Ammonium Chloride → HCID 88506623, compound

HRID 1650268Notes

Reaction equation

HRID 1650268 reaction equation
[Si:1]([O:8][C@@H:9]([C@@H:11]1[C@@H:14]([C@@H:15]([CH3:19])[C:16](=[O:18])[CH3:17])[N:13]([C:20](=[P:27]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:21]([O:23][CH2:24][CH:25]=[CH2:26])=[O:22])[C:12]1=[O:46])[CH3:10])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([N-]C(C)C)(C)C.[Li+].[CH2:55]([O:58][C:59]([N:61]1[CH2:65][CH2:64][CH2:63][C@H:62]1[CH:66]=[O:67])=[O:60])[CH:56]=[CH2:57].[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C>[CH2:55]([O:58][C:59]([N:61]1[CH2:65][CH2:64][CH2:63][C@H:62]1[CH:66]([OH:67])[CH2:17][C:16](=[O:18])[C@@H:15]([C@H:14]1[N:13]([C:20](=[P:27]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)[C:21]([O:23][CH2:24][CH:25]=[CH2:26])=[O:22])[C:12](=[O:46])[C@@H:11]1[C@H:9]([O:8][Si:1]([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2])[CH3:10])[CH3:19])=[O:60])[CH:56]=[CH2:57]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 14084566HCID 14084566, compoundHCID 53958006HCID 53958006, compound

Product 1

HCID 88506623HCID 88506623, compoundYield 73.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of diisopropylamine (7.7 ml) in tetrahydrofuran (60.0 ml) was added dropwise a 1.55M solution of n-butyllithium in n-hexane (32.3 ml) at -78° C. The mixture was allowed to warm to 0° C., stirred at 0° C. for 30 minutes, and cooled to -78° C. to give ca. 0.5M lithium diisopropylamide solution. To a solution of allyl 2-[(3S,4R)-3-{(1R)-1-t-butyldimethylsilyloxyethyl}-4-{(1R)-1-methyl-2-oxopropyl}-2-oxoazetidin-1-yl]-2-triphenylphosphoranylideneacetate (2.50 g) in tetrahydrofuran (40 ml) was added dropwise the lithium diisopropylamide solution (9.50 ml) obtained above at -78° C. After stirring for 30 minutes at -78° C., to the mixture was added a solution of (2S)-1-allyloxycarbonyl-2-formylpyrrolidine (1.39 g) in tetrahydrofuran (10.0 ml) and the mixture was allowed to warm to -30° C. over a period of 45 minutes. To this mixture was added aqueous ammonium chloride (50 ml) and diluted with ethyl acetate (200 ml). The organic layer was separated, washed in turn with water, aqueous sodium hydrogen carbonate and brine, and dried over magnesium sulfate. Evaporation of the solvent gave a residue which was chromatographed on silica gel (150 ml) eluting with a mixture of dichloromethane and acetone (9:1-8:2 V/V) to give allyl 2-[(3S,4R)-4-[(1R)-4-{(2S)-1-allyloxycarbonylpyrrolidin-2-yl}-4-hydroxy-1-methyl-2-oxobutyl]-3-{ (1R)-1-t-butyldimethylsilyloxyethyl}-2-oxoazetidin-1-yl]-2-triphenylphosphoranylideneacetate (2.36 g).

Workup

  1. customobtained above at -78° C
  2. temperatureto warm to -30° C. over a period of 45 minutes
  3. customThe organic layer was separated
  4. washwashed in turn with water, aqueous sodium hydrogen carbonate and brine
  5. dry with materialdried over magnesium sulfate
  6. customEvaporation of the solvent
  7. customgave a residue which
  8. customwas chromatographed on silica gel (150 ml)
  9. washeluting with a mixture of dichloromethane and acetone (9:1-8:2 V/V)

Sources & evidence

ORD record
ord-418d84acd7ec47718b6aff8128348163
Source dataset
uspto-grants-1990_05
Patent number
US04923857

Reaction notes

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