Tributylphosphine → 2-(1-Hydroxy-7-keto-8-oxanonyl)-3-[3-(t-butyldimethylsilyloxy)-1-trans-octenyl]-4-(t-butyldimethylsilyloxy)cyclopentanone

HRID 1447050노트

반응식

HRID 1447050 반응식
C(P(CCCC)CCCC)CCC.[Li]/[CH:15]=[CH:16]/[CH:17]([O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])[CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].[C:31]([Si:35]([CH3:44])([CH3:43])[O:36][CH:37]1[CH2:41][C:40](=[O:42])[CH:39]=[CH:38]1)([CH3:34])([CH3:33])[CH3:32].[O:45]=[CH:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][C:52]([O:54][CH3:55])=[O:53].[Cl-].[NH4+]>CCOCC.O1CCCC1.CCCCCC>[OH:45][CH:46]([CH:39]1[CH:38](/[CH:15]=[CH:16]/[CH:17]([O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])[CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH:37]([O:36][Si:35]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:44])[CH3:43])[CH2:41][C:40]1=[O:42])[CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][C:52](=[O:53])[O:54][CH3:55]

참가 물질

9

반응물 5

HCID 13831TributylphosphineHCID 25517Ammonium ChlorideHCID 3015770Methyl 7-oxoheptanoateHCID 41316994-((tert-Butyl(dimethyl)silyl)oxy)cyclopent-2-en-1-oneHCID 178506904HCID 178506904, 화합물

생성물 1

HCID 128380262-(1-Hydroxy-7-keto-8-oxanonyl)-3-[3-(t-butyldimethylsilyloxy)-1-trans-octenyl]-4-(t-butyldimethylsilyloxy)cyclopentanone

시약·촉매·용매 3

HCID 3283Diethyl Ether용매2회HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매

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온도
-78 °C

실험 절차

Cuprous chloride (229 mg; 1.2 mmoles) was weighed into a 50 ml flask, and the inside atmosphere of the flask was purged with argon. Anhydrous ether (10 ml) was added, and then 0.60 ml (2.4 mmoles) of tri-n-butylphosphine was added at room temperature, followed by stirring for 10 minutes. The mixture was then cooled to -78° C., and a solution of 1.2 mmoles of dl 1-lithio-3-(t-butyldimethylsilyloxy)-trans-octene in a mixture of anhydrous ether and anhydrous hexane was added. The mixture was stirred at -78° C. for 30 minutes, and a solution of 212 mg (1.0 mmole) of dl 4-(t-butyldimethyl-silyloxy)-2-cyclopentenone in 5 ml of anhydrous ether was added dropwise. The mixture was stirred at -78° C. for 1 hour. Then, 0.15 ml of a boron trifluoride/ether complex was added, and the mixture was stirred at -78° C. for 10 minutes, and then at -40° C. for 20 minutes. Then, 5 ml of anhydrous tetrahydrofuran was added, and a solution of 221 mg (1.4 mmoles) of methyl 7-ketoheptanoate in 5 ml of anhydrous tetrahydrofuran was added. The mixture was stirred at -40° C. for 1.5 hours. The temperature of the mixture was gradually raised to room temperature, and the product was hydrolyzed with a saturated aqueous solution of ammonium chloride and extracted with ether. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was subjected to silica gel column chromatography. From the eluates resulting from elution with hexane/ethyl acetate (=9/1), two stereoisomers, dl 2-(1-hydroxy-7-keto-8-oxanonyl)-3-[3-(t-butyldimethylsilyloxy)-1-trans-octenyl]-4-(t-butyldimethylsilyloxy)cyclopentanone, were obtained in an amount of 59 mg (TLC: Rf=0.39; developing solvent hexane/ethyl acetate=4/1) and 35 mg (TLC: Rf=0.35; developing solvent hexane/ethyl acetate=4/1), respectively.

후처리

  1. customthe inside atmosphere of the flask was purged with argon
  2. additionAnhydrous ether (10 ml) was added
  3. additionwas added
  4. stirringThe mixture was stirred at -78° C. for 30 minutes
  5. stirringThe mixture was stirred at -78° C. for 1 hour
  6. additionThen, 0.15 ml of a boron trifluoride/ether complex was added
  7. stirringthe mixture was stirred at -78° C. for 10 minutes
  8. waitat -40° C. for 20 minutes
  9. stirringThe mixture was stirred at -40° C. for 1.5 hours
  10. temperatureThe temperature of the mixture was gradually raised to room temperature
  11. extractionextracted with ether
  12. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  13. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-90df002fc41c48a38dbe1c443de6c5b9
출처 데이터셋
uspto-grants-1982_02
특허 번호
US04315032

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