Dichloromethane → HCID 86667836, compound

HRID 1913219Notes

Reaction equation

HRID 1913219 reaction equation
[CH3:1][Si:2]([CH3:39])([CH3:38])[CH2:3][CH2:4][O:5][CH2:6][N:7]([CH2:30][O:31][CH2:32][CH2:33][Si:34]([CH3:37])([CH3:36])[CH3:35])[C:8]1[N:13]2[N:14]=[CH:15][C:16](I)=[C:12]2[N:11]=[C:10]([CH2:18][CH:19]2[CH2:24][CH2:23][CH:22]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:21][CH2:20]2)[CH:9]=1.[Cl:40][C:41]1[N:46]=[CH:45][C:44](B2OC(C)(C)C(C)(C)O2)=[CH:43][CH:42]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C(Cl)Cl>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].O.O1CCOCC1>[CH3:1][Si:2]([CH3:39])([CH3:38])[CH2:3][CH2:4][O:5][CH2:6][N:7]([CH2:30][O:31][CH2:32][CH2:33][Si:34]([CH3:37])([CH3:36])[CH3:35])[C:8]1[N:13]2[N:14]=[CH:15][C:16]([C:44]3[CH:45]=[N:46][C:41]([Cl:40])=[CH:42][CH:43]=3)=[C:12]2[N:11]=[C:10]([CH2:18][CH:19]2[CH2:24][CH2:23][CH:22]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:21][CH2:20]2)[CH:9]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 62657Potassium Phosphate, TribasicHCID 27947192-Chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridineHCID 69929724HCID 69929724, compound

Product 1

HCID 86667836HCID 86667836, compound

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a 10-20 mL microwave vessel was charged ethyl 4-((7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-3-iodopyrazolo[1,5-a]pyrimidin-5-yl)methyl)cyclohexanecarboxylate (Int-4j, 2.94 g, 4.27 mmol), 6-chloropyridine-3-boronic acid pinacol ester (1.07 g, 4.48 mmol), K3PO4 (2.72 g, 12.81 mmol), and PdCl2(dppf)2.CH2Cl2 (349 mg, 0.43 mmol). To this was added 9:1 1,4-dioxane:H2O. The vial was flushed with argon, sealed, and stirred at 100° C. overnight. After 18 hours, the reaction was cooled to room temperature and diluted with DCM. The reaction was washed with water and the aqueous phase was extracted again with DCM. The combined organics were dried over Na2SO4 and the residue purified via silica gel chromatography to yield title compound as yellowish oil that crystallizes over time. Yield=1.93 g.

Workup

  1. customThe vial was flushed with argon
  2. customsealed
  3. waitAfter 18 hours
  4. temperaturethe reaction was cooled to room temperature
  5. additiondiluted with DCM
  6. washThe reaction was washed with water
  7. extractionthe aqueous phase was extracted again with DCM
  8. dry with materialThe combined organics were dried over Na2SO4
  9. customthe residue purified via silica gel chromatography

Sources & evidence

ORD record
ord-3fa2f78c4b0f40da9f100d382a9de832
Source dataset
uspto-grants-2013_12
Patent number
US08609675B2

Reaction notes

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