Pentane → 3-Trimethylstannyl-9-(hydroxymethyl)-phenanthrene

HRID 1084312Notes

Reaction equation

HRID 1084312 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[CH:6]=[C:7]([CH2:16][O:17][Si](C(C)(C)C)(C)C)[C:8]3[C:13]([C:14]=2[CH:15]=1)=[CH:12][CH:11]=[CH:10][CH:9]=3.C([Li])(C)(C)C.CCCCC.[Sn:35](Cl)([CH3:38])([CH3:37])[CH3:36].[N+](CCCC)(CCCC)(CCCC)CCCC.[F-]>C1COCC1>[CH3:36][Sn:35]([CH3:38])([CH3:37])[C:2]1[CH:3]=[CH:4][C:5]2[CH:6]=[C:7]([CH2:16][OH:17])[C:8]3[C:13]([C:14]=2[CH:15]=1)=[CH:12][CH:11]=[CH:10][CH:9]=3

Participants

7

Reactant 5

HCID 8003PentaneHCID 14016Trimethyltin chlorideHCID 2724141Tetrabutylammonium FluorideHCID 15159130[(3-Bromophenanthren-9-YL)methoxy](tert-butyl)dimethylsilaneHCID 178418306HCID 178418306, compound

Product 1

HCID 151591313-Trimethylstannyl-9-(hydroxymethyl)-phenanthreneYield 79%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Bromophenanthrene 5 (1.02 g, 2.5 mmol) was dissolved in anhydrous THF (15 mL) and cooled to -78° C. under nitrogen. To this stirred solution was added a solution of t-Butyllithium in pentane (2.2 equiv.; 5.5 mmol; 3.0 mL). After 30 minutes at -78° C., the reaction was warmed to -50° C. for 20 minutes, after which time Me3SnCl (1.1 equiv.; 2.75 mmol; 548 mg) was added as a solid. The cold bath was removed and the reaction allowed to reach ambient temperature. After 75 minutes, the reaction was quenched with water. The solvent was removed in vacuo and the residual dissolved in Et2O. Washing with water and brine was followed by drying over MgSO4, filtering and removal of solvent. The residual was dissolved in anhydrous THF and treated with a 1.0M solution of n-Bu4NF in THF (1.1 equiv.; 2.75 mmol; 2.75 mL) at ambient temperature for 5 minutes. Quenching the reaction with saturated NH4Cl was followed by removal of the solvent in vacuo. The residual was dissolved in EtOAc and washed with water and brine, dried (MgSO4), filtered and the solvent removed in vacuo. Purification by flash chromatography (25% EtOAc/hexanes) provided 733 mg (78%) of stannyl alcohol 5A as a white solid.

Workup

  1. temperaturethe reaction was warmed to -50° C. for 20 minutes
  2. customThe cold bath was removed
  3. customto reach ambient temperature
  4. waitAfter 75 minutes
  5. customthe reaction was quenched with water
  6. customThe solvent was removed in vacuo
  7. dissolutionthe residual dissolved in Et2O
  8. washWashing with water and brine
  9. dry with materialby drying over MgSO4
  10. filtrationfiltering
  11. customremoval of solvent
  12. dissolutionThe residual was dissolved in anhydrous THF
  13. customQuenching
  14. customthe reaction with saturated NH4Cl
  15. customwas followed by removal of the solvent in vacuo
  16. dissolutionThe residual was dissolved in EtOAc
  17. washwashed with water and brine
  18. dry with materialdried (MgSO4)
  19. filtrationfiltered
  20. customthe solvent removed in vacuo
  21. customPurification by flash chromatography (25% EtOAc/hexanes)

Sources & evidence

ORD record
ord-2545fba37c0845c39585490c1cec7346
Source dataset
uspto-grants-1991_04
Patent number
US05004739

Reaction notes

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