sodium hydride in tetrahydrofuran T=20°C; Methylation; 6 h;

1: 83 percent / Et3N / CHCl3 2: 89 percent / NaH / tetrahydrofuran / 6 h / 20 °C View Scheme

1.1: s-BuLi; TMEDA / tetrahydrofuran; cyclohexane / 5 h / -78 °C 1.2: 80 percent / tetrahydrofuran; cyclohexane / 0.08 h / -78 °C 2.1: (S)-BINAP; Rh(I); H2 / methanol View Scheme

1.1: s-BuLi; TMEDA / tetrahydrofuran; cyclohexane / 5 h / -78 °C 1.2: 80 percent / tetrahydrofuran; cyclohexane / 0.08 h / -78 °C 2.1: 87 percent / H2 / (S)-BINAP; RuCl2 / methanol / 11 h / 45 °C / 51716.2 Torr 3.1: 97 percent / BH3*THF / tetrahydrofuran / 3 h / 20 °C View Scheme

sec.-butyllithium 1) THF, -78 deg C, 5 min, 2) THF, -78 deg C to RT; Yield given. Multistep reaction. Yields of byproduct given;

1.1: s-BuLi; TMEDA / tetrahydrofuran; cyclohexane / 5 h / -78 °C 1.2: 80 percent / tetrahydrofuran; cyclohexane / 0.08 h / -78 °C 2.1: 87 percent / H2 / (S)-BINAP; RuCl2 / methanol / 11 h / 45 °C / 51716.2 Torr 3.1: 97 percent / BH3*THF / tetrahydrofuran / 3 h / 20 °C 4.1: 98 percent / oxalyl chloride; DMSO; DIPEA / CH2Cl2 / -78 - 20 °C View Scheme

1.1: s-BuLi; TMEDA / tetrahydrofuran; cyclohexane / 5 h / -78 °C 1.2: 80 percent / tetrahydrofuran; cyclohexane / 0.08 h / -78 °C 2.1: 87 percent / H2 / (S)-BINAP; RuCl2 / methanol / 11 h / 45 °C / 51716.2 Torr View Scheme

1.1: s-BuLi; TMEDA / tetrahydrofuran; cyclohexane / 5 h / -78 °C 1.2: 80 percent / tetrahydrofuran; cyclohexane / 0.08 h / -78 °C 2.1: 87 percent / H2 / (S)-BINAP; RuCl2 / methanol / 11 h / 45 °C / 51716.2 Torr 3.1: 97 percent / BH3*THF / tetrahydrofuran / 3 h / 20 °C 4.1: 98 percent / oxalyl chloride; DMSO; DIPEA / CH2Cl2 / -78 - 20 °C 5.1: 79 percent / n-BuLi / tetrahydrofuran; hexane / -78 - 20 °C 6.1: 94 percent / H2 / Pd/C / ethyl acetate / 24 h View Scheme