HCID 66686135, compound → HCID 68093191, compound

HRID 1778378Notes

Reaction equation

HRID 1778378 reaction equation
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[C:22]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[C:21]2[C:16]([C:17]3[CH:33]=[CH:32][O:31][C:18]=3[C:19](=[O:30])[O:20]2)=[CH:15][CH:14]=1)(=[O:11])=[O:10].[CH2:34]([N:36]([CH2:53][CH3:54])[CH2:37]/[CH:38]=[CH:39]\[Sn](CCCC)(CCCC)CCCC)[CH3:35]>O1CCOCC1>[CH2:34]([N:36]([CH2:53][CH3:54])[CH2:37]/[CH:38]=[CH:39]\[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[C:22]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[C:21]2[C:16]([C:17]3[CH:33]=[CH:32][O:31][C:18]=3[C:19](=[O:30])[O:20]2)=[CH:15][CH:14]=1)(=[O:11])=[O:10])[CH3:35]

Participants

4

Reactant 2

HCID 66686135HCID 66686135, compound2×HCID 86684726N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)amine2×

Product 1

HCID 68093191HCID 68093191, compoundYield 61.5%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

A suspension of tert-butyl 7-(2-bromo-4-fluorobenzenesulfonylamino)-4-oxo-4H-furo[2,3-c]chromene-6-carboxylate (Intermediate 56, 0.330 g) and N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)-amine (Intermediate 3, 0.493 g) in dioxane was warmed slightly then de-gassed and purged with nitrogen. tris-(Dibenzylideneacetone)dipalladium (0.056 g) and tri-tert-butylphosphonium tetrafluoroborate (0.036 g) were added and the mixture was de-gassed and purged with nitrogen again. The resultant mixture was heated at 95° C., under an atmosphere of nitrogen for 75 minutes. This was cooled and concentrated in vacuo and the residue was partitioned between water and ethyl acetate (2×). The combined organic layers were dried (MgSO4), filtered and the filtrate was concentrated in vacuo. The residue was purified by chromatography on silica, eluting with methanol and DCM, with a gradient of 0-25%. The product was triturated with ether and the resultant product was dried in vacuo at 50° C. overnight to give tert-butyl 7-[2((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-4-oxo-4H-furo[2,3-c]chromene-6-carboxylate (0.215 g) as a sand coloured solid.

Workup

  1. temperaturewas warmed slightly
  2. customthen de-gassed
  3. custompurged with nitrogen
  4. additiontris-(Dibenzylideneacetone)dipalladium (0.056 g) and tri-tert-butylphosphonium tetrafluoroborate (0.036 g) were added
  5. customthe mixture was de-gassed
  6. custompurged with nitrogen again
  7. temperatureThis was cooled
  8. concentrationconcentrated in vacuo
  9. customthe residue was partitioned between water and ethyl acetate (2×)
  10. dry with materialThe combined organic layers were dried (MgSO4)
  11. filtrationfiltered
  12. concentrationthe filtrate was concentrated in vacuo
  13. customThe residue was purified by chromatography on silica
  14. washeluting with methanol and DCM, with a gradient of 0-25%
  15. customThe product was triturated with ether
  16. dry with materialthe resultant product was dried in vacuo at 50° C. overnight

Sources & evidence

ORD record
ord-d29a88e4078e4e428d21c18393df39b4
Source dataset
uspto-grants-2016_02
Patent number
US09266896B2

Reaction notes

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