1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 86761092, compound

HRID 644966Notes

Reaction equation

HRID 644966 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2]/[CH:3]=[CH:4]/[CH3:5].[C:9]([NH:12][C:13]1[CH:18]=[CH:17][C:16]([S:19]([N:22]=[N+:23]=[N-:24])(=[O:21])=[O:20])=[CH:15][CH:14]=1)(=[O:11])[CH3:10].C1CCN2C(=NCCC2)CC1>CC#N>[C:9]([NH:12][C:13]1[CH:14]=[CH:15][C:16]([S:19]([N:22]=[N+:23]=[N-:24])(=[O:21])=[O:20])=[CH:17][CH:18]=1)(=[O:11])[CH3:10].[N+:22](=[C:2](/[CH:3]=[CH:4]/[CH3:5])[C:1]([O:7][CH3:8])=[O:6])=[N-:23]

Participants

6

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 642274(E)-Pent-3-enoic acid methyl esterHCID 51291854-Acetamidobenzenesulfonyl azide

Product 2

HCID 51291854-Acetamidobenzenesulfonyl azideHCID 86761092HCID 86761092, compoundYield 87.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Methyl (E)-2-diazo-3-pentenoate (5) was prepared using the scheme set forth in FIG. 7A. To a stirred solution of trans-pent-3-enoic acid (3.0 g, 30.0 mmol) in methanol (20 mL) was added concentrated H2SO4 (1 mL). The reaction mixture was stirred for 12 h at room temperature and then slowly neutralized with saturated sodium bicarbonate (NaHCO3). The aqueous layer was extracted with dichloromethane, and the combined organic layers were washed with brine and dried (Na2SO4). The solvent was removed under reduced pressure, and the remaining clear oil (3.30 g, 96% yield) was used for the next step, without further purification. To a stirred solution of methyl trans-pent-3-enoate (1.0 g, 8.77 mmol) and p-ABSA (3.15 g, 13.1 mmol) in CH3CN (20 mL) cooled to 0° C., was added DBU (2.66 g, 17.5 mmol) in one portion. p-ABSA (p-acetamidobenzenesulfonyl azide) was prepared using the procedure outlined in Baum et al., Synth. Commun., 17:1709ff (1987), which is hereby incorporated by reference. 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 purified by flash chromatography (SiO2, pentane) to give methyl (E)-2-diazo-3-pentenoate (5) (0.80 g, 65% yield) as an orange oil, which was stored in pentane below −10° C. until ready for use. The spectroscopic data are consistent with previously reported data (Davies et al., J. Org. Chem., 57:3186ff (1992), which is hereby incorporated by reference).

Workup

  1. customthen quenched with saturated ammonium chloride (NH4Cl)
  2. extractionThe aqueous layer was extracted with diethyl ether
  3. washthe combined organic layers were washed with brine
  4. dry with materialdried (Na2SO4)
  5. customThe solvent was removed under reduced pressure
  6. customthe residue was purified by flash chromatography (SiO2, pentane)

Sources & evidence

ORD record
ord-3976fb4aca7e4352b037e7a1b7281723
Source dataset
uspto-grants-2010_04
Patent number
US07700798B1

Reaction notes

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