Phenylsilane → HCID 10607374, compound

HRID 2396302Notes

Reaction equation

HRID 2396302 reaction equation
C([Li])CCC.C1([SiH3])C=CC=CC=1.[CH3:13][O:14][C:15]1[CH:24]=[C:23]2[C:18]([CH2:19][CH2:20][C:21]([CH3:25])=[CH:22]2)=[CH:17][CH:16]=1.[H][H]>C1COCC1>[CH3:13][O:14][C:15]1[CH:24]=[C:23]2[C:18]([CH2:19][CH2:20][CH:21]([CH3:25])[CH2:22]2)=[CH:17][CH:16]=1

Participants

6

Reactant 4

HCID 12752PhenylsilaneHCID 18988808HCID 18988808, compoundHCID 178418339ButyllithiumHCID 178418361HCID 178418361, compound

Product 1

HCID 10607374HCID 10607374, compoundYield 73.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

In a dry sealable Schlenk flask under an argon atmosphere 0.0254 g (0.043 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 (5 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. Alter equilibration, a solution of n-butyllithium (0.052 mL, 1.58 M in hexanes, 0.083 mmol. 1.91 equiv) was added and the mixture was allowed to stir for 10 min. Phenylsilane (0.016 mL, 0.126 mmol, 2.9 equiv) and 0.130 g (0.756 mmol, 18 equiv) 7-methoxy-2-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 2150 psig with hydrogen and placed in an oil bath at 70° C. The reaction mixture was allowed to stir for 44 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 distilled at reduced pressure to yield 0.097 g (0.557 mmol, 73%) of 7-methoxy-2-methyl-1.2,3,4-tetrahydronaphthalene with an ee of 90.4%.

Workup

  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 70° C
  8. stirringto stir for 44 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. distillationwas distilled at reduced pressure

Sources & evidence

ORD record
ord-d7ec9f4777454806860920a355d86240
Source dataset
uspto-grants-1996_02
Patent number
US05491233

Reaction notes

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