Phenylsilane → 6-Methoxy-1-methyl-1,2,3,4-tetrahydronaphthalene

HRID 2396299노트

반응식

HRID 2396299 반응식
C([Li])CCC.C1([SiH3])C=CC=CC=1.[CH3:13][O:14][C:15]1[CH:16]=[C:17]2[C:22](=[CH:23][CH:24]=1)[C:21]([CH3:25])=[CH:20][CH2:19][CH2:18]2.[H][H]>C1COCC1>[CH3:13][O:14][C:15]1[CH:16]=[C:17]2[C:22](=[CH:23][CH:24]=1)[CH:21]([CH3:25])[CH2:20][CH2:19][CH2:18]2

참가 물질

6

반응물 4

HCID 12752PhenylsilaneHCID 118299387-Methoxy-4-methyl-1,2-dihydronaphthaleneHCID 178418339ButyllithiumHCID 178418361HCID 178418361, 화합물

생성물 1

HCID 133961206-Methoxy-1-methyl-1,2,3,4-tetrahydronaphthalene수율 70.3%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
0 °C

실험 절차

In a dry sealable Schlenk flask under an argon atmosphere 0.0592 g (0.099 mmol) (S,S)-ethylene-1,2-bis(η5 -4,5,6,7-tetrahydro- 1 -indenyl)titanium (S)-1,1'-binaphth-2,2'-diolate was dissolved in THF (10 mL). The vessel was degassed by exposure to vacuum (2×~10 sec), put under an atmosphere of hydrogen and subsequently cooled to 0° C. in an ice water bath. After equilibration, a solution of n-butyllithium (0.122 mL, 1.58 M in hexanes, 0.193 mmol, 1.95 equiv) was added and the mixture was allowed to stir for 10 min. Phenylsilane (0.031 mL, 0.243 mmol, 2.5 equiv) and 0.378g (2.19 mmol, 22 equiv) 6-methoxy-1-methyl-3,4-dihydronaphthalene were then added. The flask was sealed and the solution moved into a dry box and transferred to a Parr® high pressure reaction vessel containing a magnetic stir bar. The pressure vessel was sealed and moved to a fume hood where it was charged to 1800 psig with hydrogen and placed in an oil bath at 68° C. The reaction mixture was allowed to stir for 132 h. The vessel was cooled to room temperature, vented and opened to air. The reaction mixture was worked up by partitioning between diethyl ether hexane (1/4) and water and separating the layers. The organic extract was concentrated and chromatographed on 50 mL silica gel to yield 0.268g (1.54 mmol, 70%) of 6-methoxy-1-methyl-1,2,3,4-tetrahydronaphthalene with an ee of 94.7%.

후처리

  1. customThe vessel was degassed by exposure to vacuum (2×~10 sec)
  2. customThe flask was sealed
  3. customthe solution moved into a dry box
  4. customtransferred to a Parr® high pressure reaction vessel
  5. additioncontaining a magnetic stir bar
  6. customThe pressure vessel was sealed
  7. customplaced in an oil bath at 68° C
  8. stirringto stir for 132 h
  9. temperatureThe vessel was cooled to room temperature
  10. customby partitioning between diethyl ether hexane (1/4) and water
  11. customseparating the layers
  12. extractionThe organic extract
  13. concentrationwas concentrated
  14. customchromatographed on 50 mL silica gel

출처 및 근거

ORD 기록
ord-76df642fb47a4fb3ba02eeaea87cc874
출처 데이터셋
uspto-grants-1996_02
특허 번호
US05491233

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