1: (S)-tert-butyl 2-(5-(4-chlorophenyl)-6,7-dimethyl-2-oxo-2,3-dihydro-1H-thieno[2,3-e][1,4]diazepin-3-yl)acetate With potassium tert-butylate in tetrahydrofuran T=-78 - 23°C; 0.5 h; 2: With diethyl chlorophosphate in tetrahydrofuran T=-10°C; 0.75 h; 3: acetic acid hydrazide in tetrahydrofuran; butan-1-ol T=23 - 90°C; 2 h;

1.1: N-ethyl-N,N-diisopropylamine; O-(6-chloro-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate / N,N-dimethyl-formamide / 16 h / 23 °C 2.1: piperidine / N,N-dimethyl-formamide / 0.5 h / 23 °C 3.1: silica gel / ethanol / 3 h / 90 °C 4.1: potassium tert-butylate / tetrahydrofuran / 0.5 h / -78 - 23 °C 4.2: 0.75 h / -10 °C 4.3: 2 h / 23 - 90 °C View Scheme

1.1: morpholine; sulfur / ethanol / 12 h / 23 - 70 °C 2.1: N-ethyl-N,N-diisopropylamine; O-(6-chloro-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate / N,N-dimethyl-formamide / 16 h / 23 °C 3.1: piperidine / N,N-dimethyl-formamide / 0.5 h / 23 °C 4.1: silica gel / ethanol / 3 h / 90 °C 5.1: potassium tert-butylate / tetrahydrofuran / 0.5 h / -78 - 23 °C 5.2: 0.75 h / -10 °C 5.3: 2 h / 23 - 90 °C View Scheme

1.1: piperidine / N,N-dimethyl-formamide / 0.5 h / 23 °C 2.1: silica gel / ethanol / 3 h / 90 °C 3.1: potassium tert-butylate / tetrahydrofuran / 0.5 h / -78 - 23 °C 3.2: 0.75 h / -10 °C 3.3: 2 h / 23 - 90 °C View Scheme

1.1: silica gel / ethanol / 3 h / 90 °C 2.1: potassium tert-butylate / tetrahydrofuran / 0.5 h / -78 - 23 °C 2.2: 0.75 h / -10 °C 2.3: 2 h / 23 - 90 °C View Scheme