Reaction SMILES: [CH3:1][C@H:2]1[CH2:7][N:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][C:9]=2[N+:14]([O-:16])=[O:15])[CH2:5][C@@H:4]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH2:3]1.ClC1C=CN=CC=1[N+]([O-])=O.CCN(CC)CC>CC(O)C>[CH3:1][CH:2]1[CH2:7][N:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][C:9]=2[N+:14]([O-:16])=[O:15])[CH2:5][CH:4]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH2:3]1
Reactant: C[C@@H]1C[C@H](NC(=O)OC(C)(C)C)CN(c2ccncc2[N+](=O)[O-])C1
Agent: O=[N+]([O-])c1cnccc1Cl
Solvent: CC(C)O
Solvent: CCN(CC)CC
Product: CC1CC(NC(=O)OC(C)(C)C)CN(c2ccncc2[N+](=O)[O-])C1
Temperature: 80 °C
Reaction time: 1.5 h
Yield: 24 %

Procedure:
tert-butyl ((cis)-5-methyl-1-(3-nitropyridin-4-yl)piperidin-3-yl)carbamate (first eluting enantiomer), tert-butyl ((cis)-5-methyl-1-(3-nitropyridin-4-yl)piperidin-3-yl)carbamate (second eluting enantiomer). A racemic mixture of cis- and trans-tert-butyl-(5-methylpiperidin-3-yl)carbamate (8.36 g, 39.0 mmol) (Preparation XXXIV, step 2) in 2-propanol (100 mL) was treated with 4-chloro-3-nitropyridine (5.11 g, 32.2 mmol, Alfa Aesar, Ward Hill, Mass.) and Et3N (16.3 mL, 117 mmol). The mixture was heated to 80° C. and stirred for 1.5 h. The reaction mixture was then concentrated under reduced pressure, treated with water and extracted with EtOAc (2×100 mL). The combined organic layers were dried over MgSO4, filtered and concentrated. The crude material was purified by silica gel chromatography (30-80% EtOAc in hexanes) to afford rac-tert-butyl (5-methyl-1-(3-nitropyridin-4-yl)piperidin-3-yl)carbamate (3.11 g, 9.25 mmol, 24% yield) as a 76:24 ratio of cis:trans diastereomers. The mixture was purified by supercritical-fluid chromatography (Chiralcel OJ-H column (21×250 mm, 5 μm), 92% liquid CO2/8% EtOH (20 mM NH3), 70 mL/min). The crude material was repurified by supercritical-fluid chromatography (Chiralcel OZ-H column (21×250 mm, 5 μm), 85% liquid CO2/15% EtOH (20 mM NH3), 70 mL/min) to afford tert-butyl ((cis)-5-methyl-1-(3-nitropyridin-4-yl)piperidin-3-yl)carbamate (first eluting peak) (900 mg, 14% yield), which eluted first from analytical supercritical-fluid chromatography (Chiralcel OZ-H column (4.6×150 mm, 5 μm), 85% liquid CO2/15% EtOH (0.1% diethylamine), 4 mL/min) and was obtained as a bright yellow crystalline solid upon evaporation of the solvent and drying. MS (ESI, pos. ion) m/z: 337.1 (M+1). 1H NMR (400 MHz, CDCl3) δ ppm 8.83 (1 H, s), 8.35 (1 H, d, J=6.1 Hz), 7.02 (1 H, br. s.), 4.43 (1 H, br. s.), 3.89 (1 H, d, J=10.2 Hz), 3.69 (1 H, br. s.), 3.09 (1 H, d, J=12.3 Hz), 2.57-2.73 (2 H, m), 2.09 (1 H, d, J=12.1 Hz), 1.84 (1 H, dd, J=11.2, 4.3 Hz), 1.47 (9 H, s), 1.01 (1 H, q, J=12.3 Hz), 0.92 (3 H, d, J=6.5 Hz); and tert-butyl ((cis)-5-methyl-1-(3-nitropyridin-4-yl)piperidin-3-yl)carbamate (second eluting enantiomer) (890 mg, 13.5% yield) eluted second analytical supercritical-fluid chromatography (same conditions as above) as a bright yellow crystalline solid upon evaporation of the solvent and drying. MS (ESI, pos. ion) m/z: 337.1 (M+1). 1H NMR (400 MHz, CDCl3) δ ppm 8.83 (1 H, s), 8.35 (1 H, d, J=6.1 Hz), 6.94-7.07 (1 H, m), 4.42 (1 H, br. s.), 3.88 (1 H, br. s.), 3.69 (1 H, br. s.), 3.09 (1 H, d, J=11.2 Hz), 2.57-2.73 (2 H, m), 2.09 (1 H, d, J=12.3 Hz), 1.84 (1 H, dd, J=11.1, 4.4 Hz), 1.47 (9 H, s), 1.01 (1 H, q, J=11.8 Hz), 0.92 (3 H, d, J=6.7 Hz).