Iodine → HCID 24853065, compound

HRID 2245368Notes

Reaction equation

HRID 2245368 reaction equation
[CH2:1]=[C:2]1[S:6]/[C:5](=[N:7]\[C:8]([N:10]2[CH2:14][CH2:13][CH2:12][CH2:11]2)=[O:9])/[N:4]([C:15]2[CH:28]=[CH:27][C:18]3[O:19][C:20]([F:26])([F:25])[C:21]([F:24])([F:23])[O:22][C:17]=3[CH:16]=2)[CH2:3]1.ICl.C(=O)([O-])[O-:32].[Cs+].[Cs+].OS([O-])=O.[Na+].II>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C(Cl)Cl.C(O)(=O)C>[OH:32][CH2:1][C:2]1[S:6]/[C:5](=[N:7]\[C:8]([N:10]2[CH2:14][CH2:13][CH2:12][CH2:11]2)=[O:9])/[N:4]([C:15]2[CH:28]=[CH:27][C:18]3[O:19][C:20]([F:25])([F:26])[C:21]([F:24])([F:23])[O:22][C:17]=3[CH:16]=2)[CH:3]=1

Participants

9

Reactant 5

HCID 807IodineHCID 10796Cesium carbonateHCID 24640Iodine chlorideHCID 23665763Sodium BisulfiteHCID 24852960HCID 24852960, compound

Product 1

HCID 24853065HCID 24853065, compound

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent2×

Procedure

The alkene (Example 22D, 23 mg, 55 μmol) and tetrabutylammonium chloride (1.2 mg, 4 μmol) were dissolved into acetic acid (500 μL) and treated with 1 M iodine monochloride (110 μL, 110 μmol) in CH2Cl2, dropwise over 1 minute. After 15 minutes, cesium carbonate (18 mg, 55 μmol) was added. After another 10 minutes, solid NaHSO3 (16 mg, 150 μmol) was added, and the resulting suspension was thoroughly stirred until the deep iodine color had changed to a light orange (15 minutes). The suspension was diluted with CH2Cl2, stirred for 2 minutes, and filtered through a glass-fritted funnel with a CH2Cl2 rinse. The filtrate was concentrated, concentrated twice from EtOAc, dissolved into 20% EtOAc/CH2Cl2, and filtered through a pad of Aldrich basic alumina (activated, Brockmann 1, ˜150 mesh, CAS #1344-28-1) with a 20→50% EtOAc/CH2Cl2 rinse. The intermediate mixture was concentrated to 13 mg, dissolved into MeOH (500 μL), and treated with 1 M aqueous Cs2CO3 (30 μL). After ˜15 minutes, the mixture was concentrated and partitioned between CH2Cl2 and pH 7 potassium phosphate buffer. The aqueous phase was separated and extracted with CH2Cl2, and the combined organic phases were dried (Na2SO4), concentrated, and chromatographed through silica (20% EtOAc/CH2Cl2, then 5% MeOH/CH2Cl2) to give the title compound. 1H NMR (300 MHz, CDCl3) δ ppm 1.86 (4H), 3.44 (4H), 4.65 (2H), 6.89 (1H), 7.23 (1H), 7.37 (1H), 7.48 (1H); MS (ESI) m/z 434 (M+H)+.

Workup

  1. waitAfter another 10 minutes
  2. customhad changed to a light orange (15 minutes)
  3. filtrationfiltered through a glass-fritted funnel with a CH2Cl2
  4. washrinse
  5. concentrationThe filtrate was concentrated
  6. concentrationconcentrated twice from EtOAc
  7. dissolutiondissolved into 20% EtOAc/CH2Cl2
  8. filtrationfiltered through a pad of Aldrich basic alumina (activated, Brockmann 1, ˜150 mesh, CAS #1344-28-1) with a 20→50% EtOAc/CH2Cl2
  9. washrinse
  10. concentrationThe intermediate mixture was concentrated to 13 mg
  11. dissolutiondissolved into MeOH (500 μL)
  12. additiontreated with 1 M aqueous Cs2CO3 (30 μL)
  13. waitAfter ˜15 minutes
  14. concentrationthe mixture was concentrated
  15. custompartitioned between CH2Cl2 and pH 7 potassium phosphate buffer
  16. customThe aqueous phase was separated
  17. extractionextracted with CH2Cl2
  18. dry with materialthe combined organic phases were dried (Na2SO4)
  19. concentrationconcentrated
  20. customchromatographed through silica (20% EtOAc/CH2Cl2

Sources & evidence

ORD record
ord-6ae02c581da44b7cabf4dfa41cd64a55
Source dataset
uspto-grants-2010_03
Patent number
US07683084B2

Reaction notes

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