Cerium(III) chloride → HCID 22857048, compound

HRID 567146Notes

Reaction equation

HRID 567146 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[Mg]Br.[C:11]1([C:17]2([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C@@H:25]3[C@@H:21]([CH2:22][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:24]3)[C:20](=[O:33])[CH2:19][CH2:18]2)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[Cl-].[Ce+3].[Cl-].[Cl-].[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C>[C:11]1([C:17]2([C:34]3[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=3)[C@@H:25]3[C@@H:21]([CH2:22][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:24]3)[C@@:20]([C:4]3[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=3[O:2][CH3:1])([OH:33])[CH2:19][CH2:18]2)[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 24636Cerium(III) chlorideHCID 25517Ammonium ChlorideHCID 53854262HCID 53854262, compoundHCID 178489560HCID 178489560, compound

Product 1

HCID 22857048HCID 22857048, compoundYield 69.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A suspension of 2-methoxyphenylmagnesium bromide (prepared from 75.3 g of 2-bromoanisole and 9.8 g of magnesium) in 100 cm3 of dry tetrahydrofuran is added dropwise at room temperature with stirring to a suspension of 20 g of (3aS,7aS)-7,7-diphenyl-2-(tert-butoxycarbonyl)perhydroisoindol-4-one and 31.6 g of anhydrous cerium chloride in 250 cm3 of dry tetrahydrofuran. The reaction mixture is stirred at room temperature for 24 hours, treated with 400 cm3 of a saturated aqueous ammonium chloride solution, diluted with 200 cm3 of ethyl acetate, washed with 300 cm3 of water (twice) and then with 300 cm3 of a saturated aqueous sodium chloride solution, dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure (2.7 kPa). The residue is chromatographed on a column of Merck silica gel (particle size 0.04-0.06 mm, diameter of 5.8 cm, height 26.5 cm), eluting under a pressure of 0.5 bar of nitrogen with a mixture of cyclohexane and ethyl acetate (80/20 by volume) and collecting 100 cm3 fractions. Fractions 9 to 29 are combined and concentrated to dryness under reduced pressure (2.7 kPa). There are obtained 17.82 g of (3aS,4S,7aS)-7,7-diphenyl-4-(2-methoxyphenyl)-2-(tert-butoxycarbonyl)perhydroisoindol-4-ol in the form of a white foam.

Workup

  1. additionis added dropwise at room temperature
  2. washwashed with 300 cm3 of water (twice) and then with 300 cm3 of a saturated aqueous sodium chloride solution
  3. dry with materialdried over magnesium sulphate
  4. filtrationfiltered
  5. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  6. customThe residue is chromatographed on a column of Merck silica gel (particle size 0.04-0.06 mm, diameter of 5.8 cm, height 26.5 cm)
  7. washeluting under a pressure of 0.5 bar of nitrogen with a mixture of cyclohexane and ethyl acetate (80/20 by volume)
  8. customcollecting 100 cm3 fractions
  9. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)

Sources & evidence

ORD record
ord-ec1c53c5dcb24d7991b8b96a647a9117
Source dataset
uspto-grants-2001_01
Patent number
US06177450B1

Reaction notes

Loading…