Triphenylphosphine → [2-(3-Methanesulfonylphenyl)ethynyl]trimethylsilane

HRID 1673012Notes

Reaction equation

HRID 1673012 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([S:8]([CH3:11])(=[O:10])=[O:9])[CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:31][Si:32]([C:35]#[CH:36])([CH3:34])[CH3:33]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Cu]I.C(N(CC)CC)C>[CH3:11][S:8]([C:4]1[CH:3]=[C:2]([C:36]#[C:35][Si:32]([CH3:34])([CH3:33])[CH3:31])[CH:7]=[CH:6][CH:5]=1)(=[O:10])=[O:9]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 2757146Benzene, 1-bromo-3-(methylsulfonyl)-

Product 1

HCID 59240077[2-(3-Methanesulfonylphenyl)ethynyl]trimethylsilane

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
82.5 °C

Procedure

Into a sealable tube was weighed 2.06 g (8.76 mmol) of 1-bromo-3-methanesulfonyl-benzene, 93 mg of palladium acetate, 122 mg of triphenylphosphine, 79 mg of copper (I) iodide, 10.0 mL of triethylamine, and 2.0 mL of trimethylsilylacetylene. The reaction vessel was sealed and was heated at 80-85° C. for 1 h then was filtered of solids with added ethyl acetate. The filtrate was concentrated in vacuo and was purified by silica gel flash chromatography (Jones Flashmaster, 50 g Silica gel, gradient elution from 100% hexanes to 40% ethyl acetate over 30 minutes). Appropriate fractions were combined and concentrated in vacuo affording (3-methanesulfonyl-phenylethynyl)-trimethylsilane as a faintly yellow oil, yield: 1.60 g (72%). 1H NMR (CDCl3): δ 8.04 (s, 1H), 7.88 (d, J=8 Hz, 1H), 7.71 (d, J=8 Hz, 1H), 3.05 (s, 3H), 0.27 (s, 9H).

Workup

  1. customInto a sealable tube was weighed
  2. customThe reaction vessel was sealed
  3. filtrationthen was filtered of solids with added ethyl acetate
  4. concentrationThe filtrate was concentrated in vacuo
  5. customwas purified by silica gel flash chromatography (Jones Flashmaster, 50 g Silica gel, gradient elution from 100% hexanes to 40% ethyl acetate over 30 minutes)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5d3b6b80013447239b7abee177bcf933
Source dataset
uspto-grants-2011_08
Patent number
US07998995B2

Reaction notes

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