Nitrogen → HCID 25140183, compound

HRID 1669158Notes

Reaction equation

HRID 1669158 reaction equation
N#N.I[C:4]1[N:5]=[N+:6]([O-:17])[C:7]2[CH:16]=[C:12]3[CH2:13][CH2:14][O:15][C:11]3=[CH:10][C:8]=2[N:9]=1.[CH2:18]([OH:21])[CH:19]=[CH2:20].C([O-])(O)=O.[Na+]>[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[O-:17][N+:6]1[C:7]2[CH:16]=[C:12]3[CH2:13][CH2:14][O:15][C:11]3=[CH:10][C:8]=2[N:9]=[C:4]([CH2:20][CH2:19][CH:18]=[O:21])[N:5]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 7858Allyl AlcoholHCID 516892Sodium BicarbonateHCID 25139486HCID 25139486, compound

Product 1

HCID 25140183HCID 25140183, compound

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

Pd(OAc)2 (53 mg, 0.24 mmol) was added to a N2-purged solution of iodide 213 (1.50 g, 4.8 mmol), allyl alcohol (0.91 mL, 13.3 mmol), nBu4NBr (1.38 g, 4.3 mmol) and NaHCO3 (880 mg, 10.5 mmol) in dry DMF (40 mL) and the solution was stirred at 60° C. for 24 h under N2. The mixture was quenched with saturated aqueous NH4Cl solution (150 mL) and filtered. The filtrate was extracted with EtOAc (5×50 mL), dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (20-50%) of EtOAc/pet. ether, to give aldehyde 214 as a dark oil, which was crystallised from MeOH to give a pale purple solid (532 mg, 45%): mp 140-142° C.; 1H NMR δ 9.92 (s, 1H, CHO), 8.26 (t, J=1.5 Hz, 1H, H-9), 7.10 (s, 1H, H-5), 4.80 (t, J=8.4 Hz, 2H, H-7), 3.43 (dt, J=8.4, 1.5 Hz, 2H, H-8), 3.29-3.33 (m, 2H, CH2), 3.06-3.10 (m, 2H, CH2); 13C NMR δ 200.4, 166.5, 165.0, 150.3, 135.2, 129.0, 116.2, 104.0, 73.1, 40.5, 29.4, 29.0; HRMS (FAB+) calcd for C12H12N3O3 (MH+) m/z 246.0879, found 246.0881.

Workup

  1. customThe mixture was quenched with saturated aqueous NH4Cl solution (150 mL)
  2. filtrationfiltered
  3. extractionThe filtrate was extracted with EtOAc (5×50 mL)
  4. customdried
  5. customthe solvent evaporated
  6. customThe residue was purified by chromatography
  7. washeluting with a gradient (20-50%) of EtOAc/pet. ether

Sources & evidence

ORD record
ord-861dc2a2d53d4a02942d50ae0160cb53
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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