(2E)-3-(4-{[(benzyloxy)carbonyl]amino}-2-fluorophenyl)prop-2-enyl diazoacetate → benzyl 3-fluoro-4-[(1S,5R,6R)-2-oxo-3-oxabicyclo[3.1.0]hex-6-yl]phenylcarbamate

HRID 1179491Notes

Reaction equation

HRID 1179491 reaction equation
[N+](=[CH:3][C:4]([O:6][CH2:7]/[CH:8]=[CH:9]/[C:10]1[CH:15]=[CH:14][C:13]([NH:16][C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[O:18])=[CH:12][C:11]=1[F:27])=[O:5])=[N-]>ClCCCl.C1(C)C=CC=CC=1>[F:27][C:11]1[CH:12]=[C:13]([NH:16][C:17](=[O:18])[O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:14]=[CH:15][C:10]=1[C@H:9]1[C@H:3]2[C@@H:8]1[CH2:7][O:6][C:4]2=[O:5]

Participants

4

Reactant 1

HCID 86600444(2E)-3-(4-{[(benzyloxy)carbonyl]amino}-2-fluorophenyl)prop-2-enyl diazoacetate

Product 1

HCID 11772207benzyl 3-fluoro-4-[(1S,5R,6R)-2-oxo-3-oxabicyclo[3.1.0]hex-6-yl]phenylcarbamate

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 1140TolueneSolvent

Procedure

A solution of (2E)-3-(4-{[(benzyloxy)carbonyl]amino}-2-fluorophenyl)prop-2-enyl diazoacetate (13.9 g, 37.5 mmol) in 1,2-dichloroethane (150 mL) was added dropwise over 14 h to a refluxing solution of bis-(N-t-butylsalicylaldiminato)copper(II) (0.82 g, 1.9 mmol, prepared as described by R. G. Charles, J. Org. Chem. 1957, 22, 677) in 1.5 L of toluene. After the addition was complete, the reaction mixture was heated another hour at reflux, then cooled, filtered and concentrated. The crude oil was purified by column chromatography (0-50% ethyl acetate-hexanes) to provide the (racemic) title compound as a yellow solid.

Workup

  1. additionAfter the addition
  2. temperaturethe reaction mixture was heated another hour
  3. temperatureat reflux
  4. temperaturecooled
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude oil was purified by column chromatography (0-50% ethyl acetate-hexanes)

Sources & evidence

ORD record
ord-dca31c1490f94582bd388d3ab6819f40
Source dataset
uspto-grants-2007_10
Patent number
US07279494B2

Reaction notes

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