Diisopropylethylamine → HCID 178497349, compound

HRID 39665Notes

Reaction equation

HRID 39665 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:22]=[CH:21][C:8]2[NH:9][C:10]([C:12]3[N:13]([CH3:20])[CH:14]=[C:15]([N+:17]([O-])=O)[N:16]=3)=[N:11][C:7]=2[CH:6]=1)=[O:4].[CH3:23][C:24]([O:27][C:28]([NH:30][C:31]1[CH:35]=[C:34]([C:36](ON2N=NC3C2=CC=CC=3)=[O:37])[N:33]([CH3:48])[CH:32]=1)=[O:29])([CH3:26])[CH3:25].CCN(C(C)C)C(C)C>CN(C=O)C.[Pd]>[CH3:1][O:2][C:3]([C:5]1[CH:22]=[CH:21][C:8]2[NH:9][C:10]([C:12]3[N:13]([CH3:20])[CH:14]=[C:15]([NH:17][C:36]([C:34]4[N:33]([CH3:48])[CH:32]=[C:31]([NH:30][C:28]([O:27][C:24]([CH3:25])([CH3:23])[CH3:26])=[O:29])[CH:35]=4)=[O:37])[N:16]=3)=[N:11][C:7]=2[CH:6]=1)=[O:4]

Participants

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 27559874-Tert-butoxycarbonylamino-1-methyl-1h-pyrrole-2-carboxylic acid benzotriazol-1yl esterHCID 178497350HCID 178497350, compound

Product 1

HCID 178497349HCID 178497349, compoundYield 25%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

Pd/C (10 wt. %, 150 mg) was added to a solution of nitro-ester 21a (1.00 g, 3.32 mmol) in DMF (100 mL) and the mixture was hydrogenated at 450 psi for 2 h at ambient temperature. The reaction mixture was filtered through Celite to remove the catalyst and the filtrate was treated immediately with Boc-Py-OBt (27a, 1.42 g, 3.98 mmol) and DIEA (20 mL) and stirred at 60° C. for 18 h. The resulting yellow solution was poured into ice water and extracted with EtOAc. The organic phase was washed with 10% citric acid, brine, and saturated aqueous sodium bicarbonate and dried with MgSO4. Evaporation of the solvent yielded the crude product as a yellow foam which was purified by column chromatography on silica gel (n-hexane/EtOAc 1:2) to give the title compound as a beige solid (409 mg, 25%). 1H NMR (300 MHz, [D6] DMSO): δ=1.45 (s, 9H), 3.82 (s, 3H), 3.87 (s, 3H), 4.16 (s, 3H), 6.88 (s, 1H), 6.99 (s, 1H), 7.60-8.20 (m, 4H), 9.11 (s, 1H), 10.23 (s, 1H), 13.03 (br s, 1H); MS (ESI): m/z: 494 [M+H]+; HR-MS (FAB): calcd for C24H28N7O5: 494.2151; found: 494.2143 [M+H]+.

Workup

  1. filtrationThe reaction mixture was filtered through Celite
  2. customto remove the catalyst
  3. extractionextracted with EtOAc
  4. washThe organic phase was washed with 10% citric acid, brine, and saturated aqueous sodium bicarbonate
  5. dry with materialdried with MgSO4
  6. customEvaporation of the solvent
  7. customyielded the crude product as a yellow foam which
  8. customwas purified by column chromatography on silica gel (n-hexane/EtOAc 1:2)

Sources & evidence

ORD record
ord-6f92f2b476ce41e5943930e60fbb166f
Source dataset
uspto-grants-2013_09
Patent number
US08524899B2

Reaction notes

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