Acetic Acid → HCID 86640928, compound

HRID 1819284Notes

Reaction equation

HRID 1819284 reaction equation
[O:1]=[C:2]1[CH2:11][CH2:10][C@@H:9]2[C@@H:4]([CH2:5][C@@H:6]([C:19]([OH:21])=[O:20])[N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:8]2)[CH2:3]1.O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ce+3].[C:33](O)(=O)[CH3:34]>C(O)C>[OH:1][C@H:2]1[CH2:11][CH2:10][C@@H:9]2[C@@H:4]([CH2:5][C@@H:6]([C:19]([O:21][CH2:33][CH3:34])=[O:20])[N:7]([C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])[CH2:8]2)[CH2:3]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 21585214Cerium trichloride heptahydrateHCID 68587535HCID 68587535, compound

Product 1

HCID 86640928HCID 86640928, compoundYield 35%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a −78° C. solution of (3S, 4aS, 8aR) 6-oxo-2-tert-butoxycarbonyl-1,2,3,4,4a, 5,6,7,8,8a-decahydroisoquinoline-3-carboxylic acid (6.88 g, 21.14 mmol)(see Preparation 2, Steps A and B, below and Scheme III, Step A generally) and cerium trichloride heptahydrate (7.9 g, 21.2 mmol) in absolute ethyl alcohol (90 mL), under nitrogen sodium borohydride (1.24 g, 32.73 mmol) was added in portions. The resulting mixture was slowly warmed up to room temperature over 5 hours. The reaction mixture was cooled down to 0° C. and acetic acid (50% in water, 25 mL) was carefully added. The resulting mixture was stirred for 1 hour at room temperature and the solvent was removed in vacuo. To the resulting material water and ethyl acetate were added and the phases separated. Aqueous layer was extracted with ethyl acetate (3×). The combined organic phases were dried, filtered and concentrated in vacuo. Flash chromatography (silicagel, 70% ethyl acetate/hexane) gave ethyl (3S, 4aS, 6S, 8aR) 6-hydroxy-2-tert -butoxycarbonyl-1,2,3,4,4a, 5,6,7,8,8a-decahydroisoquinoline-3-carboxylate (2.4 g, 35%) and the title compound (4.15 g, 60%)

Workup

  1. customTo a −78° C.
  2. customPreparation 2, Steps A and B
  3. temperatureThe reaction mixture was cooled down to 0° C.
  4. customthe solvent was removed in vacuo
  5. additionTo the resulting material water and ethyl acetate were added
  6. customthe phases separated
  7. extractionAqueous layer was extracted with ethyl acetate (3×)
  8. customThe combined organic phases were dried
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-23ea305fb30645cfbabf56b167119d80
Source dataset
uspto-grants-2009_10
Patent number
US07601738B2

Reaction notes

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