Cesium carbonate → HCID 69918812, compound

HRID 2307746Notes

Reaction equation

HRID 2307746 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:10]([O:16][C:17](=[O:19])[CH3:18])[C@@H:9]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[O:8][CH:6]1[OH:7])(=[O:3])[CH3:2].C(=O)([O-])[O-].[Cs+].[Cs+].C([O:38][C:39](=[O:49])[CH:40]([C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)[CH2:41]Br)C1C=CC=CC=1.COC(C)(C)C>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.COC>[C:1]([O:4][C@H:5]1[C@@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:10]([O:16][C:17](=[O:19])[CH3:18])[C@@H:9]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[O:8][CH:6]1[O:7][CH2:41][CH:40]([C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)[C:39]([OH:49])=[O:38])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 15413tert-Butyl methyl etherHCID 117598232,3,4,6-TETRA-O-ACETYL-D-MANNOPYRANOSEHCID 12021262HCID 12021262, compound

Product 1

HCID 69918812HCID 69918812, compound

Reagents, catalysts & solvents 2

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 8254Dimethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

A mixture that consists of 34.83 g (100 mmol) of 2,3,4,6-tetra-O-acetyl-mannopyranose, 1.39 g (5 mmol) of tetrabutylammonium chloride and 35.8 g (110 mmol) of fine-powder cesium carbonate in 400 ml of dimethyl ether is cooled to 0° C. At 0° C., 47.88 g (150 mmol) of 2-phenyl-3-bromopropionic acid benzyl ester, dissolved in 30 ml of dimethyl ether, is added in drops over 10 minutes while being stirred vigorously. It is stirred for one hour at 0° C. 250 ml of MTB (methyl-tert-butyl ether) is added, solid is filtered out, and the filtrate is evaporated to the dry state in a vacuum. The residue is taken up in 500 ml of tetrahydrofuran. 5 g of palladium (10%) on activated carbon is added thereto and hydrogenated until hydrogen absorption is completed. Then, catalyst is filtered out, it is rewashed with a little tetrahydrofuran, the organic solutions are combined and evaporated to the dry state in a vacuum, dried, and the solvent is distilled off in a vacuum. The residue is chromatographed on silica gel (mobile solvent: dichloromethane/n=hexane/ethanol/acetic acid=20:5:3:0.5). The product-containing fractions are concentrated by evaporation, dissolved in 400 ml of ethyl acetate and shaken out three times with 200 ml of water. Then, the organic phase is separated and evaporated to the dry state in a vacuum.

Workup

  1. additionis added in drops over 10 minutes
  2. stirringIt is stirred for one hour at 0° C
  3. filtrationsolid is filtered out
  4. customthe filtrate is evaporated to the dry state in a vacuum
  5. addition5 g of palladium (10%) on activated carbon is added
  6. customhydrogenated until hydrogen absorption
  7. filtrationThen, catalyst is filtered out
  8. customevaporated to the dry state in a vacuum
  9. customdried
  10. distillationthe solvent is distilled off in a vacuum
  11. customThe residue is chromatographed on silica gel (mobile solvent: dichloromethane/n=hexane/ethanol/acetic acid=20:5:3:0.5)
  12. concentrationThe product-containing fractions are concentrated by evaporation
  13. dissolutiondissolved in 400 ml of ethyl acetate
  14. stirringshaken out three times with 200 ml of water
  15. customThen, the organic phase is separated
  16. customevaporated to the dry state in a vacuum

Sources & evidence

ORD record
ord-1e23de3e0627429fb5f7dcb08b717024
Source dataset
uspto-grants-2004_12
Patent number
US06831164B2

Reaction notes

Loading…