tert-Butyl methyl ether → HCID 76621206, compound

HRID 1876927Notes

Reaction equation

HRID 1876927 reaction equation
[C:1]([O:5][C:6](=[O:28])[CH:7]([NH:16][C:17](=[O:27])[C:18]1[C:23]([CH3:24])=[CH:22][C:21]([CH3:25])=[CH:20][C:19]=1[CH3:26])[CH2:8][C:9]1[CH:14]=[CH:13][C:12](I)=[CH:11][CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[C:29]([Si](C)(C)C)#[CH:30].CC(OC)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>CCN(CC)CC.C1COCC1.[Cu]I.O>[C:1]([O:5][C:6](=[O:28])[CH:7]([NH:16][C:17](=[O:27])[C:18]1[C:23]([CH3:24])=[CH:22][C:21]([CH3:25])=[CH:20][C:19]=1[CH3:26])[CH2:8][C:9]1[CH:14]=[CH:13][C:12]([C:29]#[CH:30])=[CH:11][CH:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

9

Reactant 4

HCID 15413tert-Butyl methyl etherHCID 66111TrimethylsilylacetyleneHCID 2724141Tetrabutylammonium FluorideHCID 68945571HCID 68945571, compound

Product 1

HCID 76621206HCID 76621206, compoundYield 49.3%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

500 mg (1.01 mmol) of (2), 38 mg (0.203 mmol) of CuI and 71 mg (0.1 eq.) of PdCl2(PPh)3 were dissolved in 10 ml of Et3N. to The solution was flushed with Argon and 1.68 ml (1.216 mmol) of ethynyl-trimethyl silane were added and stirred for 2 h at room temperature. The reaction mixture was poured into MTBE, washed with saturated NaHCO3, brine and dried over Na2SO4. The solvent was removed at the evaporator. The crude product was dissolved in 20 ml of THF and cooled to −78° C. 2 ml (2 mmol) of 1 M TBAF solution in THF were added and the reaction mixture was stirred for 45 min at −78° C. 10 ml of water were added and the product was extracted with diethyl ether. The organic layer was extracted with saturated NaHCO3, brine and dried over Na2SO4. The solvent was removed at the evaporator. The product was purified by column chromatography on silica gel using ethyl acetate/hexane to give 195 mg of (3).

Workup

  1. additionwere added
  2. washwashed with saturated NaHCO3, brine
  3. dry with materialdried over Na2SO4
  4. customThe solvent was removed at the evaporator
  5. dissolutionThe crude product was dissolved in 20 ml of THF
  6. temperaturecooled to −78° C
  7. stirringthe reaction mixture was stirred for 45 min at −78° C
  8. extractionthe product was extracted with diethyl ether
  9. extractionThe organic layer was extracted with saturated NaHCO3, brine
  10. dry with materialdried over Na2SO4
  11. customThe solvent was removed at the evaporator
  12. customThe product was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-0f305c788840494c8a7d09f25f969017
Source dataset
uspto-grants-2012_11
Patent number
US08309735B2

Reaction notes

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