1.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 2.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 3.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 3.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 4.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 2.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 2.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 3.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 2.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 3.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 4.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 4.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 5.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: 89 percent / diethyl azodicarboxylate; PPh3 / benzene; toluene / 0.5 h / 20 °C 2.1: TFA / CH2Cl2 / 0.25 h / 20 °C 3.1: pyrrolidine / methanol; acetonitrile / 0.08 h / 20 °C 4.1: pyrrolidine / methanol; acetonitrile / 4 h / Heating 5.1: 88 percent / PPh3 / CCl4; acetonitrile / 0.5 h / 70 °C 6.1: KOH / methanol / 0.75 h / 80 °C 7.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 8.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 9.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 10.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 10.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 11.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: KOH / methanol / 0.75 h / 80 °C 2.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 3.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 4.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 5.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 5.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 6.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: pyrrolidine / methanol; acetonitrile / 4 h / Heating 2.1: 88 percent / PPh3 / CCl4; acetonitrile / 0.5 h / 70 °C 3.1: KOH / methanol / 0.75 h / 80 °C 4.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 5.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 6.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 7.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 7.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 8.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: 88 percent / PPh3 / CCl4; acetonitrile / 0.5 h / 70 °C 2.1: KOH / methanol / 0.75 h / 80 °C 3.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 4.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 5.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 6.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 6.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 7.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: pyrrolidine / methanol; acetonitrile / 0.08 h / 20 °C 2.1: pyrrolidine / methanol; acetonitrile / 4 h / Heating 3.1: 88 percent / PPh3 / CCl4; acetonitrile / 0.5 h / 70 °C 4.1: KOH / methanol / 0.75 h / 80 °C 5.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 6.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 7.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 8.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 8.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 9.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

1.1: TFA / CH2Cl2 / 0.25 h / 20 °C 2.1: pyrrolidine / methanol; acetonitrile / 0.08 h / 20 °C 3.1: pyrrolidine / methanol; acetonitrile / 4 h / Heating 4.1: 88 percent / PPh3 / CCl4; acetonitrile / 0.5 h / 70 °C 5.1: KOH / methanol / 0.75 h / 80 °C 6.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 7.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 8.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 9.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 9.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 10.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

cell-free extracts from Catharanthus roseus; NADPH; Adenine-flavine dinucleotide T=34°C; 2 h; biosynthesis of the product was studied; in the presence of <methyl-14C>methionine and <Ar-3H>stemmadenine; incorporation of the radiolabel into vindoline was investigated; Product distributionMechanism;