Reaction SMILES: [N:1]([CH:4]1[CH2:10][CH2:9][N:8]([C:11]2[N:15]([CH3:16])[N:14]=[CH:13][C:12]=2[N+:17]([O-:19])=[O:18])[CH2:7][CH2:6][CH:5]1O)=[N+:2]=[N-:3].COCCN(S(F)(F)[F:31])CCOC.C([O-])(O)=O.[Na+]>C(Cl)Cl.C1COCC1>[N:1]([CH:4]1[CH:5]([F:31])[CH2:6][CH2:7][N:8]([C:11]2[N:15]([CH3:16])[N:14]=[CH:13][C:12]=2[N+:17]([O-:19])=[O:18])[CH2:9][CH2:10]1)=[N+:2]=[N-:3]
Reactant: COCCN(CCOC)S(F)(F)F
Reactant: Cn1ncc([N+](=O)[O-])c1N1CCC(O)C(N=[N+]=[N-])CC1
Agent: O=C([O-])O
Agent: [Na+]
Solvent: C1CCOC1
Solvent: ClCCl
Product: Cn1ncc([N+](=O)[O-])c1N1CCC(F)C(N=[N+]=[N-])CC1
Temperature: 25 °C
Reaction time: 16 h

Procedure:
To a solution of 5-azido-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)azepan-4-ol (7.26 g, 25.8 mmol) in dry DCM (100 ml) was added dropwise deoxo-Fluor® (12.1 mL, 32.84 mmol, 50% in THF) and the mixture was stirred at room temperature for 16 hr. The mixture was cooled in an ice bath and saturated aqueous NaHCO3 solution (40 mL) was added slowly (effervescence observed) and the mixture was extracted with DCM (150 mL). The organic layer was washed with saturated aqueous NaHCO3 solution (2×30 mL), separated, passed through a phase separation cartridge and concentrated under reduced pressure. The residue was purified via silica gel column chromatography (0-100% EtOAc/isohexane) to give 4-azido-5-fluoro-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)azepane as a yellow gum (5.55 g). The reaction was repeated to provide additional material. A solution of this gum (6.40 g, 22.6 mmol) in THF/water (120 mL/24 mL) was treated with triphenylphosphine (5.93 g, 22.6 mmol) and the mixture was heated at 60° C. for 16 hr. The mixture was partitioned between EtOAc (150 mL) and water (20 mL) and the organic layer was separated, washed with brine (20 mL), passed through a phase separation cartridge and concentrated under reduced pressure. The residue was re-dissolved in MeOH and passed through an SCX column, washing with MeOH and eluting with 3-10% 7 N ammonia in MeOH/DCM to give 5-fluoro-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)azepan-4-amine as a yellow oil (5.70 g). To a solution of this oil (5.7 g, 22.1 mmol) and DIPEA (11.5 mL, 66.3 mmol) in DCM (50 mL) was added dropwise trifluoroacetic anhydride (3.38 mL, 24.3 mmol) and the mixture stirred at room temperature for 16 hr. Water (15 mL) was added and the organic phase separated, passed through a phase separation cartridge and concentrated under reduced pressure to give 2,2,2-trifluoro-N-(5-fluoro-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)azepan-4-yl)acetamide as a yellow gum (7.8 g). To a solution of this gum (7.8 g, 22.0 mmol) and ammonium formate (10.23 g, 176.0 mmol) in MeOH (100 mL) under nitrogen was added 10% palladium on carbon (585 mg, 5.5 mmol). The mixture was heated at 70° C. for 4 hr before being cooled, filtered and concentrated under reduced pressure. The residue was partitioned between water (20 mL) and DCM (100 mL) and the organic layer was separated, passed through a phase separation cartridge and concentrated under reduced pressure to give N-((4S,5S)-1-(4-amino-1-methyl-1H-pyrazol-5-yl)-5-fluoroazepan-4-yl)-2,2,2-trifluoroacetamide as a brown solid (4.72 g, 49% over four steps). 1H NMR (400 MHz, CDCl3) δ 9.03 (s, 1H), 7.19 (s, 1H), 4.90-4.76 (m, 2H), 3.66 (s, 3H), 3.52-3.43 (m, 2H), 3.12 (td, J=11.9, 5.4 Hz, 1H), 2.96 (dt, J=14.8, 4.2 Hz, 1H), 2.43-2.31 (m, 1H), 2.13-1.85 (m, 3H). Exchangeable NH2 not observed.