CID 406 → HCID 18320538, compound

HRID 357634Notes

Reaction equation

HRID 357634 reaction equation
[CH3:1][O:2][CH:3]([C:12]1[CH:17]=[C:16]([NH:18][C:19](=[O:24])[C:20]([F:23])([F:22])[F:21])[CH:15]=[C:14]([O:25][CH3:26])[CH:13]=1)P(OCC)(=O)OCC.[CH:27]12[CH2:36][CH:31]3[CH2:32][CH:33]([CH2:35][CH:29]([CH2:30]3)[C:28]1=O)[CH2:34]2.P(=O)([O-])[O-].[Li]CCCC>C1COCC1>[CH3:26][O:25][C:14]1[CH:13]=[C:12]([C:3]([O:2][CH3:1])=[C:28]2[CH:29]3[CH2:35][CH:33]4[CH2:32][CH:31]([CH2:36][CH:27]2[CH2:34]4)[CH2:30]3)[CH:17]=[C:16]([NH:18][C:19](=[O:24])[C:20]([F:21])([F:22])[F:23])[CH:15]=1

Participants

6

Reactant 4

HCID 406CID 406HCID 64151Adamantanone2×HCID 54043094HCID 54043094, compoundHCID 178418339Butyllithium2×

Product 1

HCID 18320538HCID 18320538, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-68 °C

Procedure

Phosphonate 30, dissolved in anhydrous THF, is cooled to -68° C. under an argon atmosphere. Similarly, 2-adamantanone (1.1 eq) is dissolved in anhydrous THF and cooled to -68° C. under argon in a separate flask. To the phosphonate solution is added 2.5M nBuLi is added to complete the red color of the ylid persists. At this point, 1.2 eq nBuLi is added to complete the ylid formation and the resulting colored solution is stirred at -68° C. for 5 min. While maintaining the low temperature, 2-adamantanone in THF is slowly added to the ylid over an hour. After the final addition of ketone, the reaction mixture is stirred for 2 h while warming to room temperature. The reaction is then heated at reflux for 1 h, cooled and quenched by partitioning with EtOAc and saturated NH4Cl. The organic layer is dried over Na2SO4 and chromatographed with EtOAc/hexanes on a silica gel column to give enol ether 31.

Workup

  1. temperaturecooled to -68° C. under argon in a separate flask
  2. additionis added
  3. additionis slowly added to the ylid over an hour
  4. stirringthe reaction mixture is stirred for 2 h
  5. temperaturewhile warming to room temperature
  6. temperatureThe reaction is then heated
  7. temperatureat reflux for 1 h
  8. temperaturecooled
  9. customquenched
  10. customby partitioning with EtOAc and saturated NH4Cl
  11. dry with materialThe organic layer is dried over Na2SO4
  12. customchromatographed with EtOAc/hexanes on a silica gel column

Sources & evidence

ORD record
ord-c5d099aaa7614d1d926e00ac144e6a80
Source dataset
uspto-grants-1998_11
Patent number
US05840919

Reaction notes

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