Acetic Acid → (4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-Hexahydro-6-hydroxy-8-(2-ethyl-2-methylbutyryloxy)-2-methyl-1-naphthyl]ethyl}tetrahydro-4-hydroxy-2H-pyran-2-one

HRID 400154Notes

Reaction equation

HRID 400154 reaction equation
[Si]([O:8][C@H:9]1[CH2:18][C@H:17]([O:19][C:20](=[O:27])[C:21]([CH2:25][CH3:26])([CH3:24])[CH2:22][CH3:23])[C@H:16]2[C:11]([CH:12]=[CH:13][C@H:14]([CH3:45])[C@@H:15]2[CH2:28][CH2:29][C@H:30]2[O:35][C:34](=[O:36])[CH2:33][C@H:32]([O:37][Si](C(C)(C)C)(C)C)[CH2:31]2)=[CH:10]1)(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C(O)(=O)C>O1CCCC1>[OH:8][C@H:9]1[CH2:18][C@H:17]([O:19][C:20](=[O:27])[C:21]([CH2:25][CH3:26])([CH3:24])[CH2:22][CH3:23])[C@H:16]2[C:11]([CH:12]=[CH:13][C@H:14]([CH3:45])[C@@H:15]2[CH2:28][CH2:29][C@H:30]2[O:35][C:34](=[O:36])[CH2:33][C@H:32]([OH:37])[CH2:31]2)=[CH:10]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 2724141Tetrabutylammonium FluorideHCID 15285943HCID 15285943, compound

Product 1

HCID 15285944(4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-Hexahydro-6-hydroxy-8-(2-ethyl-2-methylbutyryloxy)-2-methyl-1-naphthyl]ethyl}tetrahydro-4-hydroxy-2H-pyran-2-oneYield 98.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 600 mg (0.9 mmol) of (4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-hexahydro-6-t-butyldimethylsilyloxy-8-(2-ethyl-2-methylbutyryloxy)-2-methyl-1-naphthyl]ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Example 5, above] in 2 ml of tetrahydrofuran was added to a mixture of 12.7 ml of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride and 1.27 ml of acetic acid, and the resulting mixture was stirred at room temperature for 15 hours. At the end of this time, the tetrahydrofuran was removed from the reaction mixture by distillation under reduced pressure. The residue was then diluted with 50 ml of ethyl acetate and the diluted solution was washed twice with 50 ml each time of water, three times with 30 ml each time of a saturated aqueous solution of sodium hydrogencarbonate and once with a saturated aqueous solution of sodium chloride, in that order. The organic layer was then dried over anhydrous magnesium sulfate and removed from the mixture by filtration, after which the solvent was removed by distillation under reduced pressure. The residue was purified by flash column chromatography through silica gel, using ethyl acetate as the eluent, to give 387 mg (98% yield) of the title compound as a colorless solid. This compound was recrystallized from a mixture of hexane and ethyl acetate to produce the title compound as colorless prisms, melting at between 152° and 154° C.

Workup

  1. customAt the end of this time, the tetrahydrofuran was removed from the reaction mixture by distillation under reduced pressure
  2. additionThe residue was then diluted with 50 ml of ethyl acetate
  3. washthe diluted solution was washed twice with 50 ml each time of water, three times with 30 ml each time of a saturated aqueous solution of sodium hydrogencarbonate and once with a saturated aqueous solution of sodium chloride, in that order
  4. dry with materialThe organic layer was then dried over anhydrous magnesium sulfate
  5. customremoved from the mixture by filtration
  6. customafter which the solvent was removed by distillation under reduced pressure
  7. customThe residue was purified by flash column chromatography through silica gel

Sources & evidence

ORD record
ord-1a77a3a24e0f4be89885b7a0a43188a1
Source dataset
uspto-grants-1998_10
Patent number
US05827855

Reaction notes

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