Phenylsilane → 1-Methyltetraline

HRID 2396300Notes

Reaction equation

HRID 2396300 reaction equation
C([Li])CCC.C1([SiH3])C=CC=CC=1.[CH3:13][C:14]1[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[CH2:17][CH2:16][CH:15]=1.[H][H]>C1COCC1>[CH3:13][CH:14]1[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[CH2:17][CH2:16][CH2:15]1

Participants

6

Reactant 4

HCID 12752PhenylsilaneHCID 5823271,2-Dihydro-4-methylnaphthaleneHCID 178418339ButyllithiumHCID 178418361HCID 178418361, compound

Product 1

HCID 152621-MethyltetralineYield 70.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

In a dry sealable Schlenk flask under an argon atmosphere 0.059g (0.099 mmol) (S,S)-ethylene-1.2-bisη5 -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 (0.125 mL, 1.58 M in hexanes, 0.196 mmol, 1.96 equiv) was added and the mixture was allowed to stir for 10 min. Phenylsilane (0.033 mL, 0.259 mmol, 2.6 equiv) and 0.273 g (1.87 mmol, 19 equiv) 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 2150 psig with hydrogen and placed in an oil bath at 65° C. The reaction mixture was allowed to stir/br 184 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 0.195 g (1.31 mmol, 70%) of 1-methyl-1,2,3,4-tetrahydronaphthalene with an ee of 70 %, determined polarimetrically.

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 65° C
  8. waitThe reaction mixture was allowed to stir/br 184 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-39fbd3667dd6441ab4f687b674e5a22a
Source dataset
uspto-grants-1996_02
Patent number
US05491233

Reaction notes

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