Sodium Thiosulfate → Methyl cis(+/-)-3-acetyl-5-(4-{[(benzyloxy)carbonyl]amino}-3-methoxypiperidin-1-yl)thiophene-2-carboxylate

HRID 43948Notes

Reaction equation

HRID 43948 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[CH2:23]([O:30][C:31]([NH:33][C@H:34]1[CH2:39][CH2:38][N:37]([C:40]2[S:44][C:43]([C:45]([O:47][CH3:48])=[O:46])=[C:42]([CH:49]([OH:51])[CH3:50])[CH:41]=2)[CH2:36][C@H:35]1[O:52][CH3:53])=[O:32])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl>[C:49]([C:42]1[CH:41]=[C:40]([N:37]2[CH2:38][CH2:39][C@H:34]([NH:33][C:31]([O:30][CH2:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)=[O:32])[C@H:35]([O:52][CH3:53])[CH2:36]2)[S:44][C:43]=1[C:45]([O:47][CH3:48])=[O:46])(=[O:51])[CH3:50]

Participants

5

Reactant 3

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 68405949Methyl 5-((3R*,4S*)-4-{[(benzyloxy)carbonyl]amino}-3-methoxypiperidin-1-yl)-3-(1-hydroxyethyl)thiophene-2-carboxylate

Product 1

HCID 86648832Methyl cis(+/-)-3-acetyl-5-(4-{[(benzyloxy)carbonyl]amino}-3-methoxypiperidin-1-yl)thiophene-2-carboxylateYield 49.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The Dess-Martin reagent (305 mg, 0.72 mmol) was added to a solution of methyl 5-((3R*,4S*)-4-{[(benzyloxy)carbonyl]amino}-3-methoxypiperidin-1-yl)-3-(1-hydroxyethyl)thiophene-2-carboxylate obtained in Example (246d) (215 mg, 0.48 mmol) in dichloromethane (5 mL) at room temperature, followed by stirring for one hour. Aqueous sodium thiosulfate solution was added to the reaction solution, followed by stirring at room temperature. Then, the mixture was extracted with chloroform. The combined organic layers were dried over anhydrous magnesium sulfate. Following filtration, the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: hexane/ethyl acetate=3/1) to obtain 106 mg of the title compound as a yellow oily substance (50%).

Workup

  1. stirringby stirring at room temperature
  2. extractionThen, the mixture was extracted with chloroform
  3. dry with materialThe combined organic layers were dried over anhydrous magnesium sulfate
  4. filtrationfiltration
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. customThe resulting residue was purified by silica gel column chromatography (elution solvent: hexane/ethyl acetate=3/1)

Sources & evidence

ORD record
ord-ebe057d8dbae4ce8905e4d95bb7252b6
Source dataset
uspto-grants-2013_09
Patent number
US08536197B2

Reaction notes

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