl2 / 0.67 h / -78 - 0 °C 3.1: n-butyllithium / tetrahydrofuran; petroleum ether / 1 h / -25 °C 3.2: 97 percent / tetrahydrofuran; various solvent(s) / 1 h / 20 °C 4.1: Cp2ZrHCl / CH2Cl2 / 2 h 4.2: 89 percent / I2 / CH2Cl2; CCl4 5.1: tert-butyllithium; ZnCl2 / diethyl ether; petroleum ether / 1 h / 20 °C 5.2: 58 percent / Pd(PPh3)4 / diethyl ether; various solvent(s) / 16 h 6.1: 87 percent / TBAF / tetrahydrofuran / 20 h / 20 °C 7.1: 86 percent / H2 / Rh[(nbd)dppb]BF4 / CH2Cl2 / 4 h / 36201.3 Torr 8.1: 100 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 9.1: 93 percent / DDQ / CH2Cl2 / 1 h / 20 °C / pH 7 10.1: triethylamine / CH2Cl2 / 1.5 h / 20 °C 11.1: HF / acetonitrile / 3 h / 20 °C 12.1: 98 percent / potassium carbonate / methanol / 0.75 h 13.1: 92 percent / lithium perchlorate / acetonitrile / 24 h / 70 °C 14.1: 81 percent / diisopropylethylamine / CH2Cl2 / 28 h / 20 °C 15.1: DIBAL-H / CH2Cl2; petroleum ether / 1 h / -78 °C 16.1: 2-methyl-2-butene; NaH2PO4; NaClO2 / H2O; 2-methyl-propan-2-ol / 1 h / 0 °C 17.1: K2CO3 / dimethylformamide / 3.5 h / 20 °C 18.1: H2 / Pd/C / tetrahydrofuran; ethanol / 3 h / 10343.2 Torr 19.1: 89 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 20.1: 86 percent / potassium tert-butoxide / tetrahydrofuran / 18 h / -70 - 20 °C 21.1: 91 percent / c. HCl / methanol / 0.5 h / 20 °C 22.1: 94 percent / Pd(PPh3)4; CuI; triethylamine / 12 h / 20 °C 23.1: 94 percent / triethylamine; DAMP / CH2Cl2 / 2 h / 20 °C 24.1: PdCl2(PPh3)2; Bu3SnH / CH2Cl2 24.2: I2 / CH2Cl2 / 0 °C 24.3: potassium carbonate; methanol / -25 - 0 °C 25.1: 97 percent / Pd(PPh3)4; CuI / benzene / 4 h / 80 °C 26.1: 85 percent / P2O5 / 12 h / 20 °C 27.1: 77 percent / trisdimethylamino sulfonyl trimethylsilyldifluoride; water / dimethylformamide / 26 h / 0 °C 28.1: 84 percent / aq. NaOH / tetrahydrofuran / 30 h / 20 °C 29.1: 2,4,6-trichlorobenzoyl chloride; triethylamine; DMAP / tetrahydrofuran; toluene / 25.5 h / 0 - 20 °C 30.1: Me2BBr / CH2Cl2 / 1 h / -78 °C View Scheme

1.1: 95 percent / triphenylphosphine; imidazole; iodine / diethyl ether; acetonitrile / 0.17 h / 20 °C 2.1: tert-butyllithium; ZnCl2 / diethyl ether; petroleum ether / 1 h / 20 °C 2.2: 58 percent / Pd(PPh3)4 / diethyl ether; various solvent(s) / 16 h 3.1: 87 percent / TBAF / tetrahydrofuran / 20 h / 20 °C 4.1: 86 percent / H2 / Rh[(nbd)dppb]BF4 / CH2Cl2 / 4 h / 36201.3 Torr 5.1: 100 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 6.1: 93 percent / DDQ / CH2Cl2 / 1 h / 20 °C / pH 7 7.1: triethylamine / CH2Cl2 / 1.5 h / 20 °C 8.1: HF / acetonitrile / 3 h / 20 °C 9.1: 98 percent / potassium carbonate / methanol / 0.75 h 10.1: 92 percent / lithium perchlorate / acetonitrile / 24 h / 70 °C 11.1: 81 percent / diisopropylethylamine / CH2Cl2 / 28 h / 20 °C 12.1: DIBAL-H / CH2Cl2; petroleum ether / 1 h / -78 °C 13.1: 2-methyl-2-butene; NaH2PO4; NaClO2 / H2O; 2-methyl-propan-2-ol / 1 h / 0 °C 14.1: K2CO3 / dimethylformamide / 3.5 h / 20 °C 15.1: H2 / Pd/C / tetrahydrofuran; ethanol / 3 h / 10343.2 Torr 16.1: 89 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 17.1: 86 percent / potassium tert-butoxide / tetrahydrofuran / 18 h / -70 - 20 °C 18.1: 91 percent / c. HCl / methanol / 0.5 h / 20 °C 19.1: 94 percent / Pd(PPh3)4; CuI; triethylamine / 12 h / 20 °C 20.1: 94 percent / triethylamine; DAMP / CH2Cl2 / 2 h / 20 °C 21.1: PdCl2(PPh3)2; Bu3SnH / CH2Cl2 21.2: I2 / CH2Cl2 / 0 °C 21.3: potassium carbonate; methanol / -25 - 0 °C 22.1: 97 percent / Pd(PPh3)4; CuI / benzene / 4 h / 80 °C 23.1: 85 percent / P2O5 / 12 h / 20 °C 24.1: 77 percent / trisdimethylamino sulfonyl trimethylsilyldifluoride; water / dimethylformamide / 26 h / 0 °C 25.1: 84 percent / aq. NaOH / tetrahydrofuran / 30 h / 20 °C 26.1: 2,4,6-trichlorobenzoyl chloride; triethylamine; DMAP / tetrahydrofuran; toluene / 25.5 h / 0 - 20 °C 27.1: Me2BBr / CH2Cl2 / 1 h / -78 °C View Scheme

1.1: Cp2ZrHCl / CH2Cl2 / 2 h 1.2: 89 percent / I2 / CH2Cl2; CCl4 2.1: tert-butyllithium; ZnCl2 / diethyl ether; petroleum ether / 1 h / 20 °C 2.2: 58 percent / Pd(PPh3)4 / diethyl ether; various solvent(s) / 16 h 3.1: 87 percent / TBAF / tetrahydrofuran / 20 h / 20 °C 4.1: 86 percent / H2 / Rh[(nbd)dppb]BF4 / CH2Cl2 / 4 h / 36201.3 Torr 5.1: 100 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 6.1: 93 percent / DDQ / CH2Cl2 / 1 h / 20 °C / pH 7 7.1: triethylamine / CH2Cl2 / 1.5 h / 20 °C 8.1: HF / acetonitrile / 3 h / 20 °C 9.1: 98 percent / potassium carbonate / methanol / 0.75 h 10.1: 92 percent / lithium perchlorate / acetonitrile / 24 h / 70 °C 11.1: 81 percent / diisopropylethylamine / CH2Cl2 / 28 h / 20 °C 12.1: DIBAL-H / CH2Cl2; petroleum ether / 1 h / -78 °C 13.1: 2-methyl-2-butene; NaH2PO4; NaClO2 / H2O; 2-methyl-propan-2-ol / 1 h / 0 °C 14.1: K2CO3 / dimethylformamide / 3.5 h / 20 °C 15.1: H2 / Pd/C / tetrahydrofuran; ethanol / 3 h / 10343.2 Torr 16.1: 89 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 17.1: 86 percent / potassium tert-butoxide / tetrahydrofuran / 18 h / -70 - 20 °C 18.1: 91 percent / c. HCl / methanol / 0.5 h / 20 °C 19.1: 94 percent / Pd(PPh3)4; CuI; triethylamine / 12 h / 20 °C 20.1: 94 percent / triethylamine; DAMP / CH2Cl2 / 2 h / 20 °C 21.1: PdCl2(PPh3)2; Bu3SnH / CH2Cl2 21.2: I2 / CH2Cl2 / 0 °C 21.3: potassium carbonate; methanol / -25 - 0 °C 22.1: 97 percent / Pd(PPh3)4; CuI / benzene / 4 h / 80 °C 23.1: 85 percent / P2O5 / 12 h / 20 °C 24.1: 77 percent / trisdimethylamino sulfonyl trimethylsilyldifluoride; water / dimethylformamide / 26 h / 0 °C 25.1: 84 percent / aq. NaOH / tetrahydrofuran / 30 h / 20 °C 26.1: 2,4,6-trichlorobenzoyl chloride; triethylamine; DMAP / tetrahydrofuran; toluene / 25.5 h / 0 - 20 °C 27.1: Me2BBr / CH2Cl2 / 1 h / -78 °C View Scheme