Tri-tert-butylphosphine tetrafluoroborate → HCID 86713260, compound

HRID 928026Notes

Reaction equation

HRID 928026 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[S:8]([NH:11][C:12]1[C:21]([C:22]([O:24][CH3:25])=[O:23])=[C:20]2[C:15]([CH:16]3[CH2:26][CH:17]3[CH2:18][O:19]2)=[CH:14][CH:13]=1)(=[O:10])=[O:9].[CH2:27]([N:29]([CH2:46][CH3:47])[CH2:30]/[CH:31]=[CH:32]\[Sn](CCCC)(CCCC)CCCC)[CH3:28].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>O1CCOCC1.CS(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:27]([N:29]([CH2:46][CH3:47])[CH2:30]/[CH:31]=[CH:32]\[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[S:8]([NH:11][C:12]1[C:21]([C:22]([O:24][CH3:25])=[O:23])=[C:20]2[C:15]([CH:16]3[CH2:26][CH:17]3[CH2:18][O:19]2)=[CH:14][CH:13]=1)(=[O:10])=[O:9])[CH3:28]

Participants

7

Reactant 3

HCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 71006886HCID 71006886, compoundHCID 86684726N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)amine2×

Product 1

HCID 86713260HCID 86713260, compoundYield 75.3%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 679Dimethyl SulfoxideSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of methyl (1aRS,7bSR)-5-(2-bromobenzenesulfonylamino)-1,1a,2,7b-tetrahydro-cyclopropa[c]chromene-4-carboxylate (Intermeidate 154, 0.612 g), N,N-diethyl-N—((Z)-1-tributylstannanylprop-1-en-3-yl)amine (Intermediate 11, 1.13 g), tri-tert-butylphosphonium tetrafluoroborate (0.041 g), tris-(dibenzylideneacetone)dipalladium (0.064 g) in dioxane (12 mL) and DMSO (0.4 mL) was degassed and purged with nitrogen then heated at 100° C. for 1.5 hours. After cooling, the mixture was diluted with brine and extracted with ethyl acetate. The organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of methanol and DCM with a gradient of 0-15% to give methyl (1aRS,7bSR)-5-[2-((Z)-3-diethylamino-prop-1-enyl)benzenesulfonylamino]-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate (0.495 g) as a solid.

Workup

  1. customwas degassed
  2. custompurged with nitrogen
  3. temperatureAfter cooling
  4. additionthe mixture was diluted with brine
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with water
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customThe filtrate was evaporated to dryness
  10. customthe residue was purified by chromatography on silica
  11. washeluting with a mixture of methanol and DCM with a gradient of 0-15%

Sources & evidence

ORD record
ord-1cf2ade92f49469f85d50dc544e43bf8
Source dataset
uspto-grants-2016_03
Patent number
US09290472B2

Reaction notes

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