tert-butyl N-(azepan-4-yl)carbamate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedures as described in EXAMPLE 8 and starting with 1-ethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole and tert-butyl azepan-4-ylcarbamate, 140 was obtained as an off-white solid (16.2 mg, 12%) over 2 steps. 1H NMR (400 MHz, DMSO) δ 9.15-9.11 (s, 1H), 8.70-8.65 (d, J=9.8 Hz, 1H), 8.54-8.47 (d, J=8.1 Hz, 1H), 8.28-8.25 (d, J=7.4 Hz, 1H), 7.95-7.87 (s, 1H), 7.73-7.66 (dd, J=10.5, 5.7 Hz, 1H), 7.18-7.12 (d, J=7.7 Hz, 1H), 6.60-6.54 (t, J=6.6 Hz, 1H), 4.25-4.18 (q, J=7.3 Hz, 2H), 3.95-3.86 (s, 1H), 3.85-3.77 (m, 1H), 3.75-3.58 (ddd, J=20.2, 14.0, 9.4 Hz, 2H), 2.94-2.85 (dd, J=12.2, 6.3 Hz, 1H), 2.07-1.96 (m, 2H), 1.83-1.74 (m, 1H), 1.74-1.66 (d, J=14.4 Hz, 1H), 1.65-1.56 (ddd, J=13.0, 9.1, 4.5 Hz, 1H), 1.46-1.41 (t, J=7.3 Hz, 3H), 1.42-1.34 (dd, J=14.2, 4.0 Hz, 1H); MS (ESI) m/z: 403.2 [M+H]+

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedures as described in EXAMPLE 8 and starting with 1-ethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole and tert-butyl azepan-4-ylcarbamate, 140 was obtained as an off-white solid (16.2 mg, 12%) over 2 steps. 1H NMR (400 MHz, DMSO) δ 9.15-9.11 (s, 1H), 8.70-8.65 (d, J=9.8 Hz, 1H), 8.54-8.47 (d, J=8.1 Hz, 1H), 8.28-8.25 (d, J=7.4 Hz, 1H), 7.95-7.87 (s, 1H), 7.73-7.66 (dd, J=10.5, 5.7 Hz, 1H), 7.18-7.12 (d, J=7.7 Hz, 1H), 6.60-6.54 (t, J=6.6 Hz, 1H), 4.25-4.18 (q, J=7.3 Hz, 2H), 3.95-3.86 (s, 1H), 3.85-3.77 (m, 1H), 3.75-3.58 (ddd, J=20.2, 14.0, 9.4 Hz, 2H), 2.94-2.85 (dd, J=12.2, 6.3 Hz, 1H), 2.07-1.96 (m, 2H), 1.83-1.74 (m, 1H), 1.74-1.66 (d, J=14.4 Hz, 1H), 1.65-1.56 (ddd, J=13.0, 9.1, 4.5 Hz, 1H), 1.46-1.41 (t, J=7.3 Hz, 3H), 1.42-1.34 (dd, J=14.2, 4.0 Hz, 1H); MS (ESI) m/z: 403.2 [M+H]+

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedures as described in EXAMPLE 8 and starting with 1-ethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole and tert-butyl azepan-4-ylcarbamate, 140 was obtained as an off-white solid (16.2 mg, 12%) over 2 steps. 1H NMR (400 MHz, DMSO) δ 9.15-9.11 (s, 1H), 8.70-8.65 (d, J=9.8 Hz, 1H), 8.54-8.47 (d, J=8.1 Hz, 1H), 8.28-8.25 (d, J=7.4 Hz, 1H), 7.95-7.87 (s, 1H), 7.73-7.66 (dd, J=10.5, 5.7 Hz, 1H), 7.18-7.12 (d, J=7.7 Hz, 1H), 6.60-6.54 (t, J=6.6 Hz, 1H), 4.25-4.18 (q, J=7.3 Hz, 2H), 3.95-3.86 (s, 1H), 3.85-3.77 (m, 1H), 3.75-3.58 (ddd, J=20.2, 14.0, 9.4 Hz, 2H), 2.94-2.85 (dd, J=12.2, 6.3 Hz, 1H), 2.07-1.96 (m, 2H), 1.83-1.74 (m, 1H), 1.74-1.66 (d, J=14.4 Hz, 1H), 1.65-1.56 (ddd, J=13.0, 9.1, 4.5 Hz, 1H), 1.46-1.41 (t, J=7.3 Hz, 3H), 1.42-1.34 (dd, J=14.2, 4.0 Hz, 1H); MS (ESI) m/z: 403.2 [M+H]+

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The preparation is carried out analogously starting from 1.02 g (4.31 mmol) of 2,6-dibromopyridine and 856 mg (4.27 mmol) of azepan-4-ylcarbamic acid tert-butyl ester.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedures as described in Example 189, 3-(6-fluoropyridin-2-yl)-5-(1-methyl-1H-pyrazol-4-yl)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazolo[3,4-c]pyridine and tert-butyl azepan-4-ylcarbamate were reacted. The product was deprotected to give 188 as a white solid (47.1% over two steps). 1H NMR (400 MHz, DMSO) δ 9.02 (s, 1H), 8.55 (s, 1H), 8.11 (s, 1H), 7.83 (s, 1H), 7.60 (t, J=8.0 Hz, 1H), 7.37 (d, J=7.3 Hz, 1H), 6.61 (d, J=8.5 Hz, 1H), 4.02-3.86 (m, 4H), 3.85-3.75 (m, 1H), 3.75-3.55 (m, 3H), 2.93-2.85 (s, 1H), 2.10-1.93 (m, 2H), 1.89-1.56 (m, 3H), 1.45-1.31 (m, 1H); 2 protons not seen. LC/MS: m/z 389.2 [M+1] were reacted