Chloroform → 4-Methoxyphenyl-3-O-allyl-2,4,6-tri-O-benzyl-b-D-galactopyranoside

HRID 1067046Notes

Reaction equation

HRID 1067046 reaction equation
[CH2:1]([O:4][C@H:5]1[C@@H:19]([OH:20])[C@@H:18]([CH2:21][OH:22])[O:17][C@@H:7]([O:8][C:9]2[CH:14]=[CH:13][C:12]([O:15][CH3:16])=[CH:11][CH:10]=2)[C@@H:6]1[OH:23])[CH:2]=[CH2:3].[H-].[Na+].[CH2:26](Br)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.C(Cl)(Cl)Cl>CN(C=O)C>[CH2:1]([O:4][C@H:5]1[C@@H:19]([O:20][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@@H:18]([CH2:21][O:22][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[O:17][C@@H:7]([O:8][C:9]2[CH:10]=[CH:11][C:12]([O:15][CH3:16])=[CH:13][CH:14]=2)[C@@H:6]1[O:23][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 6212ChloroformHCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 155408674-Methoxyphenyl 3-O-prop-2-en-1-yl-beta-D-galactopyranoside

Product 1

HCID 105794064-Methoxyphenyl-3-O-allyl-2,4,6-tri-O-benzyl-b-D-galactopyranosideYield 91%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of compound 8 (1.21 g, 3.71 mmol) in anhydrous DMF (15 mL), under nitrogen and cooled at 0° C., was added NaH (116 mg, 4.83 mmol). The reaction mixture was stirred 15 minutes at 0° C. and treated with benzyl bromide (0.66 mL, 5.57 mmol). After 12 hours at room temperature, the reaction mixture was cooled at 0° C., quenched by slow addition of water and extracted with chloroform. The combined organic layers were washed with H2O, dried over anhydrous Na2SO4, filtered and the solvents were evaporated. Purification by chromatography on silica gel (ethyl acetate-petroleum ether, v/v 1:3) afforded 91% as white crystals in 91% yield (2.01 g). mp=59-61° C.; [αD]24=−23° (c 1, CHCl3); 1H NMR (500 MHz, CDCl3): δ3.48 (dd, 1H, J2,3 9.6 Hz, J3,4 2.8 Hz, H-3), 3.63 (bs, 3H, H-5, H-6a and H-6b), 3.75 (s, 3H, OMe), 3.90 (d, 1H, J4,5<1.5 Hz, H-4), 4.01 (dd, 1H, J1,2 7.8 Hz, H-2), 4.22 (m, 2H, OCH2), 4.40, 4.45, 4.64, 4.84, 4.96 and 4.97 (6 d, 1H each, JA,B 11.7 Hz, CH2Ph), 4.83 (d, 1H, H-1), 5.19 and 5.33 (2 dd, 1H each, CH═CH2), 5.95 (m, 1H, CH═CH2), 6.78 and 7.02 (2 d, 2H each, C6H4), 7.22-7.40 (m, 15H, 3C6H5). Anal. Calcd for C37H40O7 (596.7): C 74.48, H 6.76; found: C 74.32, H 6.75.

Workup

  1. waitAfter 12 hours at room temperature
  2. temperaturethe reaction mixture was cooled at 0° C.
  3. customquenched by slow addition of water
  4. extractionextracted with chloroform
  5. washThe combined organic layers were washed with H2O
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltered
  8. customthe solvents were evaporated
  9. customPurification by chromatography on silica gel (ethyl acetate-petroleum ether, v/v 1:3)
  10. customafforded 91% as white crystals in 91% yield (2.01 g)

Sources & evidence

ORD record
ord-5fd7f82a840344f3b2c806e0fc74d5c9
Source dataset
uspto-grants-2001_06
Patent number
US06245902B1

Reaction notes

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