4-(1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid tert-butyl ester → 4-(5-Amino-1-benzenesulfonyl 1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid tert-butyl ester

HRID 1257617Notes

Reaction equation

HRID 1257617 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([NH:14][C:15]2[C:20]([N+:21]([O-])=O)=[CH:19][N:18]=[C:17]3[N:24]([S:27]([C:30]4[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=4)(=[O:29])=[O:28])[CH:25]=[CH:26][C:16]=23)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>C(O)(=O)C.[OH-].[Pd+2].[OH-]>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH2:10][CH:11]([NH:14][C:15]2[C:20]([NH2:21])=[CH:19][N:18]=[C:17]3[N:24]([S:27]([C:30]4[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=4)(=[O:28])=[O:29])[CH:25]=[CH:26][C:16]=23)[CH2:12][CH2:13]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 1

HCID 673440274-(1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid tert-butyl ester

Product 1

HCID 673232814-(5-Amino-1-benzenesulfonyl 1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid tert-butyl esterYield 82%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
50 °C

Procedure

Palladium hydroxide (20% wt on carbon, 2.2 g) was added to a solution of 4-(1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid tert-butyl ester (22.0 g, 43.9 mmol) in acetic acid (220 mL) under nitrogen. The reaction was evacuated and purged with hydrogen and the reaction warmed to 50° C. for 8 hours. The reaction vessel was recharged with hydrogen gas and stirred at room temperature for 18 hours. The mixture was then filtered through Celite® and the filtrate concentrated to dryness under vacuum. The resulting residue was partitioned between DCM and sodium hydrogen carbonate (sat. aq.), the organic layer dried with sodium sulphate and concentrated under vacuum. The residues were triturated with methanol, filtered, washed with diethyl ether and air dried to afford 16.9 g (82%) of 4-(5-amino-1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid tert-butyl ester. 1H NMR (400 MHz, CDCl3) δ: 8.14 (dd, 2H), 7.85 (s, 1H), 7.54 (m, 1H), 7.49 (d, 1H), 7.45 (m, 2H), 6.52 (d, 1H), 4.80 (br s, 1H), 4.05 (s, 2H), 3.86 (m, 1H), 2.97 (t, 2H), 2.61 (m, 2H), 2.03 (d, 2H), 1.46 (s, 9H).

Workup

  1. customThe reaction was evacuated
  2. custompurged with hydrogen
  3. filtrationThe mixture was then filtered through Celite®
  4. concentrationthe filtrate concentrated to dryness under vacuum
  5. customThe resulting residue was partitioned between DCM and sodium hydrogen carbonate (sat. aq.)
  6. dry with materialthe organic layer dried with sodium sulphate
  7. concentrationconcentrated under vacuum
  8. customThe residues were triturated with methanol
  9. filtrationfiltered
  10. washwashed with diethyl ether and air
  11. customdried

Sources & evidence

ORD record
ord-b71216b9aa894781b050eb7c918abb10
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

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