Cesium fluoride → HCID 20781256, compound

HRID 2181274Notes

Reaction equation

HRID 2181274 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([S:8]([C:11]2([C:25]3[CH:30]=[C:29]([F:31])[CH:28]=[CH:27][C:26]=3[F:32])[CH2:16][CH2:15][CH:14]([NH:17][S:18]([C:21]([F:24])([F:23])[F:22])(=[O:20])=[O:19])[CH2:13][CH2:12]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.[F-].[Cs+].[CH2:35]([Sn](CCCC)(CCCC)C=C)[CH2:36]CC>O1CCOCC1.C(OCC)C.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].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>[F:32][C:26]1[CH:27]=[CH:28][C:29]([F:31])=[CH:30][C:25]=1[C:11]1([S:8]([C:5]2[CH:6]=[CH:7][C:2]([CH:35]=[CH2:36])=[CH:3][CH:4]=2)(=[O:9])=[O:10])[CH2:12][CH2:13][CH:14]([NH:17][S:18]([C:21]([F:24])([F:22])[F:23])(=[O:19])=[O:20])[CH2:15][CH2:16]1

Participants

8

Reactant 3

HCID 25953Cesium fluorideHCID 81998TributylvinyltinHCID 11577204MRK 560

Product 1

HCID 20781256HCID 20781256, compoundYield 271.5%

Reagents, catalysts & solvents 4

HCID 83681Tris(1,1-dimethylethyl)phosphineCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

Nitrogen was bubbled through a solution containing the product of Example 47 (1.0 g, 1.93 mmol), tri-t-butylphosphine (0.1 M in dioxane, 190 μl, 0.19 mmol), cesium fluoride (0.65 g, 4.28 mmol) and Pd2(dba)3 (0.10 g, 0.11 mmol) in dioxane (8 ml) in a sealed tube for 5 minutes. Tributyl(vinyl)tin (0.65 g, 2.05 mmol) was added and the mixture heated at 100° C. for 2 hours. This sequence was repeated on the same scale a further four times. All five reaction mixtures were combined and diluted with diethyl ether (50 ml) and filtered through a silica gel pad, evaporated in vacuo to give crude product which was chromatographed on silica eluting with 5-20% ethyl acetate/isohexane, then azeotroped with dichloromethane to give the desired product (2.67 g, 55%). 1H NMR (CDCl3, 360 MHz): 1.59-1.70 (2H, m), 2.02-2.06 (2H, m), 2.44 (2H, t, J=12.7 Hz), 2.61-2.65 (2H, m), 3.78 (1H, m), 5.47 (1H, d, J=10.9 Hz), 5.82 (1H, bd, J=7.8 Hz), 5.88 (1H, d, J=17.5 Hz), 6.68-6.87 (1H, m), 7.01-7.08 (2H, m), 7.32 (2H, d, J=8.3), 7.40 (2H, d, J=8.1), 10.10 (1H, s)

Workup

  1. customNitrogen was bubbled through a solution
  2. customAll five reaction mixtures
  3. filtrationfiltered through a silica gel pad
  4. customevaporated in vacuo
  5. customto give crude product which
  6. customwas chromatographed on silica eluting with 5-20% ethyl acetate/isohexane
  7. customazeotroped with dichloromethane

Sources & evidence

ORD record
ord-af1e073977194c1ab34f53a1e3c9dadd
Source dataset
uspto-grants-2005_05
Patent number
US06890956B2

Reaction notes

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