Trimethylsilylacetylene → Silane, trimethyl[[4-[(tetrahydro-2H-pyran-2-yl)oxy]phenyl]ethynyl]-

HRID 1191966Notes

Reaction equation

HRID 1191966 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH:9]2[CH2:14][CH2:13][CH2:12][CH2:11][O:10]2)=[CH:4][CH:3]=1.[CH3:15][Si:16]([C:19]#[CH:20])([CH3:18])[CH3:17]>C(NC(C)C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[O:10]1[CH2:11][CH2:12][CH2:13][CH2:14][CH:9]1[O:8][C:5]1[CH:6]=[CH:7][C:2]([C:20]#[C:19][Si:16]([CH3:18])([CH3:17])[CH3:15])=[CH:3][CH:4]=1

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 29168032H-Pyran, tetrahydro-2-(4-iodophenoxy)-

Product 1

HCID 10540306Silane, trimethyl[[4-[(tetrahydro-2H-pyran-2-yl)oxy]phenyl]ethynyl]-

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolvent

Procedure

To a degassed solution of compound 1 (9.12 g, 30 mmol) in diisopropylamine (180 ml) under nitrogen, Pd(PPh3)2Cl2 (140 mg, 0.2 mmol) and CuI (78 mg, 0.4 mmol) were added. Then trimethylsilyl acetylene (3.3 g, 33 mmol) was added dropwise to this clear solution. The reaction mixture was stirred for 2 hours at room temperature. The salt formed during the reaction procedure was filtered off and washed well with ethyl acetate. The filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (5 ml), water (25 ml) and crushed ice (10 g), then extracted with ethyl acetate. The combined organic paste was washed with brine and dried with MgSO4. The solvent was removed in vacuo and the residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1) to give a yellow oil of 2. Yield 7.9 g (96%);

Workup

  1. customThe salt formed during the reaction procedure
  2. filtrationwas filtered off
  3. washwashed well with ethyl acetate
  4. customThe filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (5 ml), water (25 ml)
  5. customcrushed ice (10 g)
  6. extractionextracted with ethyl acetate
  7. washThe combined organic paste was washed with brine
  8. dry with materialdried with MgSO4
  9. customThe solvent was removed in vacuo
  10. customthe residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1)
  11. customto give a yellow oil of 2

Sources & evidence

ORD record
ord-a385b37cc9c344fc84b49935ac09cf98
Source dataset
uspto-grants-2014_03
Patent number
US08680142B2

Reaction notes

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