Dabco → HCID 11213013, compound

HRID 917737Notes

Reaction equation

HRID 917737 reaction equation
[CH2:1]([N:4]1[C:9](=[O:10])[CH:8]=[C:7]([NH:11][C:12]2[CH:17]=[CH:16][C:15]([I:18])=[CH:14][C:13]=2[F:19])[C:6]([C:20]([NH2:22])=[O:21])=[CH:5]1)[CH:2]=C.[C:23]([O-:26])([O-])=O.[K+].[K+].C1N2CCN(CC2)C1.[O-:37]S(S([O-])=O)=O.[Na+].[Na+]>C(O)(C)(C)C.O.O=[Os](=O)(=O)=O>[OH:37][CH:2]([CH2:23][OH:26])[CH2:1][N:4]1[C:9](=[O:10])[CH:8]=[C:7]([NH:11][C:12]2[CH:17]=[CH:16][C:15]([I:18])=[CH:14][C:13]=2[F:19])[C:6]([C:20]([NH2:22])=[O:21])=[CH:5]1

Participants

8

Reactant 4

HCID 9237DabcoHCID 11430Potassium CarbonateHCID 24489Sodium DithioniteHCID 11177427HCID 11177427, compound

Product 1

HCID 11213013HCID 11213013, compoundYield 72%

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 6386tert-ButanolSolvent

Procedure

1-Allyl-4-(2-fluoro-4-iodoanilino)-6-oxo-1,6-dihydro-3-pyridinecarboxamide (400 mg, 0.97 mmol) was dissolved in a mixture of t-butanol (60 mL) and water (60 mL) and to the resulting solution was added K3Fe(CN)6 (956 mg, 2.91 mmol), K2CO3 (400 mg, 2.91 mmol), OsO4 (0.62 mL of a 4% w/w solution in water) and DABCO (108 mg, 0.97 mmol). The reaction mixture was stirred at R.T. for 15 h., then poured into 1 M Na2S2O4 (200 mL) and extracted with EtOAc (3×100 mL). The combined EtOAc extracts were washed with water (100 mL), brine (100 mL) and dried (Na2SO4). The solvent was removed under reduced pressure and the resulting oil purified by column chromatography on silica gel (5% MeOH/CH2Cl2 as eluant) to give 1-(2,3-dihydroxypropyl)-4-(2-fluoro-4-iodoanilino)-6-oxo-1,6-dihydro-3-pyridinecarboxamide as a white solid (312 mg, 72%), m.p. (EtOAc) 210-213° C. 1H NMR [(CD3)2SO, 400 MHz] δ 10.44 (s, 1H), 8.26 (s, 1H), 7.87 (br s, 1H), 7.73 (dd, J=10.2, 1.9 Hz, 1H), 7.57 (dd, J=8.4, 0.9 Hz, 1H), 7.46 (br s, 1H), 7.29 (t, J=8.5 Hz, 1H), 5.56 (d, J=0.9 Hz, 1H), 4.96 (d, J=5.5 Hz, 1H), 4.70 (t, J=4.7 Hz, 1H), 4.14 (dd, J=13.1, 3.5 Hz, 1H), 3.79-3.70 (m, 1H), 3.51 (dd, J=13.1, 8.3 Hz, 1H), 3.40-3.30 (m, 2H). Anal. Calcd for C15H15FIN3O4: C, 40.3; H, 3.4; N, 9.4. Found: C, 40.7; H, 3.7; N, 9.5.

Workup

  1. extractionextracted with EtOAc (3×100 mL)
  2. washThe combined EtOAc extracts were washed with water (100 mL), brine (100 mL)
  3. dry with materialdried (Na2SO4)
  4. customThe solvent was removed under reduced pressure
  5. customthe resulting oil purified by column chromatography on silica gel (5% MeOH/CH2Cl2 as eluant)

Sources & evidence

ORD record
ord-268a2aa34ae84ee6bde686acec9547c9
Source dataset
uspto-grants-2007_09
Patent number
US07273877B2

Reaction notes

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