sodium methylate in methanol; toluene T=25°C; 12 h;

potassium hydroxide in ethanol T=70°C; 2 h;

1: 1.) n-butyllithium, diisopropylamine / 1.) hexane, THF, -78 deg C, 15 min, 2.) THF, -78 deg C to 0 deg C, 1h 2: p-TSA, MgSO4 / toluene; CHCl3 / 3 h / 70 °C 3: H2 / Lindlar / toluene; CHCl3 / 12 h / 760 Torr 4: tert-butylamine-borane complex / CH2Cl2 / 1 h / Heating 5: 86 percent / pyridine, 4-(N,N-dimethylamino)pyridine / CH2Cl2 / 0.2 h / 0 °C 6: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 7: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 8: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 9: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 10: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme

1: 1.) n-butyllithium, diisopropylamine / 1.) hexane, THF, -78 deg C, 15 min, 2.) THF, -78 deg C to 0 deg C, 1h 2: p-TSA, MgSO4 / toluene; CHCl3 / 3 h / 70 °C 3: H2 / Lindlar / toluene; CHCl3 / 12 h / 760 Torr 4: tert-butylamine-borane complex / CH2Cl2 / 1 h / Heating 5: 86 percent / pyridine, 4-(N,N-dimethylamino)pyridine / CH2Cl2 / 0.2 h / 0 °C 6: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 7: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 8: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 9: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 10: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme

1: 86 percent / pyridine, 4-(N,N-dimethylamino)pyridine / CH2Cl2 / 0.2 h / 0 °C 2: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 3: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 4: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 5: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 6: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme

1: 74 percent / O3 / CH2Cl2 / -78 °C 2: 1.) n-butyllithium, diisopropylamine / 1.) hexane, THF, -78 deg C, 15 min, 2.) THF, -78 deg C to 0 deg C, 1h 3: p-TSA, MgSO4 / toluene; CHCl3 / 3 h / 70 °C 4: H2 / Lindlar / toluene; CHCl3 / 12 h / 760 Torr 5: tert-butylamine-borane complex / CH2Cl2 / 1 h / Heating 6: 86 percent / pyridine, 4-(N,N-dimethylamino)pyridine / CH2Cl2 / 0.2 h / 0 °C 7: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 8: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 9: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 10: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 11: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme

1: tert-butylamine-borane complex / CH2Cl2 / 1 h / Heating 2: 86 percent / pyridine, 4-(N,N-dimethylamino)pyridine / CH2Cl2 / 0.2 h / 0 °C 3: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 4: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 5: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 6: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 7: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme

1: H2 / Lindlar / toluene; CHCl3 / 12 h / 760 Torr 2: tert-butylamine-borane complex / CH2Cl2 / 1 h / Heating 3: 86 percent / pyridine, 4-(N,N-dimethylamino)pyridine / CH2Cl2 / 0.2 h / 0 °C 4: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 5: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 6: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 7: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 8: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme

1: p-TSA, MgSO4 / toluene; CHCl3 / 3 h / 70 °C 2: H2 / Lindlar / toluene; CHCl3 / 12 h / 760 Torr 3: tert-butylamine-borane complex / CH2Cl2 / 1 h / Heating 4: 86 percent / pyridine, 4-(N,N-dimethylamino)pyridine / CH2Cl2 / 0.2 h / 0 °C 5: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 6: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 7: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 8: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 9: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme

1: 2,6-di-tert-butyl-4-methylpyridine / CH2Cl2 / 1.) room temp., overnight, 2.) reflux, 30 min 2: 94 percent / tributylamine, 98percent formic acid / Pd(OAc)2(Ph3P)2 / dimethylformamide / 0.5 h / 70 °C 3: K2CO3 / CH2Cl2; methanol / 0.08 h / 25 °C 4: bis<α,α-bis(trifluoromethyl)benzenemethanolato>diphenylsulfur / CH2Cl2 / 0.25 h / 0 °C 5: 96 percent / NaOMe / toluene; methanol / 12 h / 25 °C View Scheme