反応 #674302

ord-92bcbbf725664cce8ed3c73c5ec1c9ab

反応方程式

N#N
N2
N#N
N2
C[C@@H](Oc1cc(B2OC(C)(C)C(C)(C)O2)cnc1N)c1c(Cl)ccc(F)c1Cl
(R)-3-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amine
CC(C)(C)OC(=O)N1CCC2(CC1)CC(n1cc(I)cn1)C2
tert-butyl 2-(4-iodo-1H-pyrazol-1-yl)-7-azaspiro[3.5]nonane-7-carboxylate
N#N
N2
O=C([O-])[O-].[Na+].[Na+]
Na2CO3
C[C@@H](Oc1cc(-c2cnn(C3CC4(CCN(C(=O)OC(C)(C)C)CC4)C3)c2)cnc1N)c1c(Cl)ccc(F)c1Cl
(R)-tert-butyl 2-(4-(6-amino-5-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)pyridin-3-yl)-1H-pyrazol-1-yl)-7-azaspiro[3.5]nonane-7-carboxylate
収率 73.0%

反応条件

温度
80°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    温度The mixture was cooled to room temperature
  2. 2
    濃縮concentrated
  3. 3
    その他to give black residue which
  4. 4
    抽出The aqueous phase was extracted with EtOAc (4×30 mL)
  5. 5
    洗浄The combined organic phase was washed with brine (30 mL)
  6. 6
    乾燥dried over anhydrous Na2SO4
  7. 7
    濃縮concentrated
  8. 8
    その他to give black green residue which
  9. 9
    その他was purified by CombiFlash (12 g silica gel column; EtOAc/Hexane: 0-100%)

実験手順

(R)-3-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amine (104 mg, 0.244 mmol, 1.0 equiv), tert-butyl 2-(4-iodo-1H-pyrazol-1-yl)-7-azaspiro[3.5]nonane-7-carboxylate (112 mg, 0.268 mmol, 1.1 equiv) were added to a RBF (25 mL). It was vacuumed and refilled with N2 (3 times). Dioxane (1.0 mL) and a solution of Na2CO3 (2.0 M, 0.4 mL) were added sequentially. It was vacuumed again and refilled with N2 (3 times). Pd(PPh3)2Cl2 catalyst (9 mg, 5 mol %) was added last. It was vacuumed and refilled with N2 (3 times). The mixture was then heated to 80° C. (oil bath) and stirred at this temperature under N2 for 24 hrs. The mixture was cooled to room temperature, and concentrated to give black residue which was treated with H2O (30 mL). The aqueous phase was extracted with EtOAc (4×30 mL). The combined organic phase was washed with brine (30 mL), dried over anhydrous Na2SO4, concentrated to give black green residue which was purified by CombiFlash (12 g silica gel column; EtOAc/Hexane: 0-100%) to afford 105 mg (yield 73%) of (R)-tert-butyl 2-(4-(6-amino-5-(1-(2,6-dichloro-3-fluorophenyl)ethoxy)pyridin-3-yl)-1H-pyrazol-1-yl)-7-azaspiro[3.5]nonane-7-carboxylate as a pale yellow solid.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US09226923B2uspto-grants-2016_01