Diazomethane → (11R)-dihydroartemisinic aldehyde

HRID 222868

Reaction equation

HRID 222868 reaction equation
[CH3:1][C@H:2]1[C@@H:7]2[CH2:8][CH2:9][C:10]([CH3:12])=[CH:11][C@@H:6]2[C@H:5]([C@H:13]([C:15](O)=[O:16])[CH3:14])[CH2:4][CH2:3]1.[N+](=C)=[N-]>C(OCC)C>[CH3:1][C@H:2]1[C@@H:7]2[CH2:8][CH2:9][C:10]([CH3:12])=[CH:11][C@@H:6]2[C@H:5]([C@H:13]([CH:15]=[O:16])[CH3:14])[CH2:4][CH2:3]1

Participants

4

Reactant 2

HCID 9550DiazomethaneHCID 11020893Dihydroartemisinic acid

Product 1

HCID 10857031(11R)-dihydroartemisinic aldehydeYield 48%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Dihydroartemisinic aldehyde was synthesized from the isolated dihydroartemisinic acid. The acid was converted to methyl dihydroartemisinate with excess diazomethane in diethyl ether at 0° C. for 5 minutes. The ether and diazomethane were removed under a stream of nitrogen and the methyl ester was reduced to (11R)-dihydroartemisinic alcohol with excess 1.5 M diisobutyl aluminum hydride in toluene at room temperature for 10 min under nitrogen. With subsequent extraction, oxidation to the aldehyde with pyridinium chlorochromate (Corey & Suggs 1975) and purification by HPLC the (11R)-dihydroartemisinic aldehyde was produced at an overall yield of 48% with >99% purity according to GC analysis.

Workup

  1. customThe ether and diazomethane were removed under a stream of nitrogen
  2. extractionWith subsequent extraction, oxidation to the aldehyde
  3. customwith pyridinium chlorochromate (Corey & Suggs 1975) and purification by HPLC the (11R)-dihydroartemisinic aldehyde
  4. customwas produced at an overall yield of 48% with >99% purity

Sources & evidence

ORD record
ord-64d0546a608c489d91651c8366f8319e
Source dataset
uspto-grants-2012_06
Patent number
US08207402B2

Linked notes

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