Sodium Carbonate → HCID 90338571, compound

HRID 1508780Notes

Reaction equation

HRID 1508780 reaction equation
Cl[C:2]1[CH:7]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([Cl:14])[CH:9]=2)[N:5]=[C:4]2[CH2:15][CH2:16][CH2:17][C:3]=12.[CH3:18][C:19]([C:25]1[CH:30]=[CH:29][C:28]([CH2:31]B2OC(C)(C)C(C)(C)O2)=[CH:27][CH:26]=1)([CH3:24])[C:20]([O:22][CH3:23])=[O:21].C([O-])([O-])=O.[Na+].[Na+].O1CCOCC1>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>[Cl:14][C:10]1[CH:9]=[C:8]([C:6]2[N:5]=[C:4]3[CH2:15][CH2:16][CH2:17][C:3]3=[C:2]([CH2:31][C:28]3[CH:27]=[CH:26][C:25]([C:19]([CH3:24])([CH3:18])[C:20]([O:22][CH3:23])=[O:21])=[CH:30][CH:29]=3)[CH:7]=2)[CH:13]=[CH:12][CH:11]=1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 901106754-chloro-2-(3-chlorophenyl)-6,7-dihydro-5H-cyclopenta[b]pyridineHCID 90338678HCID 90338678, compound

Product 1

HCID 90338571HCID 90338571, compoundYield 42.4%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
90 °C

Procedure

A 20-mL sealed tube, with stirrer bar, was charged with 4-chloro-2-(3-chlorophenyl)-6,7-dihydro-5H-cyclopenta[b]pyridine (0.300 g, 1.13 mmol), methyl 2-methyl-2-(4-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)phenyl)propanoate (0.361 g, 1.13 mmol), Pd(dppf)Cl2 (0.093 g, 0.11 mmol), and powdered Na2CO3 (0.361 g, 3.41 mmol). Dioxane (8 mL) and water (4 mL) were added. The resulting mixture was stirred under Ar at 90° C. for 2 d. After cooling to room temperature, the reaction mixture was filtered through celite washing the solids with ethyl acetate. The filtrate layers were separated and the organic layer was washed with saturated sodium chloride (3×10 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by chromatography on silica using hexanes/ethyl acetate (10:0 to 3:1) as eluent to afford the title compound (0.201 g, 42%) as a colorless oil. MW=419.94. 1H NMR (CDCl3, 500 MHz) δ 7.93-7.90 (m, 1H), 7.79-7.76 (m, 1H), 7.37-7.31 (m, 2H), 7.28-7.23 (m, 3H), 7.10-7.14 (m, 2H), 3.94 (s, 2H), 3.64 (s, 3H), 3.08 (t, J=7.5 Hz, 2H), 2.88 (t, J=7.5 Hz, 2H), 2.14 (quin, J=7.5 Hz, 2H), 1.56 (s, 6H); ESI MS m/z 420 [M+H]+.

Workup

  1. customA 20-mL sealed tube
  2. temperatureAfter cooling to room temperature
  3. filtrationthe reaction mixture was filtered through celite
  4. washwashing the solids with ethyl acetate
  5. customThe filtrate layers were separated
  6. washthe organic layer was washed with saturated sodium chloride (3×10 mL)
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by chromatography on silica

Sources & evidence

ORD record
ord-9e7efe01fd434f4598f902d42ead1d4a
Source dataset
uspto-grants-2015_12
Patent number
US09221843B2

Reaction notes

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