Dichloromethane → HCID 86728586, compound

HRID 1410299Notes

Reaction equation

HRID 1410299 reaction equation
[CH2:1]([O:4][C:5]1[CH:10]=[C:9]([Cl:11])[C:8]([CH2:12][C:13]2[CH:18]=[CH:17][C:16]([O:19][CH2:20][CH3:21])=[CH:15][CH:14]=2)=[CH:7][C:6]=1[C@H:22]1[C@H:27]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@@H:26]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@H:25]([O:44][CH2:45][C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C@@H:24]([CH2:52][O:53][CH2:54][C:55]2C=CC=CC=2)[O:23]1)[CH:2]=[CH2:3].ClCCl.FC(F)(F)S(O[Si](C)(C)C)(=O)=[O:67]>C(OC(=O)C)(=O)C>[C:54]([O:53][CH2:52][C@@H:24]1[C@@H:25]([O:44][CH2:45][C:46]2[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=2)[C@H:26]([O:36][CH2:37][C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C@@H:27]([O:28][CH2:29][C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C@H:22]([C:6]2[CH:7]=[C:8]([CH2:12][C:13]3[CH:14]=[CH:15][C:16]([O:19][CH2:20][CH3:21])=[CH:17][CH:18]=3)[C:9]([Cl:11])=[CH:10][C:5]=2[O:4][CH2:1][CH:2]=[CH2:3])[O:23]1)(=[O:67])[CH3:55]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 65367Trimethylsilyl triflateHCID 86714024HCID 86714024, compound

Product 1

HCID 86728586HCID 86728586, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Conditions

Temperature
-45 °C

Procedure

To a stirred −55° C. solution of (2S,3S,4R,5R,6R)-2-(2-(allyloxy)-4-chloro-5-(4-ethoxybenzyl)phenyl)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)tetrahydro-2H-pyran (19, 8.54 g, 10 mmol) from Step 3 in acetic anhydride (50 mL)/dichloromethane (50 mL) was dropwise added trimethylsilyl trifluoromethanesulfonate (4.7 mL, 26 mmol) at a rate such that the reaction temperature was maintained between −50 and −55° C. The solution was allowed to warm to −45° C. over 1.5 h prior to quenching with saturated sodium hydrogen carbonate solution. The reaction mixture was extracted with dichloromethane and the combined organic layers were washed with saturated sodium hydrogen carbonate solution prior to drying over magnesium sulfate. After filtration and concentration under reduced pressure, the crude residue was purified on a Biotage® purification apparatus (silica gel, 5 to 20% tetrahydrofuran in hexanes gradient) to yield the title compound (20, 7.8 g, 10 mmol, 100%) as a white solid.

Workup

  1. customTo a stirred −55° C.
  2. temperaturewas maintained between −50 and −55° C
  3. customto quenching with saturated sodium hydrogen carbonate solution
  4. extractionThe reaction mixture was extracted with dichloromethane
  5. washthe combined organic layers were washed with saturated sodium hydrogen carbonate solution
  6. dry with materialto drying over magnesium sulfate
  7. filtrationAfter filtration and concentration under reduced pressure
  8. customthe crude residue was purified on a Biotage® purification apparatus (silica gel, 5 to 20% tetrahydrofuran in hexanes gradient)

Sources & evidence

ORD record
ord-4266db4c9ac146998d99f10e4d9c0e90
Source dataset
uspto-grants-2014_12
Patent number
US08921412B2

Reaction notes

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