Tributylvinyltin → 5-vinyl-2,3-dihydro-1H-inden-1-one

HRID 1506493Notes

Reaction equation

HRID 1506493 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[C:7](=[O:11])[CH2:6][CH2:5]2.[CH2:12]([Sn](CCCC)(CCCC)C=C)[CH2:13]CC>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.C1(C)C=CC=CC=1>[CH:12]([C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[C:7](=[O:11])[CH2:6][CH2:5]2)=[CH2:13]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 5206955-Bromo-1-indanone

Product 1

HCID 671719145-vinyl-2,3-dihydro-1H-inden-1-oneYield 80.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a mixture of 5-bromo-2,3-dihydro-1H-inden-1-one (2 g, 9.48 mmol), tributyl(vinyl)stannane (3.32 mL, 11.37 mmol) and toluene (30 mL) in a sealed tube was added Pd(Ph3P)4 (0.548 g, 0.474 mmol). Nitrogen was bubbled through the reaction for 5 min., the vessel was sealed and heated at 100° C. for 20 hr. After cooling the reaction mixture to room temperature, ethyl acetate (20 mL), water (30 mL) and celite were added. The mixture was stirred at room temperature for 30 min. and filtered. The EtOAc layer was separated and the aqueous layer was re-extracted with ethyl acetate (3×10 mL). The combined organic extracts were dried (sodium sulfate) and concentrated under reduced pressure. Flash chromatography purification (40 g silica gel column, 5→50% ethyl acetate in hexanes) afforded 5-vinyl-2,3-dihydro-1H-inden-1-one (1.2 g, 7.59 mmol, 80% yield) as a yellow solid. The product had an HPLC ret. time=2.50 min. (condition C); LC/MS M+1=159.2.

Workup

  1. customNitrogen was bubbled through the reaction for 5 min.
  2. customthe vessel was sealed
  3. temperatureAfter cooling the reaction mixture to room temperature
  4. additionethyl acetate (20 mL), water (30 mL) and celite were added
  5. filtrationfiltered
  6. customThe EtOAc layer was separated
  7. extractionthe aqueous layer was re-extracted with ethyl acetate (3×10 mL)
  8. dry with materialThe combined organic extracts were dried (sodium sulfate)
  9. concentrationconcentrated under reduced pressure
  10. customFlash chromatography purification (40 g silica gel column, 5→50% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-dc9db3f9cc5e4ce2be46e8596993b6f8
Source dataset
uspto-grants-2015_12
Patent number
US09216972B2

Reaction notes

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