Sulfuric Acid → (1-Formyl-2-vinyl-cyclopropyl)-carbamic acid tert-butyl ester

HRID 390121Notes

Reaction equation

HRID 390121 reaction equation
[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1([CH2:13][OH:14])[CH2:10][CH:9]1[CH:11]=[CH2:12])([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.CCCCCC.C(OCC)(=O)C.S(=O)(=O)(O)O>ClCCl.[NH4+].[NH4+].[O-][Mo]([O-])(=O)=O.S([O-])([O-])(=O)=O.[Ce+3].S([O-])([O-])(=O)=O.S([O-])([O-])(=O)=O.[Ce+3]>[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1([CH:13]=[O:14])[CH2:10][CH:9]1[CH:11]=[CH2:12])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 159087TriacetoxyperiodinaneHCID 21226206Ethyl acetate hexaneHCID 68591817(1-Hydroxymethyl-2-vinylcyclopropyl)-carbamic acid tert-butyl ester

Product 1

HCID 72539642(1-Formyl-2-vinyl-cyclopropyl)-carbamic acid tert-butyl esterYield 36%

Reagents, catalysts & solvents 2

HCID 131730262Ammoniummolybdate cerium sulfateCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of the alcohol 19a (0.152 g, 0.71 mmol) in dichloromethane (5 ml) was added Dess-Martin periodinane (0.33 g, 0.78 mmol) at rt. The reaction was monitored by TLC (3:2 Hexane-ethyl acetate, UV-monitoring and staining using ammoniummolybdate-cerium sulfate in aq. 10% sulfuric acid). Staining indicates a fairly clean reaction, but UV monitoring indicates several byproducts. After 1 h the obtained yellow-red solution was diluted with dichloromethane (20 ml), then washed with 1:1 aq. 10% sodium thiosulfate/aq. saturated sodium hydrogen carbonate (3×20 ml), then dried (Na2SO4), filtered and concentrated. Flash chromatography of the residue using stepwise gradient elution (ethyl acetate in hexane 20-30%) followed by concentration of the appropriate fractions and drying the residue in vacuum overnight, gave the title compound as a colorless oil (0.054 g, 0.255 mmol, 36%).

Workup

  1. customa fairly clean reaction, but UV monitoring
  2. washwashed with 1:1 aq. 10% sodium thiosulfate/aq
  3. dry with materialsaturated sodium hydrogen carbonate (3×20 ml), then dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. washgradient elution (ethyl acetate in hexane 20-30%)
  7. customdrying the residue in vacuum overnight

Sources & evidence

ORD record
ord-209f0734bbed4a2e84d4e0096c5fdea8
Source dataset
uspto-grants-2013_02
Patent number
US08383584B2

Reaction notes

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