Diisopropylethylamine → HCID 70815046, compound

HRID 473898Notes

Reaction equation

HRID 473898 reaction equation
Br[C:2]1[CH:3]=[C:4]2[N:10]([C:11]([O:13][CH2:14][CH:15]([CH3:17])[CH3:16])=[O:12])[CH:9]=[N:8][C:5]2=[N:6][CH:7]=1.[CH3:18][C:19]([O:22][C:23]([N:25]1[CH2:31][C:30]2[CH:32]=[C:33](B(O)O)[CH:34]=[CH:35][C:29]=2[O:28][CH2:27][CH2:26]1)=[O:24])([CH3:21])[CH3:20].C(N(C(C)C)CC)(C)C>O1CCOCC1.C(OCC)(=O)C>[CH3:16][CH:15]([CH3:17])[CH2:14][O:13][C:11]([N:10]1[C:4]2[C:5](=[N:6][CH:7]=[C:2]([C:33]3[CH:34]=[CH:35][C:29]4[O:28][CH2:27][CH2:26][N:25]([C:23]([O:22][C:19]([CH3:20])([CH3:18])[CH3:21])=[O:24])[CH2:31][C:30]=4[CH:32]=3)[CH:3]=2)[N:8]=[CH:9]1)=[O:12]

Participants

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 59604707(4-(Tert-butoxycarbonyl)-2,3,4,5-tetrahydrobenzo[f][1,4]oxazepin-7-yl)boronic acidHCID 69675237HCID 69675237, compound

Product 1

HCID 70815046HCID 70815046, compoundYield 46%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

A flask was charged with isobutyl 6-bromo-1H-imidazo[4,5-b]pyridine-1-carboxylate (2.00 g, 6.82 mmol), (4-{[(1,1-dimethylethyl)oxy]carbonyl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)boronic acid (example 1, step 2) (2.00 g, 6.82 mmol), dichloro[1,1-bis(diphenylphosphino]ferrocenepalladium (II) dichloromethane adduct (0.14 g, 0.17 mmol), and diisopropylethylamine (3.50 g, 27.2 mmol) in dry dioxane (60 mL) and the mixture heated to 95° C. for 24 hours. The resulting mixture was diluted with ethyl acetate (100 mL) then washed with water (50 mL), 10% aqueous citric acid (50 mL) and brine. The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated. The residue was purified by silica gel column chromatography (ethyl acetate/hexane, 1:1) to give 1,1-dimethylethyl 7-(1-{[(2-methylpropyl)oxy]carbonyl}-1H-imidazo[4,5-b]pyridine-6-yl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (1.45 g, 46% yield) as a brown oil. MS (EI) for C25H30N4O5: 467 (MH+).

Workup

  1. washthen washed with water (50 mL), 10% aqueous citric acid (50 mL) and brine
  2. dry with materialThe organic phase was dried over anhydrous sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was purified by silica gel column chromatography (ethyl acetate/hexane, 1:1)

Sources & evidence

ORD record
ord-7956d46e44bd45b4a467c031a9175d32
Source dataset
uspto-grants-2014_01
Patent number
US08637499B2

Reaction notes

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