Réaction #1270248

ord-a0d0f20860b74280bba6a7c78fff148a

Solvants

Conditions de réaction

Température
90°CELSIUS
Conditions détaillées
See reaction.notes.procedure_details.

Traitement

  1. 1
    Autrepurged again with nitrogen
  2. 2
    Températurethe solution was cooled to room temperature
  3. 3
    AutreThe solution was purged with nitrogen
  4. 4
    Températureheated at 90° C. for 4 h
  5. 5
    Concentrationconcentrated under reduced pressure
  6. 6
    Autresonicated
  7. 7
    Filtrationfiltered
  8. 8
    Autredried
  9. 9
    AutreThe crude product was purified on a silica gel column (100% DCM 3:97 MeOH:DCM)

Mode opératoire

A solution of 5-iodo-1-(tetrahydro-2H-pyran-2-yl)-1H-indazole-3-carbaldehyde (II) (498 mg, 1.4 mmol), bis(pinacolato)diboron (426 mg, 1.6 mmol), KOAc (412 mg, 4.2 mmol) and dry DMF (10 mL) was purged with nitrogen. Pd(dppf)2Cl2 (68 mg, 0.08 mmol) was added to the reaction and purged again with nitrogen. The solution was heated at 90° C. for 2 h. Once TLC showed the disappearance of (II), the solution was cooled to room temperature. To this solution was added K3PO4 (446 mg, 2.1 mmol), N-(5-bromopyridin-3-yl)-3-methylbutanamide (XXVIII) (358 mg, 1.4 mmol), Pd(PPh3)4 (48 mg, 0.042 mmol) and water (2 mL). The solution was purged with nitrogen and heated at 90° C. for 4 h. The reaction was passed through a pad of Celite® and then concentrated under reduced pressure. The residue was suspended in water, sonicated, filtered and dried. The crude product was purified on a silica gel column (100% DCM 3:97 MeOH:DCM) to give N-(5-(3-formyl-1-(tetrahydro-2H-pyran-2-yl)-1H-indazol-5-yl)pyridin-3-yl)-3-methylbutanamide (LXXXIV) as an off white solid (239 mg, 0.59 mmol, 42% yield). 1H NMR (DMSO-d6, 500 MHz) δ ppm 0.96 (d, 6H), 1.60-1.67 (m, 1H), 1.75-1.84 (m, 1H), 2.05-2.15 (m, 3H), 2.26 (d, 2H), 2.39-2.47 (m, 1H), 3.80-3.86 (m, 1H), 3.89-3.93 (m, 1H), 6.13 (dd, 1H), 7.91 (dd, 1H), 8.06 (d, 1H), 8.36 (s, 1H), 8.39 (s, 1H), 8.63 (d, 1H), 8.81 (d, 1H), 10.23 (s, 1H); ESIMS found C23H26N4O3 m/z 407.3 (M+H).

Source

DOI: 10.6084/m9.figshare.5104873.v1Brevet: US08664241B2uspto-grants-2014_03