Imidazole → Ethyl trans-2-((tert-butyldiphenylsilyloxy)methyl)cyclopropanecarboxylate

HRID 2202259Notes

Reaction equation

HRID 2202259 reaction equation
B.C1COCC1.[CH2:7]([O:9][C:10]([C@@H:12]1[CH2:14][C@H:13]1[C:15]([OH:17])=O)=[O:11])[CH3:8].[C:18]([Si:22](Cl)([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([CH3:21])([CH3:20])[CH3:19].N1C=CN=C1>C1COCC1.O.CO>[Si:22]([O:17][CH2:15][C@@H:13]1[CH2:14][C@H:12]1[C:10]([O:9][CH2:7][CH3:8])=[O:11])([C:18]([CH3:21])([CH3:20])[CH3:19])([C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

8

Reactant 4

HCID 795ImidazoleHCID 94078tert-ButyldiphenylchlorosilaneHCID 2723981Borane;tetrahydrofuranHCID 11535603(1R,2R)-2-(ethoxycarbonyl)cyclopropane-1-carboxylic acid

Product 1

HCID 131735737Ethyl trans-2-((tert-butyldiphenylsilyloxy)methyl)cyclopropanecarboxylateYield 79%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

1M Borane-THF complex THF solution (85 mL, 84.98 mmol) was added to a solution of trans-2-(ethoxycarbonyl)cyclopropanecarboxylic acid (11.2 g, 70.82 mmol) in THF (100 mL) at 0° C., and the mixture was stirred overnight at room temperature. MeOH was added thereto, and then the gas was not generated. The reaction mixture was concentrated under reduced pressure. The residue was dissolved in DMF (50 mL), tert-butylchlorodiphenylsilane (20.10 mL, 84.98 mmol) and imidazole (5.79 g, 84.98 mmol) were added thereto, and the mixture was stirred for 5 hr. To the reaction mixture was added water, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent gradient; 2→35% ethyl acetate/hexane) to give ethyl trans-2-((tert-butyldiphenylsilyloxy)methyl)cyclopropanecarboxylate (21.40 g, 55.9 mmol, 79%) as a colorless oil.

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. dissolutionThe residue was dissolved in DMF (50 mL)
  3. stirringthe mixture was stirred for 5 hr
  4. extractionthe mixture was extracted with ethyl acetate
  5. washThe organic layer was washed with water and brine
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customthe obtained residue was purified by silica gel column chromatography (solvent gradient; 2→35% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-16305b4412bc4d2a9013982d402d7493
Source dataset
uspto-grants-2016_06
Patent number
US09365520B2

Reaction notes

Loading…