Potassium Carbonate → HCID 90015018, compound

HRID 1057038Notes

Reaction equation

HRID 1057038 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6](I)[CH:5]=[C:4]([Cl:9])[N:3]=1.CC1(C)C(C)(C)OB([C:18]2[CH2:23][CH2:22][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:20][CH:19]=2)O1.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.O.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].C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[C:6]([C:18]2[CH2:23][CH2:22][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:20][CH:19]=2)[CH:5]=[C:4]([Cl:9])[N:3]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 117373932,6-Dichloro-4-iodopyridine

Product 1

HCID 90015018HCID 90015018, compoundYield 56%

Reagents, catalysts & solvents 3

HCID 178418807HCID 178418807, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

To a mixture of 2,6-dichloro-4-iodo-pyridine (1.0 g, 3.7 mmol), tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydro-2H-pyridine-1-carboxylate (1.4 g; 4.4 mmol), potassium carbonate (1.0 g, 7.3 mmol), and Pd(dppf)Cl2 DCM (300 mg, 0.37 mmol) in 1,4-dioxane (12.0 mL) and water (3.0 mL) was capped in a large CEM microwave vial, de-gassed with N2, and heated in an oil-bath at 90° C. for overnight. It was diluted with water (100 mL), extracted with EtOAc (2×100 mL). The combined EtOAc was washed with brine, dried over MgSO4, filtered, and concentrated onto Celite. It was purified by column chromatography (ISCO0, 40 g column, eluded with 0-15% EtOAc/Heptane to give 670 mg (56%) of the title compound as a light yellow solid. 1H NMR (400 MHz, CDCl3) δ 7.21 (s, 2H), 6.32 (s, 1H), 4.12 (d, J=2.7 Hz, 2H), 3.63 (t, J=5.6 Hz, 2H), 2.45 (s, 2H), 1.49 (s, 9H). LC-MS: m/z=330 (M+H+).

Workup

  1. customwas capped in a large CEM microwave vial
  2. customde-gassed with N2
  3. additionIt was diluted with water (100 mL)
  4. extractionextracted with EtOAc (2×100 mL)
  5. washThe combined EtOAc was washed with brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated onto Celite
  9. customIt was purified by column chromatography (ISCO0, 40 g column

Sources & evidence

ORD record
ord-abfdd0d2869c4e10b70f232a25885484
Source dataset
uspto-grants-2016_07
Patent number
US09399636B2

Reaction notes

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