1,8-Diazabicyclo(5.4.0)undec-7-ene → (E)-Methyl 2-diazo-4-phenylbut-3-enoate

HRID 644967Notes

Reaction equation

HRID 644967 reaction equation
[C:1]1(/[CH:7]=[CH:8]/[CH2:9][C:10]([O:12][CH3:13])=[O:11])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CC(NC1C=CC(S([N:27]=[N+:28]=[N-])(=O)=O)=CC=1)=O.C1CCN2C(=NCCC2)CC1>CC#N>[N+:27](=[C:9](/[CH:8]=[CH:7]/[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[C:10]([O:12][CH3:13])=[O:11])=[N-:28]

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 51291854-Acetamidobenzenesulfonyl azideHCID 5370649Methyl (3E)-4-phenyl-3-butenoate

Product 1

HCID 29941320(E)-Methyl 2-diazo-4-phenylbut-3-enoateYield 80.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Methyl (E)-2-diazo-4-phenyl-3-butenoate (9) was prepared according to the procedure described in Davies, et al., J. Org. Chem., 56:3817 (1997) (“Davies II”), which is hereby incorporated by reference). The scheme is set forth in FIG. 7B. Briefly, to a stirred solution of methyl trans-4-phenylbut-3-enoate (1.0 g, 5.68 mmol) and p-ABSA (1.64 g, 6.82 mmol) in CH3CN (150 mL) cooled to 0° C., was added DBU (0.95 g, 6.25 mmol) in one portion. The reaction mixture was allowed to warm to room temperature over 7 h then quenched with saturated ammonium chloride (NH4Cl). The aqueous layer was extracted with diethyl ether, and the combined organic layers were washed with brine and dried (Na2SO4). The solvent was removed under reduced pressure, and the residue was triturated with a solution of pentane/diethyl:ether (1:1). The solid was filtered off, and the solvent was removed under reduced pressure. The residue was purified by flash chromatography (SiO2, pentane/diethyl:ether (15:1)) to give methyl (E)-2-diazo-4-phenyl-3-butenoate (9) (0.92 g, 80% yield) as an orange oil, which was stored neat at −10° C. until ready for use. The spectroscopic data are consistent with previously reported data ((Davies II, which is hereby incorporated by reference).

Workup

  1. customMethyl (E)-2-diazo-4-phenyl-3-butenoate (9) was prepared
  2. customthen quenched with saturated ammonium chloride (NH4Cl)
  3. extractionThe aqueous layer was extracted with diethyl ether
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried (Na2SO4)
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was triturated with a solution of pentane/diethyl
  8. filtrationThe solid was filtered off
  9. customthe solvent was removed under reduced pressure
  10. customThe residue was purified by flash chromatography (SiO2, pentane/diethyl:ether (15:1))

Sources & evidence

ORD record
ord-90c954ccad1f490c9a669c7d64a8ee32
Source dataset
uspto-grants-2010_04
Patent number
US07700798B1

Reaction notes

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