Triethyl phosphite → (1R,5S,6S)-2-[(4R)-pyrrolidine-2-thion-4-ylthio]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-1-methylcarbapen-2-em-3-carboxylic acid sodium salt

HRID 1081948Notes

Reaction equation

HRID 1081948 reaction equation
CC1(C)CC(=O)CC(=O)C1.O1CCOCC1.P(OCC)(OCC)OCC.C([O:30][C:31]([C:33]1[N:37]2[C:38](=[O:50])[C@H:39]([C@H:40]([O:42][Si:43]([C:46]([CH3:49])([CH3:48])[CH3:47])([CH3:45])[CH3:44])[CH3:41])[C@H:36]2[C@@H:35]([CH3:51])[C:34]=1[S:52][C@H:53]1[CH2:57][NH:56][C:55](=[S:58])[CH2:54]1)=[O:32])C=C.C(=O)([O-])O.[Na+:63]>O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C(OCC)C>[Na+:63].[NH:56]1[CH2:57][C@H:53]([S:52][C:34]2[C@H:35]([CH3:51])[C@@H:36]3[C@@H:39]([C@H:40]([O:42][Si:43]([C:46]([CH3:48])([CH3:47])[CH3:49])([CH3:44])[CH3:45])[CH3:41])[C:38](=[O:50])[N:37]3[C:33]=2[C:31]([O-:32])=[O:30])[CH2:54][C:55]1=[S:58]

Participants

9

Reactant 5

HCID 31215Triethyl phosphiteHCID 312751,4-DioxaneHCID 31358DimedoneHCID 516892Sodium BicarbonateHCID 10720094HCID 10720094, compound

Product 1

HCID 23709518(1R,5S,6S)-2-[(4R)-pyrrolidine-2-thion-4-ylthio]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-1-methylcarbapen-2-em-3-carboxylic acid sodium saltYield 91.9%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
30 °C

Procedure

Dimedone (169 mg) is dissolved in a solution of sodium hydrogen carbonate (169 mg) in water (2 ml) by ultrasonic treatment, and thereto are added dioxane (16 ml), palladium diacetate (23 mg) and triethyl phosphite (0.12 ml) under nitrogen atmosphere, and further added thereto (1R,5S,6S)-2-[(4R)-pyrrolidine-2-thion-4-ylthio]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-1-methylcarbapen-2-em-3-carboxylic acid allyl ester (1.03 g). The mixture is stirred at 30° C. for 30 minutes, and thereto is added diethyl ether (32 ml), and the mixture is stirred at 25° C. for 15 minutes, and further stirred at 5° C. for 30 minutes. The precipitated crystals are collected by filtration, washed with diethyl ether, and dried under reduced pressure at 25° C. for 17 hours to give (1R,5S,6S)-2-[(4R)-pyrrolidine-2-thion-4-ylthio]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-1-methylcarbapen-2-em-3-carboxylic acid sodium salt (885 mg).

Workup

  1. additionfurther added
  2. stirringthe mixture is stirred at 25° C. for 15 minutes
  3. stirringfurther stirred at 5° C. for 30 minutes
  4. filtrationThe precipitated crystals are collected by filtration
  5. washwashed with diethyl ether
  6. customdried under reduced pressure at 25° C. for 17 hours

Sources & evidence

ORD record
ord-dc42c43e0c094e16916fc0cb4a7f0c50
Source dataset
uspto-grants-1996_12
Patent number
US05587474

Reaction notes

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