Chlorotrimethylsilane → HCID 18657848, compound

HRID 1492814Notes

Reaction equation

HRID 1492814 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[C:13]([O:17][C:18]([N:20]1[CH2:24][C@H:23]([O:25][Si:26]([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:28])[CH3:27])[CH2:22][C@H:21]1[CH:33]1[CH2:37][N:36]([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[C:35](=[O:45])[CH2:34]1)=[O:19])([CH3:16])([CH3:15])[CH3:14].C1(C)C=CC(S([N:55]=[N+:56]=[N-:57])(=O)=O)=CC=1.C[Si](Cl)(C)C>O1CCCC1>[N:55]([CH:34]1[CH:33]([C@@H:21]2[CH2:22][C@@H:23]([O:25][Si:26]([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:28])[CH3:27])[CH2:24][N:20]2[C:18]([O:17][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:19])[CH2:37][N:36]([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[C:35]1=[O:45])=[N+:56]=[N-:57]

Participants

7

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 13661p-Toluenesulfonyl azideHCID 57097076HCID 57097076, compoundHCID 178418339Butyllithium

Product 1

HCID 18657848HCID 18657848, compoundYield 68.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

1.6M n-butyllithium (2.5 ml, 4 mmol) was dropwise added to a solution of diisopropylamine (0.64 ml, 4.6 mmol) in tetrahydrofuran (40 ml) under a nitrogen stream at -78° C. and the reaction solution was stirred for 45 minutes. A solution of (2S,4R)-N-tert-butoxycarbonyl-4-tert-butyldimethylsiloxy-2-(N-tert-butoxycarbonyl-2-pyrrolidon-4-yl)pyrrolidine (986 mg, 2 mmol, compound of Reference Example 5-1) in tetrahydrofuran (10 ml) was dropwise added to this solution, and the mixture was stirred at the same temperature for 2 hours. Then, p-toluenesulfonyl azide (945 mg, 4.8 mmol) was added thereto, and the mixture was stirred further for 1 hour. Then, trimethylsilyl chloride (1.29 ml, 10 mmol) was added to this reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure. A saturated sodium hydrogen carbonate aqueous solution was added to the residue, and then the mixture was extracted with methylene chloride (50 ml). The organic layer was washed with a saturated sodium chloride aqueous solution, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (Wakogel™ C-300, chloroform) to obtain (2S,4R)-2-(3-azido-N-tert-butoxycarbonyl-2-pyrrolidon-4-yl)-N-tert-butoxycarbonyl-4-(tert-butyldimethylsiloxy)pyrrolidine (720 mg, yield: 68.5%).

Workup

  1. stirringthe mixture was stirred at the same temperature for 2 hours
  2. stirringthe mixture was stirred further for 1 hour
  3. stirringthe mixture was stirred at room temperature for 1 hour
  4. concentrationThe reaction solution was concentrated under reduced pressure
  5. additionA saturated sodium hydrogen carbonate aqueous solution was added to the residue
  6. extractionthe mixture was extracted with methylene chloride (50 ml)
  7. washThe organic layer was washed with a saturated sodium chloride aqueous solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-39aed09e6fda47288d3c5e4e3243eea0
Source dataset
uspto-grants-1994_12
Patent number
US05374720

Reaction notes

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