N,N'-Dimethylethylenediamine → (S)-3-(4-iodophenyl)-5,5-dimethyl-4-phenyloxazolidin-2-one

HRID 525317Notes

Reaction equation

HRID 525317 reaction equation
[CH3:1][C:2]1([CH3:14])[O:6][C:5](=[O:7])[NH:4][C@H:3]1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.[I:15][C:16]1[CH:21]=[CH:20][C:19](I)=[CH:18][CH:17]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].CNCCNC>[Cu]I.O1CCOCC1>[I:15][C:16]1[CH:21]=[CH:20][C:19]([N:4]2[C@@H:3]([C:8]3[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=3)[C:2]([CH3:14])([CH3:1])[O:6][C:5]2=[O:7])=[CH:18][CH:17]=1

Participants

7

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 12208p-DiiodobenzeneHCID 62657Potassium Phosphate, TribasicHCID 2733820(S)-(+)-5,5-Dimethyl-4-phenyl-2-oxazolidinone

Product 1

HCID 89813884(S)-3-(4-iodophenyl)-5,5-dimethyl-4-phenyloxazolidin-2-oneYield 61.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A resealable tube was charged with (S)-5,5-dimethyl-4-phenyloxazolidin-2-one (commercially available from Sigma-Aldrich, Milwaukee, Wis.) (1.01 g, 5.28 mmol), 1,4-diiodobenzene (commercially available from Sigma-Aldrich, Milwaukee, Wis.) (3.48 g, 10.56 mmol), tribasic potassium phosphate (5.61 g, 26.4 mmol) and dioxane (20.0 mL). The mixture was purged with argon and then copper (I) iodide (1.006 g, 5.28 mmol) and N,N′-dimethylethylenediamine (1.137 mL, 10.56 mmol) were added. The system was purged with argon, the tube was sealed, and the reaction mixture was heated at 100° C. for 12 hours. The reaction mixture was filtered through Celite® brand filter aid and concentrated to afford a purple solid. This material was purified via column chromatography on silica gel (RediSep 80 g column, gradient elution with 0-25% EtOAc-hexane) to afford (S)-3-(4-iodophenyl)-5,5-dimethyl-4-phenyloxazolidin-2-one (1.271 g, 3.23 mmol, 61.2% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ=7.64-7.59 (m, 2H), 7.39-7.33 (m, 2H), 7.33-7.27 (m, 3H), 7.26-7.20 (m, 2H), 5.43 (s, 1H), 1.61 (s, 3H), 0.89 (s, 3H).

Workup

  1. customThe mixture was purged with argon
  2. customThe system was purged with argon
  3. customthe tube was sealed
  4. filtrationThe reaction mixture was filtered through Celite® brand
  5. filtrationfilter aid
  6. concentrationconcentrated
  7. customto afford a purple solid
  8. customThis material was purified via column chromatography on silica gel (RediSep 80 g column, gradient elution with 0-25% EtOAc-hexane)

Sources & evidence

ORD record
ord-d1ad2784ad8e407384c3aac8cb848697
Source dataset
uspto-grants-2016_05
Patent number
US09340549B2

Reaction notes

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