Ethylene → 2-[1-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2,3-dihydro-1H-inden-5-yl]thiazole

HRID 2178786Notes

Reaction equation

HRID 2178786 reaction equation
BrCCBr.C=C.Cl[Si](C)(C)C.Br[C:13]1[S:14][CH:15]=[CH:16][N:17]=1.Br[C:19]1[CH:20]=[C:21]2[C:25](=[CH:26][CH:27]=1)[CH:24]([O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[CH2:23][CH2:22]2>O1CCCC1.[Zn].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Si:29]([O:28][CH:24]1[C:25]2[C:21](=[CH:20][C:19]([C:13]3[S:14][CH:15]=[CH:16][N:17]=3)=[CH:27][CH:26]=2)[CH2:22][CH2:23]1)([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30]

Participants

9

Reactant 5

HCID 6325EthyleneHCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 764302-BromothiazoleHCID 23087566HCID 23087566, compound

Product 1

HCID 248204742-[1-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2,3-dihydro-1H-inden-5-yl]thiazoleYield 79%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

To a stirred suspension of zinc (899 mg, 13.75 mmol) in tetrahydrofuran (1.60 mL) was added 1,2-dibromoethane (0.118 mL, 1.37 mmol). The suspension was heated with a heat gun until no evolution of ethylene gas. Chlorotrimethylsilane (0.0698 mL, 0.55 mmol) and a solution of 2-bromothiazole (0.413 mL, 4.58 mmol) in tetrahydrofuran were added. After 15 min [(5-bromo-2,3-dihydro-1H-inden-1-yl)oxy](tert-butyl)dimethylsilane (1.0 g, 3.055 mmol) and tetrakis(triphenylphosphine)palladium(0) (70.6 mg, 0.0611 mmol) dissolved in tetrahydrofuran (8.00 mL) were added. The mixture was stirred for 24 h at reflux and quenched with 15 mL of brine. The organic layer was separated and the aqueous phase was extracted with methylene chloride (25 mL×3). The combined extracts were washed with brine, dried over anhydrous Na2SO4, and evaporated under reduced pressure. Chromatography on silica gel with 2.5% EtOAc/hexane afforded the desired coupling product (800 mg, 79%).

Workup

  1. additionwere added
  2. temperatureat reflux
  3. customquenched with 15 mL of brine
  4. customThe organic layer was separated
  5. extractionthe aqueous phase was extracted with methylene chloride (25 mL×3)
  6. washThe combined extracts were washed with brine
  7. dry with materialdried over anhydrous Na2SO4
  8. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-bd9cfd1d92bf456a83ecf41d02ec0518
Source dataset
uspto-grants-2015_06
Patent number
US09067921B2

Reaction notes

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