Triethylamine → HCID 131719036, compound

HRID 1647377Notes

Reaction equation

HRID 1647377 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[B:8]1[O:12]CC[O:9]1.[NH:13]([C:23]([O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[O:24])[CH2:14][C:15]([NH:17][C@H:18]([C:20]([OH:22])=[O:21])[CH3:19])=[O:16].C(N(CC)CC)C.C(P(=O)(OCC)OCC)#N>CN(C)C=O>[NH:13]([C:23]([O:25][CH2:26][C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)=[O:24])[CH2:14][C:15]([NH:17][C@H:18]([C:20]([OH:22])=[O:21])[CH3:19])=[O:16].[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[B:8]([OH:12])[OH:9]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 76257Diethyl cyanophosphonateHCID 6994034Z-Gly-ala-OHHCID 68539681HCID 68539681, compound

Product 1

HCID 131719036HCID 131719036, compoundYield 68.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of o-aminophenylboronic acid (13.7 g, 100 mmoles) in dichloromethane (200 ml) is added ethylene glycol (6.30 g, 102 mmoles). The solution is shaken for 20 minutes, and then stirred over solid sodium sulfate. Removal of the volatiles affords ethylene o-aminophenylboronate. To a flame dried three neck round bottom flask equipped with septum, stopper and gas inlet, is added ethylene o-aminophenylboronate (0.36 g, 2.20 mmoles) in dry dimethylformamide (10 ml). To this solution is added Z-Gly-Ala (0.62 g, 2.21 mmoles), triethylamine (0.62 ml, 4.45 mmoles), and finally diethyl cyanophosphonate (0.37 ml, 2.44 mmoles). After stirring the reaction at room temperature for 17 hours, the DMF is removed under reduced pressure. The remaining residue is dissolved in ethyl acetate, and washed sequentially with 10% HCl, saturated sodium bicarbonate, and brine. After drying the organic phase over magnesium sulfate, the salts are removed by filtration and filtrate concentrated in vacuum to leave (0.63 g) of Z-Gly-Ala-o- aminophenylboronic acid. This compound can be used "as is" in the present invention, or the benzyloxycarbonyl (Z) group can be removed by hydrogenolysis (see first step of Example 4).

Workup

  1. customTo a flame dried three neck round bottom flask
  2. customequipped with septum, stopper and gas inlet
  3. customthe reaction at room temperature for 17 hours
  4. customthe DMF is removed under reduced pressure
  5. dissolutionThe remaining residue is dissolved in ethyl acetate
  6. washwashed sequentially with 10% HCl, saturated sodium bicarbonate, and brine
  7. dry with materialAfter drying the organic phase over magnesium sulfate
  8. customthe salts are removed by filtration and filtrate
  9. concentrationconcentrated in vacuum

Sources & evidence

ORD record
ord-c523d738abc346df94679de8e54cfd53
Source dataset
uspto-grants-1995_07
Patent number
US05431842

Reaction notes

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