Triethylamine → Methyl 2-(4-fluoro-2-((trimethylsilyl)ethynyl)phenyl)acetate

HRID 1779011Notes

Reaction equation

HRID 1779011 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].Br[C:8]1[CH:13]=[C:12]([F:14])[CH:11]=[CH:10][C:9]=1[CH2:15][C:16]([O:18][CH3:19])=[O:17].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCN(CC)CC>C1COCC1.[Cu]I.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>[F:14][C:12]1[CH:11]=[CH:10][C:9]([CH2:15][C:16]([O:18][CH3:19])=[O:17])=[C:8]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[CH:13]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 25178031Methyl (2-bromo-4-fluorophenyl)acetate

Product 1

HCID 59457720Methyl 2-(4-fluoro-2-((trimethylsilyl)ethynyl)phenyl)acetate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
35 °C

Procedure

A suspension of (trimethylsilyl)acetylene (0.696 g, 7.08 mmol), methyl 2-(2-bromo-4-fluorophenyl)acetate (A48) (0.500 g, 2.02 mmol), PPh3 (0.053 g, 0.202 mmol), CuI (39 mg, 0.202 mmol), Et3N (1.41 mL, 10.1 mmol) and PdCl2(PPh3)2 (0.142 g, 0.202 mmol) in THF (25 mL) was heated at 35° C. for 16 hours. The resulting mixture was adsorbed onto silica gel and purified using column chromatography (Biotage Isolera, 40 g SiO2 cartridge, 0-40% EtOAc in petroleum benzine 40-60° C.) to yield the title compound A49 as a clear oil (0.212 g, 40%); LCMS-A: rt 6.830 min.

Workup

  1. custompurified
  2. customcolumn chromatography (Biotage Isolera, 40 g SiO2 cartridge, 0-40% EtOAc in petroleum benzine 40-60° C.)

Sources & evidence

ORD record
ord-445d03570856473fb14bf8cdbf5f7e32
Source dataset
uspto-grants-2016_02
Patent number
US09266864B2

Reaction notes

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