Dichloromethane → HCID 86587396, compound

HRID 966398Notes

Reaction equation

HRID 966398 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11]CC=C)[C@H:9]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:8]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:7][C@H:6]1[O:32][C@H:33]1[C@H:46]([O:47][CH2:48][C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[C@@H:45]([CH2:55][O:56][CH2:57][C:58]2[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=2)[O:44][C@@H:35]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@@H:34]1[O:64][C:65](=[O:67])[CH3:66])(=[O:3])[CH3:2].C1N2CCN(CC2)C1.ClCCl>C(O)C.C1(C)C=CC=CC=1.O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh]>[C:1]([O:4][C@@H:5]1[C@@H:10]([OH:11])[C@H:9]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:8]([CH2:23][O:24][CH2:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[O:7][C@H:6]1[O:32][C@H:33]1[C@H:46]([O:47][CH2:48][C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[C@@H:45]([CH2:55][O:56][CH2:57][C:58]2[CH:59]=[CH:60][CH:61]=[CH:62][CH:63]=2)[O:44][C@@H:35]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@@H:34]1[O:64][C:65](=[O:67])[CH3:66])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 9237DabcoHCID 86587397HCID 86587397, compound

Product 1

HCID 86587396HCID 86587396, compoundYield 49%

Reagents, catalysts & solvents 2

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)CatalystHCID 86587398Ethanol toluene waterSolvent

Procedure

1.28 g (1 eq.) of benzyl 2-O-acetyl-3-O-allyl-4,6-di-O-benzyl-β-D-gluco-pyranosyl-(1→3)-2-O-acetyl-4,6-di-O-benzyl-β-D-glucopyranoside (M=915) and 1.18 g of Dabco are dissolved in 50 ml of an ethanol/toluene/water (8/3/1; v/v/v) mixture and then 390 mg (0.3 eq.) of Wilkinson's catalyst are added thereto. The reaction medium is heated under reflux for 1 hour 30 minutes and then put to dryness. The mixture is then taken up with dichloromethane and extracted with water, with iced 1/2N HCl, with 5% NaHCO3 and then with water, dried and concentrated. The residue is then redissolved in 30 ml of an acetone/10% aq. HCl (19/1; v/v) mixture which is refluxed for 8 min. After rapid cooling to R.T., the solution is neutralised with a few drops of 5% NaHCO3 and concentrated. The whole is diluted again with dichloromethane and is extracted with water. The product is finally purified over silica gel [flash; eluent: toluene/ethyl acetate (85/15; v/v)] which thus enables isolating 600 mg of benzyl 2-O-acetyl-4,6-di-O-benzyl-β-D-glucopyranosyl-(1→3)-2-O-acetyl-4,6-di-O-benzyl-β-D-glucopyranoside (M=875).

Workup

  1. temperatureThe reaction medium is heated
  2. temperatureunder reflux for 1 hour 30 minutes
  3. extractionextracted with water, with iced 1/2N HCl, with 5% NaHCO3
  4. dry with materialwith water, dried
  5. concentrationconcentrated
  6. dissolutionThe residue is then redissolved in 30 ml of an acetone/10% aq. HCl (19/1; v/v) mixture which
  7. temperatureis refluxed for 8 min
  8. concentrationconcentrated
  9. additionThe whole is diluted again with dichloromethane
  10. extractionis extracted with water
  11. customThe product is finally purified over silica gel [flash; eluent: toluene/ethyl acetate (85/15; v/v)] which

Sources & evidence

ORD record
ord-895aca0c43d848e383a38c10a2b8c0f6
Source dataset
uspto-grants-2005_10
Patent number
US06951934B2

Reaction notes

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