HCID 67344547, compound → HCID 67342218, compound

HRID 1257650Notes

Reaction equation

HRID 1257650 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][CH:14]([NH:17][C:18]2[C:23]([N+:24]([O-])=O)=[CH:22][N:21]=[C:20]3[N:27]([S:30]([C:33]4[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=4)(=[O:32])=[O:31])[CH:28]=[CH:29][C:19]=23)[CH2:13][CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>C(O)(=O)C.[Zn]>[CH2:1]([O:8][C:9]([N:11]1[CH2:12][CH2:13][CH:14]([NH:17][C:18]2[C:23]([NH2:24])=[CH:22][N:21]=[C:20]3[N:27]([S:30]([C:33]4[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=4)(=[O:32])=[O:31])[CH:28]=[CH:29][C:19]=23)[CH2:15][CH2:16]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 67344547HCID 67344547, compound

Product 1

HCID 67342218HCID 67342218, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
60 °C

Procedure

Zinc (24 g) was added to a solution of 4-(1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid benzyl ester (21.3 g, 40 mmol) in acetic acid (150 mL) and heated to 60° C. for 30 minutes. After cooling the mixture was filtered and the filtrate concentrated to dryness under vacuum. The resulting residue was partitioned between ethyl acetate and sodium hydrogen carbonate (sat. aq.), the organics layer dried with sodium sulphate and concentrated under vacuum. Purification by column chromatography on silica gel (gradient: 100% ethyl acetate) afforded 14.7 g (75%) of 4-(5-amino-1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridine-4-ylamino)-piperidine-1-carboxylic acid benzyl ester as a purple residue. 1H NMR (400 MHz, CDCl3) δ: 8.16-8.11 (m, 2H), 7.87 (s, 1H), 7.58-7.41 (m, 4H), 7.35 (m, 5H), 6.52 (d, 1H), 5.13 (s, 2H), 4.89 (br s, 1H), 4.11 (m, 2H), 3.95-3.84 (m, 1H), 3.10-2.96 (m, 2H), 2.10-2.05 (m, 1H), 1.54-1.40 (m, 2H).

Workup

  1. temperatureAfter cooling the mixture
  2. filtrationwas filtered
  3. concentrationthe filtrate concentrated to dryness under vacuum
  4. customThe resulting residue was partitioned between ethyl acetate and sodium hydrogen carbonate (sat. aq.)
  5. dry with materialthe organics layer dried with sodium sulphate
  6. concentrationconcentrated under vacuum
  7. customPurification by column chromatography on silica gel (gradient: 100% ethyl acetate)

Sources & evidence

ORD record
ord-515e387919304c42802cd9d24f49d76d
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

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