Pyridine → N-(2-hydroxy-2-(4-(5-(2-(1-phenylcyclohexyl)ethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)-beta-alanine

HRID 71271Notes

Reaction equation

HRID 71271 reaction equation
N1C(F)=NC(F)=NC=1F.[C:10]1([C:16]2([CH2:22][CH2:23][C:24]([OH:26])=O)[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]2)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.N1C=CC=CC=1.[OH:33][CH:34]([C:46]1[CH:51]=[CH:50][C:49](/[C:52](=[N:54]/O)/[NH2:53])=[CH:48][CH:47]=1)[CH2:35][NH:36][CH2:37][CH2:38][C:39]([O:41]C(C)(C)C)=[O:40].C(N(C(C)C)CC)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1>ClCCl.C(OCC)(=O)C>[OH:33][CH:34]([C:46]1[CH:47]=[CH:48][C:49]([C:52]2[N:53]=[C:24]([CH2:23][CH2:22][C:16]3([C:10]4[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=4)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21]3)[O:26][N:54]=2)=[CH:50][CH:51]=1)[CH2:35][NH:36][CH2:37][CH2:38][C:39]([OH:41])=[O:40]

Participants

10

Conditions

Temperature
75 °C

Procedure

Cyanuric fluoride (0.018 mL, 0.215 mmol) was added to a mixture of 3-(1-phenylcyclohexyl)propanoic acid (50 mg, 0.215 mmol) and pyridine (0.017 mL, 0.215 mmol) in dichloromethane (5 mL). After 1 h, the reaction mixture was diluted with dichloromethane and washed with 1M aq. HCl solution. The organic layer was dried (MgSO4), filtered and concentrated. The residue was diluted with ethyl acetate and washed with saturated aqueous NaCl solution. The organic layer was dried (MgSO4), filtered and concentrated. This crude residue was dissolved in acetonitrile (5 mL). (Z)-tert-butyl 3-(2-hydroxy-2-(4-(N′-hydroxycarbamimidoyl)phenyl)ethylamino)propanoate (69.6 mg, 0.215 mmol) and diisopropylethyl amine (0.038 mL, 0.215 mmol) were added and the mixture was heated to 75° C. After 2 h, a 1M solution of tetra-n-butylammonium fluoride in THF (0.215 mL, 0.215 mmol) was added and the mixture was heated at 75° C. overnight. The reaction mixture was diluted with ethyl acetate and washed with saturated aqueous NaCl solution. The organic layer was dried (MgSO4), filtered and concentrated. The crude residue was treated with 1:1 mixture of dichloromethane and trifluoroacetic acid for 1 h. The mixture was concentrated, diluted with AcCN, filtered, and purified by HPLC (HPLC conditions: Phenomenex Luna C18 5 micron column (250×30 mm); 25-100% AcCN/water (0.1% TFA); 25 minute gradient; 20 mL/min) to obtain N-(2-hydroxy-2-(4-(5-(2-(1-phenylcyclohexyl)ethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)-beta-alanine (35 mg, 24% yield) as a colorless oil. 1H NMR (400 MHz, DMSO-d6): δ ppm 8.63 (1H, d), 7.95 (2H, d, J=8.57 Hz), 7.56 (2H, d, J=8.35 Hz), 7.30-7.45 (4H, m), 6.33 (1H, br, s), 4.95 (1H, dd, J=10.11, 2.2 Hz), 3.13-3.32 (3H, m), 2.99-3.09 (1H, m), 2.69 (2H, td, J=7.25, 2.64 Hz), 2.52-2.59 (2H, m), 2.15 (2H, d, J=14.5 Hz), 1.16-1.72 (11H, m).

Workup

  1. washwashed with 1M aq. HCl solution
  2. dry with materialThe organic layer was dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. additionThe residue was diluted with ethyl acetate
  6. washwashed with saturated aqueous NaCl solution
  7. dry with materialThe organic layer was dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. dissolutionThis crude residue was dissolved in acetonitrile (5 mL)
  11. waitAfter 2 h
  12. temperaturethe mixture was heated at 75° C. overnight
  13. washwashed with saturated aqueous NaCl solution
  14. dry with materialThe organic layer was dried (MgSO4)
  15. filtrationfiltered
  16. concentrationconcentrated
  17. additionThe crude residue was treated with 1:1 mixture of dichloromethane and trifluoroacetic acid for 1 h
  18. concentrationThe mixture was concentrated
  19. additiondiluted with AcCN
  20. filtrationfiltered
  21. custompurified by HPLC (HPLC conditions: Phenomenex Luna C18 5 micron column (250×30 mm); 25-100% AcCN/water (0.1% TFA); 25 minute gradient; 20 mL/min)

Sources & evidence

ORD record
ord-b9cad290b8a1410c92ddfca95b8afcde
Source dataset
uspto-grants-2014_09
Patent number
US08822510B2

Reaction notes

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