Sodium Nitrite → racemic trans [3-(6-benzenesulfonyl-6H-1,2,3,5,6-pentaaza-as-indacen-1-yl)-cyclopentyl]-carbamic acid tert-butyl ester

HRID 1257685Notes

Reaction equation

HRID 1257685 reaction equation
[N:1]([O-])=O.[Na+].[C:5]([O:9][C:10](=[O:37])[NH:11][C@H:12]1[CH2:16][CH2:15][C@H:14]([NH:17][C:18]2[C:23]([NH2:24])=[CH:22][N:21]=[C:20]3[N:25]([S:28]([C:31]4[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=4)(=[O:30])=[O:29])[CH:26]=[CH:27][C:19]=23)[CH2:13]1)([CH3:8])([CH3:7])[CH3:6]>C(O)(=O)C>[C:5]([O:9][C:10](=[O:37])[NH:11][C@H:12]1[CH2:16][CH2:15][C@H:14]([N:17]2[C:18]3[C:23](=[CH:22][N:21]=[C:20]4[C:19]=3[CH:27]=[CH:26][N:25]4[S:28]([C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)(=[O:30])=[O:29])[N:24]=[N:1]2)[CH2:13]1)([CH3:8])([CH3:6])[CH3:7]

Participants

4

Reactant 2

HCID 23668193Sodium NitriteHCID 131730636racemic trans [3-(5-amino-1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridin-4-ylamino)-cyclopentyl]-carbamic acid tert-butyl ester

Product 1

HCID 131730637racemic trans [3-(6-benzenesulfonyl-6H-1,2,3,5,6-pentaaza-as-indacen-1-yl)-cyclopentyl]-carbamic acid tert-butyl esterYield 87.2%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Sodium nitrite (612 mg, 8.87 mmol) was added to a stirred solution of racemic trans [3-(5-amino-1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridin-4-yl amino)-cyclopentyl]-carb amic acid tert-butyl ester (3.80 g, 8.06 mmol) in acetic acid (50 mL). Stirring was continued for 45 minutes at room temperature and then the solvent removed in vacuo. The residue was dissolved in ethyl acetate, washed (saturated sodium hydrogen carbonate (3×) and brine) and concentrated to dryness. Purification by column chromatography on silica gel (gradient: DCM to ethyl acetate) gave 3.39 g (87%) of racemic trans [3-(6-benzenesulfonyl-6H-1,2,3,5,6-pentaaza-as-indacen-1-yl)-cyclopentyl]-carbamic acid tert-butyl ester as a beige solid. LCMS (Method B, ESI): RT=4.00 min, m+H=483.3; 1H NMR (400 MHz, DMSO) δ: 9.20 (s, 1H), 8.15 (m, 3H), 7.73 (t, 1H), 7.63 (t, 2H), 7.45 (d, 1H), 7.15 (d, 1H), 5.65 (m, 1H), 4.21 (m, 1H), 2.44 (m, 2H, partially obscured by DMSO), 2.16 (m, 3H), 1.65 (m, 1H), 1.40 (s, 9H).

Workup

  1. customthe solvent removed in vacuo
  2. dissolutionThe residue was dissolved in ethyl acetate
  3. washwashed (saturated sodium hydrogen carbonate (3×) and brine)
  4. concentrationconcentrated to dryness
  5. customPurification by column chromatography on silica gel (gradient: DCM to ethyl acetate)

Sources & evidence

ORD record
ord-3fc28a980ce74760a069d2c41ad03a78
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

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