Acetic Acid → HCID 59262203, compound

HRID 644739Notes

Reaction equation

HRID 644739 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][N:9]2[CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C@@H:11]([CH3:22])[CH2:10]2)=[CH:4][CH:3]=1.CO[C:25]([CH3:27])=[CH2:26].C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C([O-])(O)=O.[Na+]>ClCCCl>[CH3:22][C@H:11]1[CH2:10][N:9]([CH2:8][C:5]2[CH:6]=[CH:7][C:2]([NH:1][CH:25]([CH3:27])[CH3:26])=[CH:3][CH:4]=2)[CH2:14][CH2:13][N:12]1[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 83002-MethoxypropeneHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 592622171,1-Dimethylethyl (2S)-4-[(4-aminophenyl)methyl]-2-methyl-1-piperazinecarboxylate

Product 1

HCID 59262203HCID 59262203, compoundYield 76.3%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent2×

Procedure

To a stirred solution of 1,1-dimethylethyl (2S)-4-[(4-aminophenyl)methyl]-2-methyl-1-piperazinecarboxylate (D2) (0.30 g, 1 mmol) in dry 1,2 DCE (5 mL) was added sequentially 2-methoxypropene (0.141 mL, 1.5 mmol), acetic acid (0.056 mL, 1 mmol) and sodium triacetoxyborohydride (0.313 g, 1.5 mmol). Further 1,2 DCE (5 mL) was added and the reaction mixture was stirred under argon at room temperature for 16 hours. Saturated NaHCO3 (15 mL) was added and reaction mixture stirred for a further 1 hour. The aqueous layer was then extracted with DCM (×3) and the combined organic layers were dried (Na2SO4) and concentrated in vacuo. The crude material was purified by column chromatography eluting with 0-100% ether/petroleum ether to give the title compound (0.265 g). δH (CDCl3, 400 MHz) 7.09 (2H, d), 6.54 (2H, d), 4.16 (1H, br.s), 3.78 (1H, d), 3.61 (1H, sp), 3.49 (1H, s), 3.42 (2H, m), 3.28 (1H, d), 3.08 (1H, td), 2.75 (1H, d), 2.59 (1H, d), 1.95 (1H, dd), 1.94 (1H, m), 1.45 (9H, s), 1.20 (9H, m). MS (AP+): 370.3 (MNa+), 248.3, no molecular ion (MH+) observed.

Workup

  1. customreaction mixture
  2. stirringstirred for a further 1 hour
  3. extractionThe aqueous layer was then extracted with DCM (×3)
  4. dry with materialthe combined organic layers were dried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customThe crude material was purified by column chromatography
  7. washeluting with 0-100% ether/petroleum ether

Sources & evidence

ORD record
ord-864ae3dc3ed94c6099a1491a3efb8907
Source dataset
uspto-grants-2010_04
Patent number
US07700599B2

Reaction notes

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