Lithium Chloride → HCID 86723436, compound

HRID 2201193Notes

Reaction equation

HRID 2201193 reaction equation
[CH3:1][N:2]1[C:14](=[O:15])[N:13]([CH3:16])[C:12](=[O:17])[C:11]2[C:3]1=[C:4]1[N:9]([C:10]=2[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[NH:8][CH2:7][CH:6]=[C:5]1OS(C(F)(F)F)(=O)=O.[Li+].[Cl-].[CH3:34][C:35]1[N:36]=[C:37]([Sn](CCCC)(CCCC)CCCC)[S:38][CH:39]=1>C1COCC1.CCOC(C)=O.[Cu](I)I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:1][N:2]1[C:3]2=[C:4]3[C:5]([C:37]4[S:38][CH:39]=[C:35]([CH3:34])[N:36]=4)=[CH:6][CH2:7][NH:8][N:9]3[C:10]([C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)=[C:11]2[C:12](=[O:17])[N:13]([CH3:16])[C:14]1=[O:15]

Participants

8

Reactant 3

HCID 433294Lithium ChlorideHCID 164271304-Methyl-2-(tributylstannyl)-1,3-thiazole2×HCID 86723435HCID 86723435, compound

Product 1

HCID 86723436HCID 86723436, compound

Reagents, catalysts & solvents 4

HCID 83717Copper iodideCatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Trifluoro-methanesulfonic acid 5,7-dimethyl-6,8-dioxo-9-phenyl-1,2,5,6,7,8-hexahydro-1,5,7,9a-tetraaza-fluoren-4-yl ester (step 5) (280 mg, 0.614 mmol), LiCl (2.60 mg, 0.061 mmol), copper iodide (11.68 mg, 0.061 mmol) and 4-methyl-2-tributylstannanyl-thiazole (Intermediate J) (4.45 g, 11.46 mmol) were combined in THF (15 ml) and PdCl2(dppf) (44.9 mg, 0.061 mmol) was added. The mixture was heated at reflux for 1 hour. The reaction mixture was cooled to RT and diluted with EtOAc. The mixture was washed with dil. NH4OH(aq), 1M KF(aq) and brine. The organic phase was dried over sodium sulphate and evaporated under reduced pressure. Purification of the residue by chromatography on silica, eluting with EtOAc/hexane, afforded the title compound as a crude pale brown solid.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 1 hour
  3. washThe mixture was washed with dil. NH4OH(aq), 1M KF(aq) and brine
  4. dry with materialThe organic phase was dried over sodium sulphate
  5. customevaporated under reduced pressure
  6. customPurification of the residue by chromatography on silica
  7. washeluting with EtOAc/hexane

Sources & evidence

ORD record
ord-c0566791960a44beaa568cae03367b94
Source dataset
uspto-grants-2016_06
Patent number
US09359381B2

Reaction notes

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