Trichloroacetonitrile → HCID 90330613, compound

HRID 590685

Reaction equation

HRID 590685 reaction equation
ClC(Cl)(Cl)C(OC1[O:41][C@@H:40]([CH3:42])[C@@H:29]([O:30][CH2:31][C:32]2C=CC(OC)=CC=2)[C@@H:18](OCC2C=CC(OC)=CC=2)[C@@H]1OCC1C=CC(OC)=CC=1)=N.[CH3:45][O:46][C:47]1[CH:82]=[CH:81][C:50]([CH2:51][O:52][C@H:53]2[C@H:59]([O:60][CH2:61][C:62]3[CH:67]=[CH:66][C:65]([O:68][CH3:69])=[CH:64][CH:63]=3)[C@H:58]([O:70][CH2:71][C:72]3[CH:77]=[CH:76][C:75]([O:78][CH3:79])=[CH:74][CH:73]=3)[C@H:57]([CH3:80])[O:56][CH:54]2[OH:55])=[CH:49][CH:48]=1.ClC(Cl)(Cl)C#N.[H-].[Na+].CC1C(=O)C(O)=C(C)O1.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C>C(OCC)C>[CH3:45][O:46][C:47]1[CH:48]=[CH:49][C:50]([CH2:51][O:52][C@H:53]2[C@H:59]([O:60][CH2:61][C:62]3[CH:67]=[CH:66][C:65]([O:68][CH3:69])=[CH:64][CH:63]=3)[C@H:58]([O:70][CH2:71][C:72]3[CH:73]=[CH:74][C:75]([O:78][CH3:79])=[CH:76][CH:77]=3)[C@H:57]([CH3:80])[O:56][C@H:54]2[O:55][C:42]2[C:40](=[O:41])[CH:29]([CH3:18])[O:30][C:31]=2[CH3:32])=[CH:81][CH:82]=1

Participants

8

Reactant 6

HCID 11011TrichloroacetonitrileHCID 19309FuraneolHCID 24758Sodium hydrideHCID 65367Trimethylsilyl triflateHCID 11763113HCID 11763113, compoundHCID 90330564HCID 90330564, compound

Product 1

HCID 90330613HCID 90330613, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

The solution of 2,3,4-tri-O-(4-methoxybenzyl)-L-fucopyranose trichloroacetimidate (a/β mixture, prepared from 85 mmol of 2,3,4-tri-O-(4-methoxybenzyl)-L-fucopyranose and trichloroacetonitrile in the presence of NaH in quantitative yield) in diethyl ether (100 ml) was added to a mixture of 2,5-dimethyl-4-hydroxy-3-oxo-(2H)-furan (85 mmol) and TMS-triflate (1.2 ml) in diethyl ether (200 ml) at −14° C. After 3 hours the cooling bath was removed and the stirring continued for 1 hour. The reaction mixture was diluted with ethyl acetate and extracted with sat. NaHCO3-solution (3×150 ml) and brine (150 ml). The organic phase was dried over Na2SO4 and evaporated. The resulting syrup was purified by column chromatography yielding 23.27 g of 2,5-dimethyl-3-oxo-(2H)-furan-4-yl 2,3,4-tri-O-(4-methoxybenzyl)-α-L-fucopyranoside as a thick yellow syrup in a 1:1 mixture of diastereoisomers. Selected NMR chemical shifts in CDCl3: anomeric protons: 5.32 and 5.57 ppm, J1,2=3.4 Hz; anomeric carbons: 113.81 and 113.95 Hz.

Workup

  1. customAfter 3 hours the cooling bath was removed
  2. additionThe reaction mixture was diluted with ethyl acetate
  3. extractionextracted with sat. NaHCO3-solution (3×150 ml) and brine (150 ml)
  4. dry with materialThe organic phase was dried over Na2SO4
  5. customevaporated
  6. customThe resulting syrup was purified by column chromatography

Sources & evidence

ORD record
ord-ceee4822e4a846c49414600cd0503d47
Source dataset
uspto-grants-2016_01
Patent number
US09234225B2

Linked notes

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