Acetic Acid → HCID 10962242, compound

HRID 2232673Notes

Reaction equation

HRID 2232673 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Si:11]([O:18][C@@H:19]1[CH2:23][C@H:22]([CH2:24][OH:25])[C@@H:21]([CH2:26][C:27]#[CH:28])[C@H:20]1/[CH:29]=[CH:30]/[C@@H:31]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].C(N(CC)CC)C.C(O)(=O)C.[Cl-].[NH4+]>ClCCl>[Si:11]([O:18][C@@H:19]1[CH2:23][C@H:22]([CH:24]=[O:25])[C@H:21]([CH2:26][C:27]#[CH:28])[C@H:20]1/[CH:29]=[CH:30]/[C@@H:31]([O:37][Si:38]([C:41]([CH3:42])([CH3:44])[CH3:43])([CH3:40])[CH3:39])[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12]

Participants

8

Reactant 6

HCID 176Acetic AcidHCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 13964339HCID 13964339, compound

Product 1

HCID 10962242HCID 10962242, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-50 °C

Procedure

Oxalyl chloride (5.08 g; 40 mmoles) and 60 ml of dichloromethane were taken into a nitrogen-purged 500 ml eggplant-shaped flask, and cooled to -50° C. A solution of 6.24 g (80 mmoles) of dimethyl sulfoxide in 20 ml of dichloromethane was added, and the mixture was stirred for 30 minutes. A solution of 9.09 g (17.9 mmoles) of (1R,2R,3R,4S)-1-t-butyldimethylsilyloxy-2-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-4-hydroxymethyl-3-(2-propynyl)cyclopentane (32) in 40 ml of dichloromethane was added, and the mixture was stirred at -50° C. for 30 minutes. Subsequently, 10.1 g (100 mmoles) of triethylamine was added, and the mixture was stirred at -50° C. for 30 minutes. Acetic acid (7.2 g; 120 mmoles) was added, and the mixture was stirred for 10 minutes. The reaction mixture was poured into saturated aqueous ammonium chloride solution and extracted with dichloromethane. The organic layer was washed successively with saturated aqueous potassium hydrogensulfate and saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure to give 9.05 g (yield of the crude product 100%) of (1R,2R,3R,4S)-1-t-butyldimethylsilyloxy-2-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-4-formyl-3-(2-propynyl)cyclopentane (20).

Workup

  1. custompurged 500 ml eggplant-shaped flask
  2. stirringthe mixture was stirred at -50° C. for 30 minutes
  3. stirringthe mixture was stirred at -50° C. for 30 minutes
  4. stirringthe mixture was stirred for 10 minutes
  5. extractionextracted with dichloromethane
  6. washThe organic layer was washed successively with saturated aqueous potassium hydrogensulfate and saturated aqueous sodium chloride solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customThe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-986abe10fc0d4b29b688e6d4d4dd6914
Source dataset
uspto-grants-1988_11
Patent number
US04788319

Reaction notes

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