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

HRID 1976376Notes

Reaction equation

HRID 1976376 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C@H:6]2[CH2:18][C@@H:17]3O[C@@:16]3([CH2:20]O)[C@@H:7]2[C@H:8]([O:11][C:12](=[O:15])[NH:13][CH3:14])[O:9][CH:10]=1)=[O:4].C(N(CC)CC)C.CS([Cl:33])(=O)=O>ClCCl>[CH3:1][O:2][C:3]([C:5]1[C@H:6]2[CH2:18][CH:17]=[C:16]([CH2:20][Cl:33])[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 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 86755120(1S,4aS,6S,7R,7aR)-6,7-epoxy-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,6,7,7a-hexahydrocyclopenta [c] pyrane-4-carboxylic acid methylester

Product 1

HCID 56979085(1S,4aS,7aR)-7-(chloromethyl)-1-(methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylesterYield 24%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2.0 g of (1S,4aS,6S,7R,7aR)-6,7-epoxy-7 -(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,6,7,7a-hexahydrocyclopenta [c] pyrane-4-carboxylic acid methylester described in Example 19 were dissolved in dichloromethane followed by addition of 2.5 ml of triethylamine and 1.4 ml of methanesulfonylchloride while stirring and cooling with ice. After stirring for 12 hours at the same temperature, the reaction mixture was 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 pale yellow oil from the hexane-ether eluate in the form of (1S,4aS,7aR)-7-(chloromethyl)-1-(methylcarbamoyloxy )-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylester (770 mg, yield: 24%). The physicochemical properties of this compound are described below.

Workup

  1. temperaturecooling with ice
  2. stirringAfter stirring for 12 hours at the same temperature
  3. extractionthe reaction mixture was extracted with ethyl-acetate
  4. washAfter washing the organic phase with saturated aqueous sodium bicarbonate and brine, it
  5. dry with materialwas dried over magnesium sulfate
  6. distillationAfter distilling off the solvent under reduced pressure
  7. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-44bcc818174d443bbd13476bca6a5152
Source dataset
uspto-grants-2001_05
Patent number
US06225478B1

Reaction notes

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