m-Chloroperbenzoic acid → HCID 25010057, compound

HRID 2093231Notes

Reaction equation

HRID 2093231 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][C:12]([C:15]([O:17][CH3:18])=[O:16])=[CH:11][C:10]=2[CH3:19])=[CH:5][C:4]=1[C:20]1[CH:25]=[CH:24][C:23]([C:26]([F:29])([F:28])[F:27])=[CH:22][C:21]=1[CH2:30][N:31]1[C@@H:35]([CH3:36])[C@@H:34]([C:37]2[CH:42]=[CH:41][N:40]=[CH:39][CH:38]=2)[O:33][C:32]1=[O:43].[Cl:44]C1C=CC=C(C(OO)=O)C=1>C(Cl)Cl.O=P(Cl)(Cl)Cl>[Cl:44][C:39]1[CH:38]=[C:37]([C@H:34]2[O:33][C:32](=[O:43])[N:31]([CH2:30][C:21]3[CH:22]=[C:23]([C:26]([F:28])([F:29])[F:27])[CH:24]=[CH:25][C:20]=3[C:4]3[CH:5]=[C:6]([C:9]4[CH:14]=[CH:13][C:12]([C:15]([O:17][CH3:18])=[O:16])=[CH:11][C:10]=4[CH3:19])[CH:7]=[CH:8][C:3]=3[O:2][CH3:1])[C@H:35]2[CH3:36])[CH:42]=[CH:41][N:40]=1

Participants

5

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 25009503HCID 25009503, compound

Product 1

HCID 25010057HCID 25010057, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 24813Phosphorus oxychlorideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of methyl 4′-methoxy-2-methyl-2″-{[(4S,5R)-4-methyl-2-oxo-5-pyridin-4-yl-1,3-oxazolidin-3-yl]methyl}-4″-(trifluoromethyl)-1,1′:3′,1″-terphenyl-4-carboxylate (175 mg, 0.296 mmol) in CH2Cl2 (15 mL) at 0° C. under N2, was added 3-chloroperbenzoic acid (146 mg, 0.593 mmol) as a powder. The mixture was stirred at 0° C. for 15 min. Then it was allowed to warm up to room temperature and stirred for 2 h. The reaction mixture was diluted with CH2Cl2 and washed with satd Na2SO3 (1×) followed satd K2CO3 (2×). The organic layer was dried (Na2SO4), filtered and the solvent was evaporated in vacuo. The residue obtained was dissolved in POCl3 (10 mL). The resulting solution was heated at 110° C. under N2 for 2 h. Then it was allowed to warm to room temperature and stirred for 2 h. The reaction was concentrated in vacuo. The residue was diluted with EtOAc (50 mL) and water (10 mL) and washed with satd NaHCO3 (20 mL). The aqueous layer was extracted with EtOAc (2×40 mL). The combined organic layers were dried (Na2SO4), filtered and the solvent was evaporated in vacuo. The residue was purified by flash chromatography on silica gel to give methyl 2″-{[(4S,5R)-5-(2-chloropyridin-4-yl)-4-methyl-2-oxo-1,3-oxazolidin-3-yl]methyl}-4′-methoxy-2-methyl-4″-(trifluoromethyl)-1,1′:3′,1″-terphenyl-4-carboxylate. LCMS calc.=625.2; found=625.0 (M+1)−. 1H NMR (500 MHz, CDCl3, 1:1 mixture of atropisomers) δ 8.40 (s, 0.5 H); 8.39 (s, 0.5 H); 7.97 (s, 1 H); 7.90 (t, J=5.8 Hz, 1 H); 7.72 (s, 0.5 H); 7.69-7.63 (m, 1.5 H); 7.48 (d, J=11.8 Hz, 0.5 H); 7.44 (s, 0.5 H); 7.43-7.37 (m, 1 H); 7.32-7.26 (m, 1 H); 7.24 (s, 0.5 H); 7.20 (s, 0.5 H); 7.16 (d, J=2.2 Hz, 0.5 H); 7.14 (d, J=2.2 Hz, 0.5 H); 7.12-7.06 (m, 1.5 H); 7.05 (d, J=5.1 Hz, 0.5H); 5.42 (d, J=8.1 Hz, 0.5H); 5.18 (d, J=8.1 Hz, 0.5 H); 4.92 (dd, J=15.9, 18.5 Hz, 1 H); 4.19 (d, J=15.8 Hz, 0.5 H); 3.99 (d, J=15.8 Hz, 0.5 H); 3.95 (s, 3 H); 3.88 (s, 3 H); 3.81-3.75 (m, 1 H); 2.39 (s, 1.5 H); 2.35 (s, 1.5 H); 0.60 (d, J=6.5 Hz, 1.5 H); 0.49 (d, J=6.5 Hz, 1.5 H).

Workup

  1. temperatureto warm up to room temperature
  2. stirringstirred for 2 h
  3. washwashed with satd Na2SO3 (1×)
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. filtrationfiltered
  6. customthe solvent was evaporated in vacuo
  7. customThe residue obtained
  8. temperatureThe resulting solution was heated at 110° C. under N2 for 2 h
  9. temperatureto warm to room temperature
  10. stirringstirred for 2 h
  11. concentrationThe reaction was concentrated in vacuo
  12. additionThe residue was diluted with EtOAc (50 mL) and water (10 mL)
  13. washwashed with satd NaHCO3 (20 mL)
  14. extractionThe aqueous layer was extracted with EtOAc (2×40 mL)
  15. dry with materialThe combined organic layers were dried (Na2SO4)
  16. filtrationfiltered
  17. customthe solvent was evaporated in vacuo
  18. customThe residue was purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-0aaa19899591483c8ca435dd3b8adfb7
Source dataset
uspto-grants-2013_05
Patent number
US08440702B2

Reaction notes

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