Potassium Carbonate → HCID 71285035, compound

HRID 1481714Notes

Reaction equation

HRID 1481714 reaction equation
Br[C:2]1[CH:10]=[CH:9][C:8]2[N:7]3[CH2:11][CH2:12][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:14][C:6]3=[CH:5][C:4]=2[CH:3]=1.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.C([O-])(=O)C.[K+].Cl[C:46]1[C:55]([CH2:56][CH3:57])=[CH:54][C:49]([C:50]([O:52][CH3:53])=[O:51])=[C:48]([O:58][CH3:59])[N:47]=1.C([O-])([O-])=O.[K+].[K+]>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:18]([O:17][C:15]([N:13]1[CH2:12][CH2:11][N:7]2[C:8]3[CH:9]=[CH:10][C:2]([C:46]4[C:55]([CH2:56][CH3:57])=[CH:54][C:49]([C:50]([O:52][CH3:53])=[O:51])=[C:48]([O:58][CH3:59])[N:47]=4)=[CH:3][C:4]=3[CH:5]=[C:6]2[CH2:14]1)=[O:16])([CH3:21])([CH3:20])[CH3:19]

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 712847451,1-Dimethylethyl 8-bromo-3,4-dihydropyrazino[1,2-a]indole-2(1H)-carboxylateHCID 89421769HCID 89421769, compound

Product 1

HCID 71285035HCID 71285035, compoundYield 30%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent2×

Conditions

Temperature
120 °C

Procedure

To a vial was added tert-butyl 8-bromo-3,4-dihydropyrazino[1,2-a]indole-2(1H)-carboxylate (0.318 g, 0.9 mmol), bis(pinacolato)diboron (0.3 g, 1.2 mmol), potassium acetate (0.27 g, 2.7 mmol), and Pd(dppf)Cl2 (26 mg, 4 mol %). The vial was evacuated and back filled with argon. Dioxane (3 mL) was added, the vial was sealed under argon and heated to 120° C. for 18 h. The reaction mixture was then cooled to room temperature and methyl 6-chloro-5-ethyl-2-methoxynicotinate (0.23 g, 1.0 mmol) was added along with K2CO3 (0.38 g, 2.7 mmol) and H2O (300 μL). The vial was sealed again under argon and heated to 120° C. for a further 12 h. The reaction mixture was then cooled to room temperature and diluted with H2O (20 mL). The aqueous layer was extracted with CH2Cl2 (3×50 mL). The combined organics were dried over Na2SO4, filtered, and concentrated. The crude residue was purified on silica gel (1:1 hexanes/EtOAc) to afford the title compound as a clear oil (0.12 g, 30%).

Workup

  1. customThe vial was evacuated
  2. additionback filled with argon
  3. additionDioxane (3 mL) was added
  4. customthe vial was sealed under argon
  5. temperatureThe reaction mixture was then cooled to room temperature
  6. customThe vial was sealed again under argon
  7. temperatureheated to 120° C. for a further 12 h
  8. temperatureThe reaction mixture was then cooled to room temperature
  9. extractionThe aqueous layer was extracted with CH2Cl2 (3×50 mL)
  10. dry with materialThe combined organics were dried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe crude residue was purified on silica gel (1:1 hexanes/EtOAc)

Sources & evidence

ORD record
ord-ab9aaf2345914d55837542856deb0661
Source dataset
uspto-grants-2016_08
Patent number
US09409905B2

Reaction notes

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