N,N,N',N'-Tetramethylethylenediamine → HCID 69448484, compound

HRID 1593012Notes

Reaction equation

HRID 1593012 reaction equation
CN(CCN(C)C)C.C([Mg]C1C=CC=CC=1)C1C=CC(SC)=CC=1.[Br-].[CH3:26][N:27]1[C@H:31]([CH3:32])[C@H:30]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[N:29]([C:39](=[O:47])[CH:40]=[CH:41][C:42]2[S:43][CH:44]=[CH:45][CH:46]=2)[C:28]1=[O:48].[O-:49][S:50]([C:53](F)(F)F)(=O)=[O:51].C([B+]CCCC)CCC.Cl[C:67]1[CH:72]=[CH:71][CH:70]=[C:69](C(OO)=O)[CH:68]=1>O1CCCC1.[Cu]I>[CH3:53][S:50]([C:67]1[CH:72]=[CH:71][C:70]([C@H:41]([C:42]2[S:43][CH:44]=[CH:45][CH:46]=2)[CH2:40][C:39]([N:29]2[C@@H:30]([C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C@@H:31]([CH3:32])[N:27]([CH3:26])[C:28]2=[O:48])=[O:47])=[CH:69][CH:68]=1)(=[O:51])=[O:49]

Participants

8

Reactant 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 70297m-Chloroperbenzoic acidHCID 69448973HCID 69448973, compoundHCID 178418657HCID 178418657, compoundHCID 178503171HCID 178503171, compound

Product 1

HCID 69448484HCID 69448484, compoundYield 64%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Copper (I) iodide (1.3 g, 6.89 mmol) was suspended in tetrahydrofuran (10 mL) under argon and TMEDA (1.14 mL, 7.58 mmol) was added as a single portion. After stirring for 10 min the solution was cooled to −78° C. and 4-thioanisyl phenylmagnesium bromide (14 mL, 6.89 mmol) was added dropwise. The resulting solution was then stirred for a further 30 min at −78° C. To this mixture was then added slowly a mixture of (4S,5R)-1,5-dimethyl-4-phenyl-3-(3-thiophen-2-yl-acryloyl)-imidazolidin-2-one (1.13 g) and dibutylboron triflate (4.2 mL, 4.14 mmol) in tetrahydrofuran (10 mL) at −78° C. and then the resulting mixture was stirred and allowed to warm to room temperature overnight. The reaction was then quenched with saturated aqueous ammonium chloride and washed with concentrated tetrasodium EDTA solution. The organics were then separated, concentrated and redissolved in ethyl acetate (100 mL). meta-Chloroperbenzoic acid (1.7 g, 6.9 mmol) was added as a single portion and the solution stirred for 2 h. This was then quenched with 2M aqueous sodium hydroxide solution and the resulting precipitate collected by filtration. This gave the sub-titled compound (1.06 g, 64%) as a white solid; NMR (CDCl3): 0.80 (d, 3H), 2.83 (s, 3H), 3.00 (s, 3H), 3.72 (dd, 1H), 3.85 (m, 1H), 4.05 (dd, 1H), 4.95 (t, 1H), 5.22 (d, 1H), 6.90 (m, 3H), 7.21 (m, 5H), 7.44 (d, 2H), 7.79 (d, 2H); LCMS: 483 (MH+).

Workup

  1. stirringThe resulting solution was then stirred for a further 30 min at −78° C
  2. additionTo this mixture was then added slowly
  3. stirringthe resulting mixture was stirred
  4. temperatureto warm to room temperature overnight
  5. customThe reaction was then quenched with saturated aqueous ammonium chloride
  6. washwashed with concentrated tetrasodium EDTA solution
  7. customThe organics were then separated
  8. concentrationconcentrated
  9. dissolutionredissolved in ethyl acetate (100 mL)
  10. stirringthe solution stirred for 2 h
  11. customThis was then quenched with 2M aqueous sodium hydroxide solution
  12. filtrationthe resulting precipitate collected by filtration

Sources & evidence

ORD record
ord-c6f8a16a8fc649f395fcfafcc6a979e6
Source dataset
uspto-grants-2007_11
Patent number
US07294636B2

Reaction notes

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