tert-Butyl 4-((2-amino-5-chloro-3-nitrobenzoyloxy)methyl)-4-(4-fluorophenyl)piperidine-1-carboxylate → tert-Butyl 4-((2,3-diamino-5-chlorobenzoyloxy)methyl)-4-(4-fluorophenyl)piperidine-1-carboxylate

HRID 913936Notes

Reaction equation

HRID 913936 reaction equation
[NH2:1][C:2]1[C:31]([N+:32]([O-])=O)=[CH:30][C:29]([Cl:35])=[CH:28][C:3]=1[C:4]([O:6][CH2:7][C:8]1([C:21]2[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=2)[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]1)=[O:5]>C(OCC)(=O)C.[Pd]>[NH2:1][C:2]1[C:31]([NH2:32])=[CH:30][C:29]([Cl:35])=[CH:28][C:3]=1[C:4]([O:6][CH2:7][C:8]1([C:21]2[CH:22]=[CH:23][C:24]([F:27])=[CH:25][CH:26]=2)[CH2:9][CH2:10][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:12][CH2:13]1)=[O:5]

Participants

4

Reactant 1

HCID 57546235tert-Butyl 4-((2-amino-5-chloro-3-nitrobenzoyloxy)methyl)-4-(4-fluorophenyl)piperidine-1-carboxylate

Product 1

HCID 57545959tert-Butyl 4-((2,3-diamino-5-chlorobenzoyloxy)methyl)-4-(4-fluorophenyl)piperidine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of tert-butyl 4-((2-amino-5-chloro-3-nitrobenzoyloxy)methyl)-4-(4-fluorophenyl)piperidine-1-carboxylate (700 mg, 1.4 mmol) in ethyl acetate (20 mL) under nitrogen was added palladium (10% on carbon, 140 mg). The flask was flushed with hydrogen and shaken under 60 psi of hydrogen overnight. The reaction was filtered through celite and concentrated to give 715 mg (quant.) as a foam semi-solid which was used without purification. tR=3.19 (Sunfire C18 4.6×50 mm, A=90% H2O/10% ACN, B=90% ACN/10% H2O, Modifier 0.1% TFA, 0.00 min=0% B, 4.0 min=100% B, 5.0 min=100% B, Flow rate=4 mL/min. Mass spec.: 377.88 (MH-Boc)+.

Workup

  1. customThe flask was flushed with hydrogen
  2. filtrationThe reaction was filtered through celite and
  3. concentrationconcentrated
  4. customto give 715 mg (quant.) as a foam semi-solid which
  5. customwas used without purification
  6. customA=90% H2O/10% ACN, B=90% ACN/10% H2O, Modifier 0.1% TFA, 0.00 min=0% B, 4.0 min=100% B, 5.0 min=100% B, Flow rate=4 mL/min

Sources & evidence

ORD record
ord-9c72e1872457498897c0eabf2a0c10d8
Source dataset
uspto-grants-2011_09
Patent number
US08026257B2

Reaction notes

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