反应 #1135852

ord-eff8864938524174bb8304a264a1fa27

反应方程式

O=P([O-])([O-])[O-].[K+].[K+].[K+]
K3PO4
O=C(NCC1CC1)c1cncc(Br)c1
5-bromo-N-(cyclopropylmethyl)nicotinamide
O=Cc1nn(C2CCCCO2)c2ccc(I)cc12
5-iodo-1-(tetrahydro-2H-pyran-2-yl)-1H-indazole-3-carbaldehyde
CC1(C)OB(B2OC(C)(C)C(C)(C)O2)OC1(C)C
bis(pinacolato)diboron
CC(=O)[O-].[K+]
KOAc
O=Cc1nn(C2CCCCO2)c2ccc(-c3cncc(C(=O)NCC4CC4)c3)cc12
N-(cyclopropylmethyl)-5-(3-formyl-1-(tetrahydro-2H-pyran-2-yl)-1H-indazol-5-yl)nicotinamide
收率 90.0%

溶剂

反应条件

温度
80°CELSIUS
详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    其他purged again with nitrogen
  2. 2
    温度the solution was cooled to r.t
  3. 3
    其他The solution was purged with nitrogen
  4. 4
    温度heated at 90° C. for 3 h
  5. 5
    浓缩concentrated under reduced pressure
  6. 6
    workup.DISSOLUTIONThe residue was dissolved in DCM
  7. 7
    洗涤washed with water and brine
  8. 8
    干燥dried over MgSO4
  9. 9
    其他evaporated under vacuum
  10. 10
    其他The crude product was purified on a silica gel column (100% EtOAc→2:98 MeOH:DCM)

实验过程

A solution of 5-iodo-1-(tetrahydro-2H-pyran-2-yl)-1H-indazole-3-carbaldehyde (I) (1.068 g, 3.0 mmol), bis(pinacolato)diboron (0.914 g, 3.6 mmol), KOAc (0.883 g, 9.0 mmol) and dry DMF (20 mL) was purged with nitrogen. PdCl2(dppf)2 was added to the reaction and purged again with nitrogen. The solution was heated at 80° C. for 2 h. Once TLC showed the disappearance of (I), the solution was cooled to r.t. To this solution was added K3PO4 (0.955 g, 4.5 mmol), 5-bromo-N-(cyclopropylmethyl)nicotinamide (XVII) (0.765 g, 3.0 mmol), Pd(PPh3)4 (104 mg, 0.09 mmol) and water (2 mL). The solution was purged with nitrogen and heated at 90° C. for 3 h. The reaction was passed through a pad of Celite and then concentrated under reduced pressure. The residue was dissolved in DCM and washed with water and brine, dried over MgSO4 and then evaporated under vacuum. The crude product was purified on a silica gel column (100% EtOAc→2:98 MeOH:DCM) to give N-(cyclopropylmethyl)-5-(3-formyl-1-(tetrahydro-2H-pyran-2-yl)-1H-indazol-5-yl)nicotinamide (XXXI) as a yellow solid (1.09 g, 2.7 mmol, 90% yield). 1H NMR (DMSO-d6) δ ppm 0.20-0.31 (m, 2H), 0.35-0.57 (m, 2H), 1.65 (m, 2H), 1.74-1.87 (m, 1H), 2.10 (d, J=12.06 Hz, 2H), 2.35-2.44 (m, 1H), 3.10-3.27 (m, 3H), 3.78-3.99 (m, 2H), 6.14 (d, J=7.35 Hz, 1H), 7.90-8.14 (m, 2H), 8.50 (d, J=12.5, 2H), 9.05 (dd, J=14.60, 1.98 Hz, 2H), 10.25 (s, 1H); ESIMS found C23H24N4O3 m/z 405 (M+H).

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US09381192B2uspto-grants-2016_07