Tert-butyl (3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)carbamate → 2-(2-aminopyridin-3-yl)-5,6-dihydrothieno[2,3-c]pyridin-7(4H)-one

HRID 2091575Notes

Reaction equation

HRID 2091575 reaction equation
CC1(C)C(C)(C)OB([C:9]2[C:10]([NH:15]C(=O)OC(C)(C)C)=[N:11][CH:12]=[CH:13][CH:14]=2)O1.Br[C:25]1[S:34][C:28]2[C:29](=[O:33])[NH:30][CH2:31][CH2:32][C:27]=2[CH:26]=1>CCCCO.C([O-])([O-])=O.[Na+].[Na+].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:15][C:10]1[C:9]([C:25]2[S:34][C:28]3[C:29](=[O:33])[NH:30][CH2:31][CH2:32][C:27]=3[CH:26]=2)=[CH:14][CH:13]=[CH:12][N:11]=1

Participants

6

Reactant 2

HCID 45925650Tert-butyl (3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)carbamateHCID 513419322-Bromo-5,6-dihydrothieno(2,3-c)pyridin-7(4H)-one

Product 1

HCID 706544642-(2-aminopyridin-3-yl)-5,6-dihydrothieno[2,3-c]pyridin-7(4H)-oneYield 88.1%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 2631-ButanolSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
100 °C

Procedure

A solution of tert-butyl (3-(4,4,5,5-tetra methyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)carbamate (416 mg, 1.3 mmol), 2-bromo-5,6-dihydrothieno[2,3-c]pyridin-7(4H)-one (300 mg, 1.3 mmol) and Pd(PPh3)4 (23 mg, 0.02 mmol) in n-BuOH (3 mL) and 2M Na2CO3 (3 mL) was degassed under bubbling nitrogen and the reaction was heated 2 h at 100° C. Upon completion, the reaction was filtered and concentrated under reduced pressure, then partitioned between DCM (10 mL) water (10 mL). The layers were separated and the aqueous layer was extracted with DCM (3×10 mL). The combined organics were dried over Na2SO4 and concentrated. The concentrate was slurried in EtOAc, sonicated and filtered to afford 2-(2-aminopyridin-3-yl)-5,6-dihydrothieno[2,3-c]pyridin-7(4H)-one (281 mg, 88% yield) as a white solid. 1H NMR (300 MHz, MeOH) δ ppm 7.99 (dd, J=5.0, 1.3 Hz, 1H), 7.62 (dd, J=7.5, 1.4 Hz, 1H), 7.25 (s, 1H), 6.76 (dd, J=7.5, 5.1 Hz, 1H), 3.61 (t, J=7.0 Hz, 2H), 2.97 (t, J=7.1 Hz, 2H); MS (EI) m/z=246.3 [M+1]+.

Workup

  1. filtrationUpon completion, the reaction was filtered
  2. concentrationconcentrated under reduced pressure
  3. custompartitioned between DCM (10 mL) water (10 mL)
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with DCM (3×10 mL)
  6. dry with materialThe combined organics were dried over Na2SO4
  7. concentrationconcentrated
  8. customsonicated
  9. filtrationfiltered

Sources & evidence

ORD record
ord-29250a5b170b4924a90225f070b9f0b8
Source dataset
uspto-grants-2013_05
Patent number
US08440652B2

Reaction notes

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