Rh(I)-(R)BINAP in tetrahydrofuran 1.) -70 deg C, 2.) 0 gradC, 14 d;

water; hydrogen T=160°C; P=30003 Torr; Autoclave;

1.1: cerium(III) chloride heptahydrate / tetrahydrofuran; methanol / 0.5 h / 7 °C / |Inert atmosphere 1.2: -33 - -20 °C 2.1: Lipase PS 'amano’ IM / hexadeuterioacetone / 48 h / 25 °C / |Inert atmosphere 3.1: 1,1,1-triethoxyethane; hydroquinone / water / 36.75 h / 25 - 144 °C 4.1: sulfuric acid / 41 h / 29 - 79 °C 5.1: methanol / 25 - 65 °C View Scheme

water; hydrogen T=160°C; P=30003 Torr; Autoclave;

1: hydrogen; water / 160 °C / 30003 Torr / |Autoclave 2: hydrogen / 36 h / 180 °C / 30003 Torr / |Autoclave View Scheme

1: 76 percent / PPTs / tetrahydrofuran / 18 h / Ambient temperature 2: LiAlH4, LiI / various solvent(s); toluene / 0.5 h / -20 - -13 °C 3: 50 percent / Et3N, pancreatin, vinyl acetate / various solvent(s) / 7 h / Ambient temperature 4: DMAP / pyridine / 16 h / Ambient temperature 5: p-TsOH / ethanol / 2 h / Ambient temperature View Scheme

1: 76 percent / PPTs / tetrahydrofuran / 18 h / Ambient temperature 2: LiAlH4, LiI / various solvent(s); toluene / 0.5 h / -20 - -13 °C 3: 45 percent / Et3N, pancreatin, vinyl acetate / various solvent(s) / 7 h / Ambient temperature 4: p-TsOH / ethanol / 2 h / Ambient temperature View Scheme

1: NaOAc / tetrahydrofuran / 15 h / 35 °C 2: Cl2, Et3N / diethyl ether / 1.5 h / 26 - 29 °C View Scheme

1.1: cerium(III) chloride heptahydrate / tetrahydrofuran; methanol / 0.5 h / 7 °C / |Inert atmosphere 1.2: -33 - -20 °C 2.1: Lipase PS 'amano’ IM / hexadeuterioacetone / 48 h / 25 °C / |Inert atmosphere 3.1: 1,1,1-triethoxyethane; hydroquinone / water / 36.75 h / 25 - 144 °C 4.1: sulfuric acid / 41 h / 29 - 79 °C 5.1: methanol / 25 - 65 °C 6.1: 4-(N,N-dimethlyamino)pyridine; triethylamine / tetrahydrofuran / 35 - 65 °C / |Inert atmosphere; |Molecular sieve 7.1: 4-(N,N-dimethlyamino)pyridine; triethylamine / dichloromethane / 0.17 h / 27 °C / |Inert atmosphere 7.2: 35 - 40 °C / |Inert atmosphere View Scheme

1: 36 percent / DBU / CH2Cl2 / 72 h / Ambient temperature 2: LiAlH4, LiI / toluene; various solvent(s) / 1.) -20 deg C, 1 h, 2.) -20 deg C to 0 deg C, 0.5 h, 3.) 0 deg C to 15 deg C, 4 h 3: 58 mg / p-TsOH / ethanol / 8 h / 55 °C View Scheme