Diisopropylamine → HCID 66750599, compound

HRID 643920Notes

Reaction equation

HRID 643920 reaction equation
[Li]CCCC.C(NC(C)C)(C)C.[C:13]([N:18]1[C@@H:22]([CH3:23])[C@@H:21]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[O:20][C:19]1=[O:30])(=[O:17])[CH2:14][CH2:15][CH3:16].C[C@H]1[C@@H](C2C=CC=CC=2)OC(=O)N1.Br[CH2:45][C:46]1[CH:51]=[CH:50][C:49]([O:52][CH3:53])=[CH:48][C:47]=1[CH:54]=[CH2:55]>C1COCC1>[CH3:53][O:52][C:49]1[CH:50]=[CH:51][C:46]([CH2:45][C@@H:14]([CH2:15][CH3:16])[C:13]([N:18]2[C@@H:22]([CH3:23])[C@@H:21]([C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)[O:20][C:19]2=[O:30])=[O:17])=[C:47]([CH:54]=[CH2:55])[CH:48]=1

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 8531614-Methyl-5-phenyl-2-oxazolidinone, (4S,5R)-HCID 10868611HCID 10868611, compoundHCID 58027315HCID 58027315, compoundHCID 178418339Butyllithium

Product 1

HCID 66750599HCID 66750599, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

n-BuLi (21.3 mL, 53.3 mmol, 2.5 M in hexane) is added to a solution of diisopropylamine (8.2 mL, 58.1 mmol) in THF (150 mL) at −78° C. and the mixture is stirred at −78° C. for 10 min. A solution of (4S,5R)-3-butyryl-4-methyl-5-phenyloxazolidin-2-one (11.99 g, 48.5 mmol, prepared from (4S,5R)-4-methyl-5-phenyloxazolidin-2-one based on the procedure described in Tetrahedron Letters, 1986, 27, page 3311-3314) in THF (50 mL) is added. The mixture is stirred at −78° C. for 30 min. Finally, a solution of 1-bromomethyl-4-methoxy-2-vinylbenzene (11.1 g, crude) in THF (30 mL) is added. The mixture is stirred at −78° C. for 10 min and warmed to RT over 1 h and is continued to be stirred at RT for 15 h. The mixture is partitioned between EtOAc and sat. NH4Cl solution. The organic extract is dried with MgSO4, concentrated and purified by chromatography to give the title compound as an oil: 1H NMR (CDCl3) δ 0.68 (d, J=7 Hz, 3H), 0.95 (t, J=7 Hz, 3H), 1.52-1.59 (m, 1H), 1.73-1.79 (m, 1H), 2.80-2.85 (m, 1H), 2.98-3.04 (m, 1H), 3.78 (s, 3H), 4.14-4.20 (m, 1H), 4.70-4.75 (m, 1H), 5.34 (dd, J=1.3, 11 Hz, 1H), 5.57 (d, J=7.3 Hz, 1H), 5.63 (dd, J=1.3, 17 Hz, 1H), 6.72 (dd, J=2.5, 8 Hz, 1H), 6.99 (d, J=2.8 Hz, 1H), 7.04 (dd, J=11, 17 Hz, 1H), 7.13 (d, J=8 Hz, 1H), 7.21-7.24 (m, 2H), 7.35-7.40 (m, 3H).

Workup

  1. additionis added
  2. stirringThe mixture is stirred at −78° C. for 30 min
  3. stirringThe mixture is stirred at −78° C. for 10 min
  4. temperaturewarmed to RT over 1 h
  5. stirringto be stirred at RT for 15 h
  6. customThe mixture is partitioned between EtOAc and sat. NH4Cl solution
  7. extractionThe organic extract
  8. dry with materialis dried with MgSO4
  9. concentrationconcentrated
  10. custompurified by chromatography

Sources & evidence

ORD record
ord-d0a877e13e3a4483ac59e260614f0334
Source dataset
uspto-grants-2010_04
Patent number
US07700633B2

Reaction notes

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