Triethylamine → Methyl 2-(2-((trimethylsilyl)ethynyl)phenyl)acetate

HRID 1711081Notes

Reaction equation

HRID 1711081 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:9]([O:11][CH3:12])=[O:10].C(N(CC)CC)C.[CH3:20][Si:21]([C:24]#[CH:25])([CH3:23])[CH3:22]>COCCOC.[Cu]I.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:20][Si:21]([C:24]#[C:25][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:9]([O:11][CH3:12])=[O:10])([CH3:23])[CH3:22]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 640185Methyl 2-(2-iodophenyl)acetate

Product 1

HCID 59457733Methyl 2-(2-((trimethylsilyl)ethynyl)phenyl)acetateYield 69.4%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a solution of ester 318 (7.50 g, 27.2 mmol) in dry DME (125 mL) at 0° C. was added triethylamine (6.0 mL, 4.3 g, 43 mmol), copper (I) iodide (1.00 g, 5.25 mmol), and bis(triphenylphosphine) palladium (II) chloride (0.65 g, 0.93 mmol). The mixture was degassed with a stream of N2 for 5 min, then trimethylsilylacetylene (5.8 mL, 4.1 g, 41 mmol) was added and the reaction mixture was warmed to room temperature and stirred for 24 h. It was concentrated under reduced pressure, partitioned between ethyl acetate and water, washed with brine, dried (anhydrous MgSO4), filtered and concentrated. Flash chromatography of the residue (eluent 4% ethyl acetate/hexanes) afforded title compound 319 (4.65 g, 69% yield). 1H NMR (400 MHz, CDCl3) δ (ppm): 7.22 (dd, J=7.4, 0.8 Hz, 1H); 7.07-6.95 (m, 3H); 3.58 (s, 2H); 3.45 (s, 3H); 0.00 (s, 9H). LCMS: (M+H) 247.1.

Workup

  1. customThe mixture was degassed with a stream of N2 for 5 min
  2. concentrationIt was concentrated under reduced pressure
  3. custompartitioned between ethyl acetate and water
  4. washwashed with brine
  5. dry with materialdried (anhydrous MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-68a6e7286b45420faba7e009d3d1fb37
Source dataset
uspto-grants-2010_09
Patent number
US07790729B2

Reaction notes

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