Cerium(III) chloride → HCID 22857048, compound

HRID 375420Notes

Reaction equation

HRID 375420 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-]>O1CCCC1.[Cl-].[NH4+].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 3

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

Product 1

HCID 22857048HCID 22857048, compoundYield 69.8%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolventHCID 25517Ammonium ChlorideSolvent

Procedure

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

Workup

  1. additionis added dropwise
  2. washwashed with 300 cm3 of water (twice) and then with 300 cm3 of an aqueous saturated solution of sodium chloride
  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 Merck silica gel column (particle size 0.04-0.06 mm, diameter 5.8 cm, height 26.5 cm)
  7. washby eluting under a pressure of 0.5 bar of nitrogen with a mixture of cyclohexane and ethyl acetate (80/20 by volume)
  8. customcollecting fractions of 100 cm3
  9. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)

Sources & evidence

ORD record
ord-a652b0b114854222baf84c07d3e26b6c
Source dataset
uspto-grants-1996_01
Patent number
US05484804

Reaction notes

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