Acetonitrile → HCID 86592513, compound

HRID 1374398Notes

Reaction equation

HRID 1374398 reaction equation
C([Li])CCC.CCCCCC.[NH2:12][C:13]([O:15][CH2:16][C@@H:17]1[CH2:22][C:21]([C:23]2[N:24]=[C:25]([SH:28])[S:26][CH:27]=2)=[CH:20][CH2:19][N:18]1[C:29]([O:31][CH2:32][CH:33]=[CH2:34])=[O:30])=[O:14].O(P(OC1C=CC=CC=1)O[C:44]1[C@H:50]([CH3:51])[C@H:49]2[N:46]([C:47](=[O:59])[C@@H:48]2[C@H:52]([O:54][Si:55]([CH3:58])([CH3:57])[CH3:56])[CH3:53])[C:45]=1[C:60]([O:62][CH2:63][CH:64]=[CH2:65])=[O:61])C1C=CC=CC=1.C(#N)C>C1COCC1.CN(C=O)C>[CH2:32]([O:31][C:29]([N:18]1[CH2:19][CH:20]=[C:21]([C:23]2[N:24]=[C:25]([S:28][C:44]3[C@H:50]([CH3:51])[C@H:49]4[N:46]([C:47](=[O:59])[C@@H:48]4[C@H:52]([O:54][Si:55]([CH3:56])([CH3:57])[CH3:58])[CH3:53])[C:45]=3[C:60]([O:62][CH2:63][CH:64]=[CH2:65])=[O:61])[S:26][CH:27]=2)[CH2:22][C@H:17]1[CH2:16][O:15][C:13]([NH2:12])=[O:14])=[O:30])[CH:33]=[CH2:34]

Participants

8

Reactant 5

HCID 6342AcetonitrileHCID 8058HexaneHCID 86592502HCID 86592502, compoundHCID 178418339ButyllithiumHCID 178459664HCID 178459664, compound

Product 1

HCID 86592513HCID 86592513, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of n-butyllithium in hexane (1.56M, 68 ml, 0.11 mmol) was added at −70° C. to a solution of allyl(2S)-2-{[(aminocarbonyl)oxy]methyl}-4-(2-mercapto-1,3-thiazol-4-yl)-3,6-dihydro-1(2 H)-pyridinecarboxylate (37.8 mg, 0.11 mmol) in THF (1 ml)/DMF (0.5 ml). The mixture was warmed to 0° C. and then stirred for 15 minutes. To the reaction solution was added at 0° C. a solution of allyl (4R,5R,6S)-3-[(diphenoxyphosphino)oxy]-4-methyl-7-oxo-6-{(1R)-1-[(trimethylsilyl)oxy]ethyl}-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate in acetonitrile (30%, 0.42 g, 0.22 mmol) and the solution was allowed to stand in a refrigerator for 13 hours. To the reaction solution was added ice water and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. After removal of the solvent in vacuo, the residue was purified with silica gel chromatography (hexane/ethyl acetate) to give crude allyl (4R,5S,6S)-3-{[4-((2S)-1-[(allyloxy)carbonyl]-2-{[(aminocarbony)oxy]methyl}-1,2,3,6-tetrahydro-4-pyridinyl)-1,3-thiazol-2-yl]sulfanyl}-4-methyl-7-oxo-6-{(1R)-1-[(trimethylsilyl)oxy]ethyl}-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (154 mg).

Workup

  1. waitto stand in a refrigerator for 13 hours
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with a saturated aqueous sodium chloride solution
  4. dry with materialdried over anhydrous sodium sulfate
  5. customAfter removal of the solvent in vacuo
  6. customthe residue was purified with silica gel chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-f6f67fb870b84aad8652a712749b4c9e
Source dataset
uspto-grants-2007_01
Patent number
US07163936B2

Reaction notes

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