Chlorotrimethylsilane → (1RS,5RS,6RS)ethyl 6-fluoro-2-oxobicyclo[3.1.0]hex-3-en-6-carboxylate

HRID 2271283

반응식

HRID 2271283 반응식
[F:1][C:2]1([C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:7]2[CH:3]1[CH2:4][CH2:5][C:6]2=[O:8].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].C([Li])CCC.C[Si](C)(C)N[Si](C)(C)C.Cl[Si](C)(C)C>CCCCCC.O1CCCC1>[F:1][C:2]1([C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:7]2[CH:3]1[CH:4]=[CH:5][C:6]2=[O:8]

참가 물질

8

반응물 5

HCID 6397ChlorotrimethylsilaneHCID 13838HexamethyldisilazaneHCID 2733832Lithium HexamethyldisilazideHCID 9964278HCID 9964278, 화합물HCID 178418339Butyllithium

생성물 1

HCID 69853125(1RS,5RS,6RS)ethyl 6-fluoro-2-oxobicyclo[3.1.0]hex-3-en-6-carboxylate수율 88.7%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매

실험 절차

Under a nitrogen atmosphere, 19.5 g of (1RS,5RS,6RS)ethyl 6-fluoro-2-oxobicyclo[3.1.0]hexane-6-carboxylate dissolved into 230 ml of tetrahydrofuran at −78° C. was added dropwise to 230 ml of a tetrahydrofuran solution of lithium bis(trimethylsilyl)amide which was prepared from 78 ml of n-butyllithium (1.61M hexane solution) and 20.3 g of 1,1,1,3,3,3-hexamethyldisilazane. After stirring at this temperature for 1 hour, 19.8 ml of chlorotrimethylsilane was added thereto, and this was stirred at room temperature for 1.5 hours. After carrying out of concentration of the reaction solution under reduced pressure, anhydrous hexane was added to the residue, the resulting inorganic salt was filtered off, and the filtrate was further concentrated under reduced pressure. After the residue was dissolved into 240 ml of acetonitrile, 25.9 g of palladium acetate was added thereto, and then it was stirred at room temperature for one day. The reaction solution was diluted with 240 ml of diethyl ether, the palladium was filtered off by use of celite, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel: Wako gel C200 (made by Wako Pure Chemical Industries Ltd.), eluent: hexane-ethyl acetate=9:1 to 5:1), yielding 17.1 g of (1RS,5RS,6RS)ethyl 6-fluoro-2-oxobicyclo[3.1.0]hex-3-en-6-carboxylate.

후처리

  1. stirringthis was stirred at room temperature for 1.5 hours
  2. additionwas added to the residue
  3. filtrationthe resulting inorganic salt was filtered off
  4. concentrationthe filtrate was further concentrated under reduced pressure
  5. dissolutionAfter the residue was dissolved into 240 ml of acetonitrile, 25.9 g of palladium acetate
  6. additionwas added
  7. stirringit was stirred at room temperature for one day
  8. additionThe reaction solution was diluted with 240 ml of diethyl ether
  9. filtrationthe palladium was filtered off by use of celite
  10. concentrationthe filtrate was concentrated under reduced pressure
  11. customThe residue was purified by column chromatography (silica gel: Wako gel C200 (made by Wako Pure Chemical Industries Ltd.), eluent: hexane-ethyl acetate=9:1 to 5:1)

출처 및 근거

ORD 기록
ord-bd0ce99e4d4640e3a6a6f664f8fec9b7
출처 데이터셋
uspto-grants-2001_12
특허 번호
US06333428B1

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