Trifluoroacetic acid → HCID 70229222, compound

HRID 2306891Notes

Reaction equation

HRID 2306891 reaction equation
C/[C:2](/[C:8]([O-:10])=[O:9])=[C:3](/[CH3:7])\[C:4]([O-])=O.F[C:12](F)(F)[C:13]([OH:15])=[O:14].[CH2:18]([N:25](COC)C[Si](C)(C)C)C1C=CC=CC=1.C([O-])([O-])=O.[Na+].[Na+].[C:40](Cl)([O:42][CH2:43][CH:44]1[C:56]2[C:51](=[CH:52][CH:53]=[CH:54][CH:55]=2)[C:50]2[C:45]1=[CH:46][CH:47]=[CH:48][CH:49]=2)=[O:41]>C(Cl)Cl.O1CCOCC1>[C:40]([N:25]1[CH2:18][C@@H:4]([CH2:12][C:13]([OH:15])=[O:14])[C@H:3]([CH2:2][C:8]([OH:10])=[O:9])[CH2:7]1)([O:42][CH2:43][CH:44]1[C:56]2[C:51](=[CH:52][CH:53]=[CH:54][CH:55]=2)[C:50]2[C:45]1=[CH:46][CH:47]=[CH:48][CH:49]=2)=[O:41]

Participants

8

Reactant 5

HCID 6422Trifluoroacetic acidHCID 10340Sodium CarbonateHCID 343679-Fluorenylmethyl chloroformateHCID 353442Benzyl(methoxymethyl)((trimethylsilyl)methyl)amineHCID 53249654(E)-2,3-dimethylbut-2-enedioate

Product 1

HCID 70229222HCID 70229222, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent2×

Procedure

Dimethylfumarate (38.7 g, 268 mmol) was dissolved in 1 l CH2Cl2, and trifluoroacetic acid added (3 ml, 40 mmol). The Azomethine ylide precursor N-Benzyl-N-Methoxymethyl-N-(Trimethylsilylmethyl)-amine was added dropwise with stirring (60.4 g, 255 mmol). The solution was stirred overnight at RT. The solvent was removed and the crude product was redissolved in 1.5 l methanol. 300 ml 1 N HCl was added, the solution degassed with Ar, and 10 g 10% Pd/C added. H2 was bubbled through then the solution stirred under a H2 balloon until the material was consumed (24 hr). The catalyst was filtered, the solvent removed and the residue redissolved in 500 ml H2O and 500 ml dioxane to which was added 32 g (300 mmol) Na2CO3. A solution of Fmoc-Cl (66 g, 255 mmol) in 500 ml dioxane was added dropwise. The solution was stirred 16 h, acidified to pH 3 and the solvent evaporated. The residue was extracted with EtOAc, washed with water, brine dried with MgSO4 and evaporated. 92 g title product was obtained.

Workup

  1. additionwas added dropwise
  2. stirringThe solution was stirred overnight at RT
  3. customThe solvent was removed
  4. dissolutionthe crude product was redissolved in 1.5 l methanol
  5. addition300 ml 1 N HCl was added
  6. customthe solution degassed with Ar, and 10 g 10% Pd/C
  7. additionadded
  8. customH2 was bubbled through then the solution
  9. stirringstirred under a H2 balloon until the material
  10. customwas consumed (24 hr)
  11. filtrationThe catalyst was filtered
  12. customthe solvent removed
  13. dissolutionthe residue redissolved in 500 ml H2O
  14. stirringThe solution was stirred 16 h
  15. customthe solvent evaporated
  16. extractionThe residue was extracted with EtOAc
  17. washwashed with water, brine
  18. dry with materialdried with MgSO4
  19. customevaporated

Sources & evidence

ORD record
ord-b276e629f53f44d7861c03e5d861b9a9
Source dataset
uspto-grants-2004_12
Patent number
US06828427B1

Reaction notes

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