반응 #674295

ord-a37fc8f051724aec9244c9a4b3868890

반응 방정식

O=C([O-])[O-].[Na+].[Na+]
Na2CO3
N#N
N2
CC(C)(C)OC(=O)N1CC2(CC(n3cc(Br)cn3)C2)C1
tert-Butyl 6-(4-bromo-1H-pyrazol-1-yl)-2-azaspiro[3.3]heptane-2-carboxylate
CC(Oc1cc(B2OC(C)(C)C(C)(C)O2)cnc1N)c1c(Cl)ccc(F)c1Cl
(±)-3-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amine
N#N
N2
CC(Oc1cc(-c2cnn(C3CC4(C3)CN(C(=O)OC(C)(C)C)C4)c2)cnc1N)c1c(Cl)ccc(F)c1Cl
(±)-tert-butyl 6-(4-(6-amino-5-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)pyridin-3-yl)-1H-pyrazol-1-yl)-2-azaspiro[3.3]heptane-2-carboxylate
수율 45.0%

용매

반응 조건

온도
90°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    기타It was degassed again
  2. 2
    workup.ADDITIONrefilled with N2 (2 times)
  3. 3
    온도(heating bath) for 16 hrs
  4. 4
    온도The reaction mixture was cooled to room temperature
  5. 5
    workup.ADDITIONH2O (30 mL) was added
  6. 6
    추출The aqueous phase was extracted with EtOAc (30 mL) and DCM (3×30 mL)
  7. 7
    건조The combined organic phase was dried over anhydrous Na2SO4
  8. 8
    농축concentrated by evaporation in vacuo
  9. 9
    기타to give black residue which
  10. 10
    기타was purified by CombiFlash (40 g silica gel column, Hexane/EtOAc)

실험 절차

tert-Butyl 6-(4-bromo-1H-pyrazol-1-yl)-2-azaspiro[3.3]heptane-2-carboxylate (145 mg, 0.42 mmol) and (±)-3-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amine (268 mg, 0.63 mmol) were added to a round bottom flask. It was vacuumed and refilled with N2 (3 times). DME (2.0 mL) and a solution of Na2CO3 (2.0 M, 1.0 mL) were sequentially added. It was vacuumed and refilled with N2 (3 times). Pd(PPh3)2Cl2 (14.7 mg, 0.021 mmol) was added. It was degassed again refilled with N2 (2 times). The mixture was stirred at 90° C. (heating bath) for 16 hrs. The reaction mixture was cooled to room temperature and H2O (30 mL) was added. The aqueous phase was extracted with EtOAc (30 mL) and DCM (3×30 mL). The combined organic phase was dried over anhydrous Na2SO4, concentrated by evaporation in vacuo to give black residue which was purified by CombiFlash (40 g silica gel column, Hexane/EtOAc) to afford (±)-tert-butyl 6-(4-(6-amino-5-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)pyridin-3-yl)-1H-pyrazol-1-yl)-2-azaspiro[3.3]heptane-2-carboxylate (106 mg, 45%) as a off-white solid.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US09226923B2uspto-grants-2016_01