Iodine → HCID 86594933, compound

HRID 723298Notes

Reaction equation

HRID 723298 reaction equation
[Mg].II.Br[CH2:5][CH:6]([CH3:8])[CH3:7].[C:9]([OH:12])(=[O:11])[CH3:10].[C:13]([OH:16])(=[O:15])[CH3:14].[C:17]([OH:20])(=[O:19])[CH3:18].[C:21]([OH:24])(=[O:23])[CH3:22].Br[C@@:26]1([O:35][C@H:34]([CH2:36][OH:37])[C@H:32]([OH:33])[C@H:30]([OH:31])[C@H:28]1[OH:29])[OH:27]>C(OCC)C.CC(O)=O.O>[C:9]([OH:12])(=[O:11])[CH3:10].[C:13]([OH:16])(=[O:15])[CH3:14].[C:17]([OH:20])(=[O:19])[CH3:18].[C:21]([OH:24])(=[O:23])[CH3:22].[CH2:5]([C@:26]1([O:35][C@H:34]([CH2:36][OH:37])[C@H:32]([OH:33])[C@H:30]([OH:31])[C@H:28]1[OH:29])[OH:27])[CH:6]([CH3:8])[CH3:7]

Participants

8

Reactant 4

HCID 807IodineHCID 65551-Bromo-2-methylpropaneHCID 5462224Magnesium2×HCID 86594934HCID 86594934, compound

Product 1

HCID 86594933HCID 86594933, compoundYield 69%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

Magnesium turnings (4.2 g) were suspended in diethyl ether (45 mL) and then initiated with a crystal of I2. 1-Bromo-2-methylpropane (1.37 mL, 12 mmol) was then added to the magnesium suspension. The mixture turned a cloudy white after the flask was heated with α heat gun. A solution of 1-bromo-α-D-galactose tetraacetate 4 (4.307 g, 10.5 mmol) in diethyl ether (10 mL) was added dropwise into the Grignard reaction mixture. The reaction went to completion after the mixture was heated at reflux for 4 h. The mixture was slowly poured into water (300 mL). Glacial AcOH (11 mL) was added. The mixture was separated and the aqueous layer was concentrated. The residue was treated with acetic anhydride (150 ML) and pyridine (150 mL) overnight. The resulting mixture was diluted with water (300 mL), extracted with diethyl ether (3×250 mL), washed with water (2×150 mL), and dried with magnesium sulfate. The solvent was removed under reduced pressure. The product was purified by flash chromatography (silica gel, 2:3 ethyl acetate/hexane) to afford 5 as a white solid (2.80 g, 7.24 mmol, 69%).

Workup

  1. temperaturewas heated with α heat gun
  2. temperaturewas heated
  3. temperatureat reflux for 4 h
  4. customThe mixture was separated
  5. concentrationthe aqueous layer was concentrated
  6. additionThe residue was treated with acetic anhydride (150 ML) and pyridine (150 mL) overnight
  7. additionThe resulting mixture was diluted with water (300 mL)
  8. extractionextracted with diethyl ether (3×250 mL)
  9. washwashed with water (2×150 mL)
  10. dry with materialdried with magnesium sulfate
  11. customThe solvent was removed under reduced pressure
  12. customThe product was purified by flash chromatography (silica gel, 2:3 ethyl acetate/hexane)

Sources & evidence

ORD record
ord-0da910e4a6ab491c9331f7441143a74b
Source dataset
uspto-grants-2006_11
Patent number
US07141394B2

Reaction notes

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