Acetone → HCID 22857740, compound

HRID 2259515Notes

Reaction equation

HRID 2259515 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][CH2:9][C@H:10]([C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH2:26][O:27][CH:28]2[CH2:33][CH2:32][CH2:31][CH2:30][O:29]2)[CH:21]=1)[O:11][CH2:12][C:13]1([CH2:16][C:17]([OH:19])=[O:18])[CH2:15][CH2:14]1.[Li][CH2:35]CCC.[CH3:39][C:40]([CH3:42])=[O:41].[NH4+].[Cl-]>C1COCC1>[OH:41][C:40]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][CH2:9][C@H:10]([C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH2:26][O:27][CH:28]2[CH2:33][CH2:32][CH2:31][CH2:30][O:29]2)[CH:21]=1)[O:11][CH2:12][C:13]1([CH2:16][C:17]([O:19][CH3:35])=[O:18])[CH2:15][CH2:14]1)([CH3:42])[CH3:39]

Participants

6

Reactant 4

HCID 180Acetone2×HCID 25517Ammonium ChlorideHCID 22857727HCID 22857727, compoundHCID 178418339Butyllithium

Product 1

HCID 22857740HCID 22857740, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a frozen solution of the acid of Example 14, Step 7 (2.216 g, 4.28 mmol) in 30 mL of THF at -100° C. was added 1.6M BuLi in hexanes (5.9 mL) and the mixture was stirred at -78° C. for 30 min. Acetone (630 μL, 8.6 mmol) was then added and the mixture was stirred at -78° C. for 1 hr. and was then allowed to warm to -20° C. Saturated aq. NH4Cl was then added and the products were extracted in EtOAc. At 0° C., diazomethane ~0.5M was added. When the esterification was completed, the excess of CH2N2 was quenched with AcOH. The solution was dried over Na2SO4, concentrated and stripped with toluene. Hash chromatography of the residue with EtOAc:hexane 15:85 to 35:65 afforded first, the reduced starting material (desbromo), second, the product of addition of acetone α to the ester and third, the title product.

Workup

  1. stirringthe mixture was stirred at -78° C. for 1 hr
  2. temperatureto warm to -20° C
  3. extractionthe products were extracted in EtOAc
  4. additionAt 0° C., diazomethane ~0.5M was added
  5. customthe excess of CH2N2 was quenched with AcOH
  6. dry with materialThe solution was dried over Na2SO4
  7. concentrationconcentrated
  8. customHash chromatography of the residue with EtOAc:hexane 15:85 to 35:65 afforded first

Sources & evidence

ORD record
ord-11561e89342648b5bc28947e024bd710
Source dataset
uspto-grants-1995_12
Patent number
US05472964

Reaction notes

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