Tributylvinyltin → HCID 22323781, compound

HRID 1506314Notes

Reaction equation

HRID 1506314 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[C:15]2[C:10]([C:11](=[O:17])[CH2:12][CH2:13][O:14]2)=[CH:9][CH:8]=1)(=O)=O.[CH2:20]([Sn](CCCC)(CCCC)C=C)[CH2:21]CC.[Cl-].[Li+]>O1CCOCC1.[Pd].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.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>[CH:20]([C:7]1[CH:16]=[C:15]2[C:10]([C:11](=[O:17])[CH2:12][CH2:13][O:14]2)=[CH:9][CH:8]=1)=[CH2:21]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 103571863,4-Dihydro-4-oxo-2H-1-benzopyran-7-yl 1,1,1-trifluoromethanesulfonate

Product 1

HCID 22323781HCID 22323781, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 4-oxochroman-7-yl trifluoromethanesulfonate (Preparation 2C, 2.00 g, 6.75 mmol) in dioxane (10 mL) in a sealed tube was added sequentially tributyl(vinyl) stannane (2.18 mL, 7.43 mmol) and lithium chloride (0.859 g, 20.3 mmol). The mixture was degassed under reduced pressure and charged with nitrogen (2×). To the mixture was added tetrakis(triphenylphosphine) palladium(0) (0.780 g, 0.675 mmol), and the mixture was stirred under a strong stream of nitrogen for 5 min. The reaction mixture was sealed, immersed in an oil bath at 100° C., and stirred overnight. The reaction mixture was cooled to room temperature and filtered under reduced pressure. The solid was washed with ethyl acetate (4×50 mL), and the filtrate was concentrated. The crude product mixture was diluted with ether (˜100 mL), sonicated for several minutes, and filtered (the cake was rinsed with ether). The filtrate was concentrated under reduced pressure, and the residue was purified by flash silica gel chromatography using a mixture of ethyl acetate in hexane (5%-12%-15%) to give 7-vinylchroman-4-one (0.938 g, 5.38 mmol, 80% yield) as a yellow oil. The product had a HPLC ret. time=1.93 min. (condition A); LC/MS M+1=174.9; 1H NMR (400 MHz, CDCl3) δ ppm 2.78-2.85 (m, 2H), 4.52-4.58 (m, 2H), 5.42 (d, J=10.78 Hz, 1H), 5.88 (d, J=17.61 Hz, 1H), 6.69 (dd, J=17.61, 11.00 Hz, 1H), 6.98 (d, J=1.54 Hz, 1H), 7.09 (dd, J=8.25, 1.43 Hz, 1H), and 7.87 (d, J=8.14 Hz, 1H).

Workup

  1. customThe mixture was degassed under reduced pressure
  2. additioncharged with nitrogen (2×)
  3. customThe reaction mixture was sealed
  4. customimmersed in an oil bath at 100° C.
  5. stirringstirred overnight
  6. filtrationfiltered under reduced pressure
  7. washThe solid was washed with ethyl acetate (4×50 mL)
  8. concentrationthe filtrate was concentrated
  9. additionThe crude product mixture was diluted with ether (˜100 mL)
  10. customsonicated for several minutes
  11. filtrationfiltered (the cake
  12. washwas rinsed with ether)
  13. concentrationThe filtrate was concentrated under reduced pressure
  14. customthe residue was purified by flash silica gel chromatography
  15. additiona mixture of ethyl acetate in hexane (5%-12%-15%)

Sources & evidence

ORD record
ord-4aeae0af2d6a44dcac5d47aa2619c8ab
Source dataset
uspto-grants-2015_12
Patent number
US09216972B2

Reaction notes

Loading…