m-Chloroperbenzoic acid → HCID 68545922, compound

HRID 1446093Notes

Reaction equation

HRID 1446093 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N:27]2[CH2:31][CH:30]([CH2:32][OH:33])[O:29][C:28]2=[O:34])[CH:5]=[CH:6][C:7]=1[C:8]1[CH:9]=[N:10][C:11]([O:14][CH:15]2[CH2:20][O:19][C:18]3=[N:21][C:22]([N+:24]([O-:26])=[O:25])=[CH:23][N:17]3[CH2:16]2)=[CH:12][CH:13]=1.[C:35]([O:39][P:40](N(C(C)C)C(C)C)[O:41][C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:38])([CH3:37])[CH3:36].N1C=NN=N1.C1C=C(Cl)C=C(C(OO)=[O:66])C=1>CCOC(C)=O.C(Cl)Cl.CO.ClCCl.C1COCC1>[F:1][C:2]1[CH:3]=[C:4]([N:27]2[CH2:31][CH:30]([CH2:32][O:33][P:40](=[O:66])([O:39][C:35]([CH3:36])([CH3:37])[CH3:38])[O:41][C:42]([CH3:43])([CH3:44])[CH3:45])[O:29][C:28]2=[O:34])[CH:5]=[CH:6][C:7]=1[C:8]1[CH:9]=[N:10][C:11]([O:14][CH:15]2[CH2:20][O:19][C:18]3=[N:21][C:22]([N+:24]([O-:26])=[O:25])=[CH:23][N:17]3[CH2:16]2)=[CH:12][CH:13]=1.[F:1][C:2]1[CH:3]=[C:4]([N:27]2[CH2:31][CH:30]([CH2:32][O:33][P:40](=[O:41])([OH:66])[OH:39])[O:29][C:28]2=[O:34])[CH:5]=[CH:6][C:7]=1[C:8]1[CH:9]=[N:10][C:11]([O:14][CH:15]2[CH2:20][O:19][C:18]3=[N:21][C:22]([N+:24]([O-:26])=[O:25])=[CH:23][N:17]3[CH2:16]2)=[CH:12][CH:13]=1

Participants

10

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 853005Di-tert-butyl N,N-DiisopropylphosphoramiditeHCID 68545481HCID 68545481, compoundHCID 178418441HCID 178418441, compound

Product 2

HCID 68545922HCID 68545922, compoundYield 166.9%HCID 68550409HCID 68550409, compound

Reagents, catalysts & solvents 4

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

Phosphoric acid di-tert-butyl ester 3-{3-fluoro-4-[6-(2-nitro-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazin-6-yloxy)-pyridin-3-yl]-phenyl}-2-oxo-oxazolidin-5-ylmethyl ester was prepared according to the scheme shown in FIG. 16. In a round bottom flask was added 3-{3-Fluoro-4-[6-(2-nitro-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazin-6-yloxy)-pyridin-3-yl]-phenyl}-5-hydroxymethyl-oxazolidin-2-one (53 mg, 0.1 mmol), Diisopropyl-phosphoramidous acid di-tert-butyl ester (0.078 mL, 0.3 mmol), tetrazole (0.68 mL, ˜0.31 mmol, 0.45 M in MeCN), 15 mL dry THF and 2 mL dry dichloromethane. The resulting reaction mixture was stirred at room temperature for 16 hours before it was then cooled to −78° C. mCPBA (34 mg, 0.15 mmol) was added and the resulting solution was stirred at −78° C. for 2 hours. It was then warmed up to room temperature and diluted with 100 mL EtOAc, washed with saturated aqueous NaHCO3 (2×100 mL), brine, and dried over Na2SO4. Preparative TLC (CH2Cl2/MeOH, v/v, 10:1) gave the titled compound (46 mg, 70% yield) as white solid. ESI MS m/z 664 (M+H). 1H NMR (CDCl3) δ 8.29 (s, 1H), 7.79-7.84 (m, 1H), 7.58 (dd, J=12.8, 2.0 Hz, 1H), 7.45 (s, 1H), 7.39 (t, J=8.8 Hz, 1H), 7.33 (dd, J=8.8, 2.4 Hz, 1H), 6.86 (d, J=8.8 Hz, 1H), 5.77-5.82 (m, 1H), 4.84-4.92 (m, 1H), 4.84 (dd, J=12.4, 2.8 Hz, 1H), 4.55 (dd, J=12.4, 1.6 Hz, 1H), 4.41 (d, J=2.8 Hz, 2H), 4.04-4.27 (m, 4H), 1.49 (s, 9H), 1.45 (s, 9H).

Workup

  1. customThe resulting reaction mixture
  2. additionwas added
  3. stirringthe resulting solution was stirred at −78° C. for 2 hours
  4. temperatureIt was then warmed up to room temperature
  5. washwashed with saturated aqueous NaHCO3 (2×100 mL), brine
  6. dry with materialdried over Na2SO4

Sources & evidence

ORD record
ord-96376ecfb86b4e3ea5916d796585e523
Source dataset
uspto-grants-2010_02
Patent number
US07666864B2

Reaction notes

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