Benzoic Acid → (1S,4aS,7aR)-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylester

HRID 1976372Notes

Reaction equation

HRID 1976372 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]2[CH2:18][CH:17]=[CH:16][CH:7]2[CH:8]([O:11][C:12](=[O:15])[NH:13][CH3:14])[O:9][CH:10]=1)=[O:4].[C:19](O)(=[O:26])C1C=CC=CC=1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>O1CCCC1>[CH3:1][O:2][C:3]([C:5]1[C@H:6]2[CH2:18][CH:17]=[C:16]([CH2:19][OH:26])[C@@H:7]2[C@H:8]([O:11][C:12](=[O:15])[NH:13][CH3:14])[O:9][CH:10]=1)=[O:4]

Participants

5

Reactant 3

HCID 243Benzoic AcidHCID 2724141Tetrabutylammonium FluorideHCID 867566731-(Methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylester

Product 1

HCID 57107324(1S,4aS,7aR)-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylesterYield 98.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

28.5 g of the above (1S, 4aS, 7aR )-7-(tert-butyldiemthylsilyloxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylester were dissolved in tetrahydrofuran followed by addition of 35 g of benzoic acid. Next, 143 ml of tetra-n-butylammonium fluoride (1.0 M, tetrahydrofuran solution) were dropped in followed by stirring for 24 hours at room temperature. The reaction mixture was then extracted with ethyl acetate. After washing the organic phase with saturated aqueous sodium bicarbonate and brine, it was dried over magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain a colorless powder from the hexane-ether eluate in the form of (1S,4aS,7aR)-7-(hydroxy-methyl)-1-(methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylester (20.0 g, yield: 98.4%). The physicochemical properties of this compound are described in Table 66, Compound No. I-315.

Workup

  1. extractionThe reaction mixture was then extracted with ethyl acetate
  2. washAfter washing the organic phase with saturated aqueous sodium bicarbonate and brine, it
  3. dry with materialwas dried over magnesium sulfate
  4. distillationAfter distilling off the solvent under reduced pressure
  5. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-3b59b4c262f44436a8acc50fd5538f92
Source dataset
uspto-grants-2001_05
Patent number
US06225478B1

Reaction notes

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