1.1: titanium(IV) isopropylate; n-butyllithium / tetrahydrofuran; hexane / 2 h / -78 - 50 °C / Inert atmosphere 1.2: Inert atmosphere 2.1: hydrogenchloride; water / tetrahydrofuran / 15 h / 20 °C View Scheme

1.1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / dimethyl sulfoxide / 23 h / 20 °C / Inert atmosphere 2.1: n-butyllithium; N,N,N',N,-tetramethylethylenediamine / tetrahydrofuran; hexane / 0.05 h / -98 °C / Inert atmosphere 2.2: 2 h / -98 - -60 °C / Inert atmosphere 2.3: Inert atmosphere 3.1: Cl2Ni(1,2-bis(diphenylphosphino)ethane); 1,1-dimethylethylmagnesium chloride / tetrahydrofuran; dichloromethane / 20 °C / Inert atmosphere 3.2: 20 °C / Inert atmosphere 4.1: diisopropyl-carbodiimide / dichloromethane / 24 h / 20 °C / Inert atmosphere 5.1: titanium(IV) isopropylate; n-butyllithium / tetrahydrofuran; hexane / 2 h / -78 - 50 °C / Inert atmosphere 5.2: Inert atmosphere 6.1: hydrogenchloride; water / tetrahydrofuran / 15 h / 20 °C View Scheme

1.1: n-butyllithium; N,N,N',N,-tetramethylethylenediamine / tetrahydrofuran; hexane / 0.05 h / -98 °C / Inert atmosphere 1.2: 2 h / -98 - -60 °C / Inert atmosphere 1.3: Inert atmosphere 2.1: Cl2Ni(1,2-bis(diphenylphosphino)ethane); 1,1-dimethylethylmagnesium chloride / tetrahydrofuran; dichloromethane / 20 °C / Inert atmosphere 2.2: 20 °C / Inert atmosphere 3.1: diisopropyl-carbodiimide / dichloromethane / 24 h / 20 °C / Inert atmosphere 4.1: titanium(IV) isopropylate; n-butyllithium / tetrahydrofuran; hexane / 2 h / -78 - 50 °C / Inert atmosphere 4.2: Inert atmosphere 5.1: hydrogenchloride; water / tetrahydrofuran / 15 h / 20 °C View Scheme

1.1: tert.-butyl lithium / tetrahydrofuran; pentane / 0.08 h / -78 °C / Inert atmosphere 1.2: 0.17 h / -78 °C / Inert atmosphere 1.3: -78 °C / Inert atmosphere 2.1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / dimethyl sulfoxide / 23 h / 20 °C / Inert atmosphere 3.1: n-butyllithium; N,N,N',N,-tetramethylethylenediamine / tetrahydrofuran; hexane / 0.05 h / -98 °C / Inert atmosphere 3.2: 2 h / -98 - -60 °C / Inert atmosphere 3.3: Inert atmosphere 4.1: Cl2Ni(1,2-bis(diphenylphosphino)ethane); 1,1-dimethylethylmagnesium chloride / tetrahydrofuran; dichloromethane / 20 °C / Inert atmosphere 4.2: 20 °C / Inert atmosphere 5.1: diisopropyl-carbodiimide / dichloromethane / 24 h / 20 °C / Inert atmosphere 6.1: titanium(IV) isopropylate; n-butyllithium / tetrahydrofuran; hexane / 2 h / -78 - 50 °C / Inert atmosphere 6.2: Inert atmosphere 7.1: hydrogenchloride; water / tetrahydrofuran / 15 h / 20 °C View Scheme

1: 1.) B(OMe)3 / 2.) PdCl2(dppf) / 1.) THF, 2.) reflux, 27 h 2: 1.) n-BuLi, 9-MeO-9-BBN / 2.) PdCl2(dppf) / 1.) THF, hexane, -78 deg C to r.t., 2.) reflux, 15 h 3: 74 percent / H2 / 5percent Pd/C, ethylenediamine / methanol / 0.42 h / 760 Torr 4: 95 percent / 70percent aq. TBAF / ethyl acetate / 0.5 h View Scheme

1: 83 percent / imidazole / tetrahydrofuran / Ambient temperature 2: 1.) n-BuLi, 9-MeO-9-BBN / 2.) PdCl2(dppf) / 1.) THF, hexane, -78 deg C to r.t., 2.) reflux, 15 h 3: 74 percent / H2 / 5percent Pd/C, ethylenediamine / methanol / 0.42 h / 760 Torr 4: 95 percent / 70percent aq. TBAF / ethyl acetate / 0.5 h View Scheme

1: 86 percent / MCPBA / CH2Cl2 / 48 h / Ambient temperature 2: 83 percent / imidazole / tetrahydrofuran / Ambient temperature 3: 1.) n-BuLi, 9-MeO-9-BBN / 2.) PdCl2(dppf) / 1.) THF, hexane, -78 deg C to r.t., 2.) reflux, 15 h 4: 74 percent / H2 / 5percent Pd/C, ethylenediamine / methanol / 0.42 h / 760 Torr 5: 95 percent / 70percent aq. TBAF / ethyl acetate / 0.5 h View Scheme

1: 1.) n-BuLi, 9-MeO-9-BBN / 2.) PdCl2(dppf) / 1.) THF, hexane, -78 deg C to r.t., 2.) reflux, 15 h 2: 74 percent / H2 / 5percent Pd/C, ethylenediamine / methanol / 0.42 h / 760 Torr 3: 95 percent / 70percent aq. TBAF / ethyl acetate / 0.5 h View Scheme

1: 1.) B(OMe)3, 2.) KBr / 2.) PdCl2(dppf) / 1.) THF, 2.) reflux 2: 1.) n-BuLi, 9-MeO-9-BBN / 2.) PdCl2(dppf) / 1.) THF, hexane, -78 deg C to r.t., 2.) reflux, 15 h 3: 74 percent / H2 / 5percent Pd/C, ethylenediamine / methanol / 0.42 h / 760 Torr 4: 95 percent / 70percent aq. TBAF / ethyl acetate / 0.5 h View Scheme

1: 74 percent / H2 / 5percent Pd/C, ethylenediamine / methanol / 0.42 h / 760 Torr 2: 95 percent / 70percent aq. TBAF / ethyl acetate / 0.5 h View Scheme