Hexane → HCID 18657882, compound

HRID 1492823Notes

Reaction equation

HRID 1492823 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]#[CH:10].CCCCCC.[C:17]([O:21][C:22]([N:24]1[CH2:28][C@H:27]([O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[CH2:26][C@H:25]1[CH:37]=[O:38])=[O:23])([CH3:20])([CH3:19])[CH3:18].[Cl-].[NH4+]>O1CCCC1.C([Li])CCC.C(OCC)(=O)C>[C:17]([O:21][C:22]([N:24]1[CH2:28][C@H:27]([O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[CH2:26][C@H:25]1[CH:37]([OH:38])[C:10]#[C:9][CH2:8][O:7][CH:2]1[CH2:3][CH2:4][CH2:5][CH2:6][O:1]1)=[O:23])([CH3:20])([CH3:19])[CH3:18]

Participants

8

Reactant 4

HCID 8058HexaneHCID 25517Ammonium ChlorideHCID 98609Tetrahydro-2-(2-propynyloxy)-2H-pyranHCID 10969557tert-Butyl (2S,4R)-4-((tert-butyldimethylsilyl)oxy)-2-formylpyrrolidine-1-carboxylate

Product 1

HCID 18657882HCID 18657882, compoundYield 90.2%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 178418339ButyllithiumSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of propargyl 2-tetrahydropyranyl ether (15.2 g, 109 mmol) in tetrahydrofuran (165 ml), 1.6 N n-butyllithium in hexane (68.1 ml, 109 mmol) was added in a nitrogen stream under cooling with ice, and the mixture was stirred under cooling with ice for 1 hour. The mixture was cooled to -78° C. and added to a solution of (2S,4R)-N-tert-butoxycarbonyl-4-tert-butyl-dimethylsiloxy-2-formylpyrrolidine (31.7 g, 90.2 mmol in tetrahydrofuran (150 ml) obtained by Reference Example 1-3) in a nitrogen stream at -78° C. and the mixture was stirred for 1 hour at the same temperature. After the reaction mixture was raised to -20° C. and stirred at the same temperature for 1.5 hours, a saturated ammonium chloride aqueous solution (150 ml) was added thereto and stirred. Ethyl acetate was added hereto and the organic layer was washed with water a saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (Wakogel™ C-300, hexane-ethyl acetate 1:1) to obtain (2S,4R)-N-tert-butoxycarbonyl-4-tert-butyldimethylsiloxy-2-[1-hydroxy-4-(2-tetrahydropyranyloxy)-2-butynyl]pyrrolidine (38.2 g, yield: 90%).

Workup

  1. temperatureunder cooling with ice
  2. temperatureunder cooling with ice for 1 hour
  3. stirringthe mixture was stirred for 1 hour at the same temperature
  4. temperatureAfter the reaction mixture was raised to -20° C.
  5. stirringstirred at the same temperature for 1.5 hours
  6. stirringstirred
  7. washthe organic layer was washed with water a saturated sodium chloride aqueous solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-9343b462334f4a3aa729ac4afb80417e
Source dataset
uspto-grants-1994_12
Patent number
US05374720

Reaction notes

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