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Phosphate → (1R,5S,6S)-2-[(4R)-pyrrolidine-2-thion-4-ylthio]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-1-methylcarbapen-2-em-3-carboxylic acid isobutyryloxymethyl ester

HRID 36497
Notes
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Reaction equation

HRID 36497 reaction equation
C([C@H:5]([O:27][SiH:28]([CH3:30])[CH3:29])[C@H:6]1[C:13](=[O:14])[N:12]2[C@@H:7]1[C@@H:8]([CH3:26])[C:9](=O)[S:10][CH:11]2[C:15]([O:17][CH2:18][O:19][C:20](=[O:24])[CH:21]([CH3:23])[CH3:22])=[O:16])(C)(C)C.[C:31]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:50][C:51]([CH3:54])([O-])[CH3:52].[K+].P(Cl)(OC1C=CC=CC=1)(OC1C=CC=CC=1)=O.S[C@@H:74]1[CH2:78][NH:77][C:76](=[S:79])[CH2:75]1.C(N(C(C)C)CC)(C)C.P([O-])([O-])([O-])=O>C1(C)C=CC=CC=1.C(#N)C>[Si:28]([O:27][C@@H:5]([C@H:6]1[C:13](=[O:14])[N:12]2[C:11]([C:15]([O:17][CH2:18][O:19][C:20](=[O:24])[CH:21]([CH3:22])[CH3:23])=[O:16])=[C:9]([S:10][C@H:74]3[CH2:78][NH:77][C:76](=[S:79])[CH2:75]3)[C@H:8]([CH3:26])[C@H:7]12)[CH3:31])([C:51]([CH3:54])([CH3:52])[CH3:50])([CH3:30])[CH3:29]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

10

Reactant 7

HCID 1061PhosphateHCID 11776TriphenylphosphineHCID 75654Diphenyl chlorophosphateHCID 81531DiisopropylethylamineHCID 11051701(4S)-4-mercaptopyrrolidin-2-thioneHCID 23665647Potassium tert-butoxide
HCID 131718995
isobutyryloxymethyl (5R,6S,7S)-7-[(R)-1-tert-butyldimethylsilyloxymethyl]-5-methyl-4,8-dioxo-1-aza-3-thia-bicyclo-[4.2.0]octan-2-carboxylate

Product 1

HCID 11103665(1R,5S,6S)-2-[(4R)-pyrrolidine-2-thion-4-ylthio]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-1-methylcarbapen-2-em-3-carboxylic acid isobutyryloxymethyl esterYield 42.2%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
-40 °C

Procedure

In 10 ml of toluene were dissolved 500 mg of isobutyryloxymethyl (5R,6S,7S)-7-[(R)-1-tert-butyldimethylsilyloxymethyl]-5-methyl-4,8-dioxo-1-aza-3-thia-bicyclo-[4.2.0]octan-2-carboxylate and 277 mg of triphenylphosphine, 130 mg of potassium tert-butoxide was added thereto under nitrogen gas at -40° C. while stirring, and the mixture was stirred at the same temperature for 50 minutes. To the reaction mixture was added dropwise 10 ml of acetonitrile solution containing 312 mg of diphenyl chlorophosphate at -40° C., and the mixture was stirred for 40 minutes. To the reaction mixture were added 155 mg of (4S)-4-mercaptopyrrolidin-2-thione and 148 mg of diisopropylethylamine, and the mixture was stirred at -20° C. for 80 minutes, and then at -5° C. for 1.5 hours. The reaction mixture was poured into a 0.1M phosphate buffer (pH 7.0) and extracted with ethyl acetate. After the extract was washed and dried, the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (solvent; n-hexane:ethyl acetate:chloroform=5:5:1) to obtain 248 mg of isobutyryloxymethyl (1R,5S,6S)-6-[(R)-1-tert-butyldimethylsilyloxyethyl]-2-[(4R)-pyrrolidin-2-thion-4-ylthio]-1-methylcarbapen-2-em-3-carboxylate.

Workup

  1. additionwas added
  2. stirringthe mixture was stirred at the same temperature for 50 minutes
  3. stirringthe mixture was stirred for 40 minutes
  4. stirringthe mixture was stirred at -20° C. for 80 minutes
  5. extractionextracted with ethyl acetate
  6. washAfter the extract was washed
  7. customdried
  8. customthe solvent was removed under reduced pressure
  9. customThe residue was purified by silica gel column chromatography (solvent; n-hexane:ethyl acetate:chloroform=5:5:1)

Sources & evidence

ORD record
ord-aecf9b53f27947c0b6ec1f7fbcb48698
Source dataset
uspto-grants-1995_05
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05414081

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes