Acetyl chloride → HCID 67270128, compound

HRID 20025Notes

Reaction equation

HRID 20025 reaction equation
[Si:1]([O:8][CH2:9][C@H:10]1[O:14][C:13]([CH3:16])([CH3:15])[N:12]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C@H:11]1[CH2:24][C:25]1[CH:30]=[CH:29][N:28]=[CH:27][CH:26]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[C:31](Cl)(=O)C.C[Mg]Br.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C1COCC1.C(OCC)(=O)C>[Si:1]([O:8][CH2:9][C@H:10]1[O:14][C:13]([CH3:16])([CH3:15])[N:12]([C:17]([O:19][C:20]([CH3:21])([CH3:22])[CH3:23])=[O:18])[C@H:11]1[CH2:24][C:25]1[CH:26]=[CH:27][N:28]=[C:29]([CH3:31])[CH:30]=1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 6367Acetyl chlorideHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 67269665HCID 67269665, compoundHCID 178418573HCID 178418573, compound

Product 1

HCID 67270128HCID 67270128, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

(4S,5S)-Tert-butyl 5-((tert-butyldimethylsilyloxy)methyl)-2,2-dimethyl-4-(pyridin-4-ylmethyl)oxazolidine-3-carboxylate (0.150 g, 0.344 mmol) was dissolved in THF (3.5 mL) and cooled to 0° C. Acetyl chloride (0.0256 ml, 0.361 mmol) was added and the reaction was stirred 30 minutes before METHYLMAGNESIUM BROMIDE (0.294 ml, 0.412 mmol) was added. The reaction was stirred 1 hr. at 0° C. and then warmed to RT and quenched with saturated ammonium chloride and diluted with EtOAc and water. The layers were separated and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with a 9:1 aqueous solution of saturated ammonium chloride/ammonium hydroxide, water, brine, and dried over sodium sulfate. The crude product was dissolved in isopropylacetate (4 mL) and heated to 50° C. before DDQ (0.117 g, 0.515 mmol) was added. After 30 minutes the reaction was cooled and diluted with ethyl acetate and washed twice with saturated sodium bicarbonate, once with water, brine, and dried over sodium sulfate. The mixture was passed through a plug of silica gel with 2:1 Hexanes/EtOAc and concentrated to afford the title compound, MS m/z: 451.3(100%, M+1)).

Workup

  1. additionwas added
  2. temperatureat 0° C. and then warmed to RT
  3. customquenched with saturated ammonium chloride
  4. additiondiluted with EtOAc and water
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with EtOAc
  7. washThe combined organic layers were washed with a 9:1 aqueous solution of saturated ammonium chloride/ammonium hydroxide, water, brine
  8. dry with materialdried over sodium sulfate
  9. dissolutionThe crude product was dissolved in isopropylacetate (4 mL)
  10. additionwas added
  11. temperatureAfter 30 minutes the reaction was cooled
  12. washwashed twice with saturated sodium bicarbonate, once with water, brine
  13. dry with materialdried over sodium sulfate
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-92e11d13934544a5826c16166ebba383
Source dataset
uspto-grants-2010_06
Patent number
US07745484B2

Reaction notes

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