Sodium Hydroxide → tert-Butyl [(3S,5R)-5-methyl-1-(3-nitro-1-oxido-6,7-dihydro-5H-cyclopenta[b]pyridin-4-yl)piperidin-3-yl]carbamate

HRID 1499517Notes

Reaction equation

HRID 1499517 reaction equation
[CH3:1][C@H:2]1[CH2:7][N:6]([C:8]2[C:13]([N+:14]([O-:16])=[O:15])=[CH:12][N:11]=[C:10]3[CH2:17][CH2:18][CH2:19][C:9]=23)[CH2:5][C@@H:4]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:3]1.C1C=C(Cl)C=C(C(OO)=[O:36])C=1.[O-]S([O-])(=S)=O.[Na+].[Na+].[OH-].[Na+]>C(Cl)Cl>[CH3:1][C@H:2]1[CH2:7][N:6]([C:8]2[C:13]([N+:14]([O-:16])=[O:15])=[CH:12][N+:11]([O-:36])=[C:10]3[CH2:17][CH2:18][CH2:19][C:9]=23)[CH2:5][C@@H:4]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:3]1

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 86726747tert-Butyl [(3S,5R)-5-methyl-1-(3-nitro-6,7-dihydro-5H-cyclopenta[b]pyridin-4-yl)piperidin-3-yl]carbamate

Product 1

HCID 90296528tert-Butyl [(3S,5R)-5-methyl-1-(3-nitro-1-oxido-6,7-dihydro-5H-cyclopenta[b]pyridin-4-yl)piperidin-3-yl]carbamateYield 59.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of tert-butyl [(3S,5R)-5-methyl-1-(3-nitro-6,7-dihydro-5H-cyclopenta[b]pyridin-4-yl)piperidin-3-yl]carbamate (32.3 mg, 0.086 mmol) in DCM (0.50 mL) at 0° C. was added mCPBA (25.0 mg, 0.112 mmol). The reaction mixture was stirred at room temperature for 1 h. The mixture was treated with Na2S2O3 solution, followed by 1N NaOH, and stirred for 30 min. at room temperature. The organic layer was separated, dried, filtered and concentrated under vacuum to give the crude N-oxide product. The crude product was purified by preparative LC-MS (XBridge™ preparative C18 5 μm OBD™ column, 30×10 mm, 60 mL/min., eluting with a gradient of MeCN and water with 0.1% NH4OH) to afford the sub-title compound (20 mg, 40%). LCMS calc. for C19H29N4O5 (M+H)+: m/z=393.2. Found: 393.1.

Workup

  1. stirringstirred for 30 min. at room temperature
  2. customThe organic layer was separated
  3. customdried
  4. filtrationfiltered
  5. concentrationconcentrated under vacuum
  6. customto give the crude N-oxide product
  7. customThe crude product was purified by preparative LC-MS (XBridge™ preparative C18 5 μm OBD™ column, 30×10 mm, 60 mL/min.
  8. washeluting with a gradient of MeCN and water with 0.1% NH4OH)

Sources & evidence

ORD record
ord-4821b88a7337470dba72c1847bb351f4
Source dataset
uspto-grants-2015_12
Patent number
US09200004B2

Reaction notes

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