Ammonium Chloride → 5-[(4S,5R)-4,6-diacetoxy-1-hydroxy-5-(1-methoxy-1-methylethyloxy)-2-hexen-1-yl]-4-octyl-4-trimethylsilyloxy-2-cyclopentenone

HRID 1886228Notes

Reaction equation

HRID 1886228 reaction equation
[CH2:1]([C:9]1([O:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[CH2:13][C:12](=[O:14])[CH:11]=[CH:10]1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].C(N(C(C)C)CC)(C)C.O1C=CC=C1C([O-])=O.O1C=CC=C1C([O-])=O.O1C=CC=C1C([O-])=O.C([B+3]CCCC)CCC.[C:62]([O:65][C@H:66]([C@H:71]([O:77][C:78]([O:81][CH3:82])([CH3:80])[CH3:79])[CH2:72][O:73][C:74](=[O:76])[CH3:75])[CH:67]=[CH:68][CH:69]=[O:70])(=[O:64])[CH3:63].[Cl-].[NH4+]>CCOCC.CCCCCC>[C:62]([O:65][C@H:66]([C@H:71]([O:77][C:78]([O:81][CH3:82])([CH3:80])[CH3:79])[CH2:72][O:73][C:74](=[O:76])[CH3:75])[CH:67]=[CH:68][CH:69]([CH:13]1[C:12](=[O:14])[CH:11]=[CH:10][C:9]1([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])[O:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[OH:70])(=[O:64])[CH3:63]

Participants

8

Reactant 5

HCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 137677604-Octyl-4-trimethylsilyloxy-2-cyclopentenoneHCID 57122051(4S,5R)-4,6-diacetoxy-5-(1-methoxy-1-methylethyloxy)-2-hexenalHCID 178440533HCID 178440533, compound

Product 1

HCID 678636745-[(4S,5R)-4,6-diacetoxy-1-hydroxy-5-(1-methoxy-1-methylethyloxy)-2-hexen-1-yl]-4-octyl-4-trimethylsilyloxy-2-cyclopentenoneYield 59.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution composed of 1 g (3.55 mmoles) of 4-octyl-4-trimethylsilyloxy-2-cyclopentenone, 5 ml of dry hexane and 5 ml of dry ether was cooled to -78° C. under a nitrogen stream, and 870 microliters (5 mmoles) of diisopropylethylamine and then 4.6 ml (4.6 mmoles) of dibutylboron trifurate (lM CH2Cl2 solution) were added. The mixture was stirred at -78° C. for 1 hour. An ether solution (3 ml) of 1070 mg (3.55 mmoles) of (4S,5R)-4,6-diacetoxy-5-(1-methoxy-1-methylethyloxy)-2-hexenal was added, and the mixture was stirred for 2 hours. After the reaction, an aqueous solution of ammonium chloride was added to terminate the reaction, and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with an aqueous potassium hydrogen sulfate solution, an aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution in this sequence, and dried over anhydrous magnesium sulfate solution. The solvent was evaporated under reduced pressure, and the resulting oily product was subjected to Florisil column chromatography (hexane:ethyl acetate: 5:1→3:1) to give 1.24 g (59%) of an aldol product.

Workup

  1. stirringthe mixture was stirred for 2 hours
  2. customAfter the reaction
  3. customto terminate
  4. customthe reaction
  5. extractionthe reaction mixture was extracted with ethyl acetate
  6. washThe organic layer was washed with an aqueous potassium hydrogen sulfate solution
  7. dry with materialan aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution in this sequence, and dried over anhydrous magnesium sulfate solution
  8. customThe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-15c5bf96cbd4451b8202bfd0767bf77a
Source dataset
uspto-grants-1992_09
Patent number
US05149711

Reaction notes

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