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Sodium Iodide → 1-cyclopentyl-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-6-(3-hydroxy-3-methyl-1-butyn-1-yl)-1H-indazole-4-carboxamide

HRID 85473
Notes
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Reaction equation

HRID 85473 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:16]([NH:18][CH2:19][C:20]2[C:21](=[O:28])[NH:22][C:23]([CH3:27])=[CH:24][C:25]=2[CH3:26])=[O:17])[C:5]2[CH:6]=[N:7][N:8]([CH:11]3[CH2:15][CH2:14][CH2:13][CH2:12]3)[C:9]=2[CH:10]=1.[I-].[Na+].C1CCN2C(=NCCC2)CC1.[CH3:42][C:43]([OH:47])([C:45]#[CH:46])[CH3:44]>[Zn].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.C1COCC1.CCOC(C)=O.O.CS(C)=O>[CH:11]1([N:8]2[C:9]3[CH:10]=[C:2]([C:46]#[C:45][C:43]([OH:47])([CH3:44])[CH3:42])[CH:3]=[C:4]([C:16]([NH:18][CH2:19][C:20]4[C:21](=[O:28])[NH:22][C:23]([CH3:27])=[CH:24][C:25]=4[CH3:26])=[O:17])[C:5]=3[CH:6]=[N:7]2)[CH2:15][CH2:14][CH2:13][CH2:12]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

10

Reactant 4

HCID 5238Sodium IodideHCID 82582-Methyl-3-butyn-2-olHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 545970746-bromo-1-cyclopentyl-N-[(4,6-dimethyl-2-oxo-1,2-dihydropyridin-3-yl)methyl]-1H-indazole-4-carboxamide

Product 1

HCID 545973031-cyclopentyl-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-6-(3-hydroxy-3-methyl-1-butyn-1-yl)-1H-indazole-4-carboxamide

Reagents, catalysts & solvents 5

HCID 23994ZincCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 21939870Tetrahydrofuran ethyl acetateSolvent

Conditions

Temperature
85 °C

Procedure

To a 10 mL microwave vial containing a mixture of 6-bromo-1-cyclopentyl-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-1H-indazole-4-carboxamide (0.12 g, 0.271 mmol), sodium iodide (8.11 mg, 0.054 mmol) and zinc (3.54 mg, 0.054 mmol) were added DMSO (2.5 mL), TEA (0.075 mL, 0.541 mmol), and DBU (0.082 mL, 0.541 mmol). The suspension was stirred and degassed with N2 for 5 min. Next added in 2-methyl-3-butyn-2-ol (0.131 mL, 1.353 mmol) and Pd(Ph3P)4 (0.031 g, 0.027 mmol). The reaction vial was sealed and stirred with heating at 85° C. (heat block) for 3 h. The mixture was then diluted into water and 20% THF/EtOAc. The contents were stirred and the layers were separated. The organic layer was washed with brine, dried over MgSO4, filtered through Celite, and concentrated in vacuo. The residue was dried on hi-vacuum pump overnight. The crude product was purified by silica gel chromatography (eluent: 5-80% gradient chloroform (containing 10% 2M ammonia in methanol) in DCM). The collected product was purified by reverse phase HPLC (Gradient B: 15-75%; A: Water+0.1% TFA. B: CH3CN+0.1% TFA). The product was suspended in 10% MeOH/CHCl3. Next added 0.5 g Silicycle carbonate resin and stirred for 15 min. After standing for 10 min, the contents were filtered through celite and concentrated in vacuo. The product was further concentrated from DCM and MTBE and then dried in hi-vac oven at 45° C. overnight. The title compound was collected as a white solid (38 mg, 30%); 1H NMR (400 MHz, DMSO-d6) δ ppm 1.47-1.52 (m, 6H), 1.64-1.73 (m, 2H), 1.80-1.91 (m, 2H), 1.92-2.02 (m, 2H), 2.06-2.15 (m, 5H), 2.18-2.23 (m, 3H), 4.28-4.38 (m, 2H), 5.25 (quin, J=7.07 Hz, 1H), 5.52 (s, 1H), 5.84-5.91 (m, 1H), 7.54 (d, J=1.01 Hz, 1H), 7.93 (s, 1H), 8.35 (s, 1H), 8.60 (t, J=4.93 Hz, 1H), 11.51 (br. s., 1H); LC-MS (ES) m/z=446.9 [M+H]

Workup

  1. additionTo a 10 mL microwave vial containing
  2. customdegassed with N2 for 5 min
  3. customThe reaction
  4. customvial was sealed
  5. stirringstirred
  6. temperature(heat block) for 3 h
  7. stirringThe contents were stirred
  8. customthe layers were separated
  9. washThe organic layer was washed with brine
  10. dry with materialdried over MgSO4
  11. filtrationfiltered through Celite
  12. concentrationconcentrated in vacuo
  13. customThe residue was dried on hi-vacuum pump overnight
  14. customThe crude product was purified by silica gel chromatography (eluent: 5-80% gradient chloroform (containing 10% 2M ammonia in methanol) in DCM)
  15. customThe collected product was purified by reverse phase HPLC (Gradient B
  16. additionNext added 0.5 g Silicycle carbonate resin
  17. stirringstirred for 15 min
  18. filtrationthe contents were filtered through celite and
  19. concentrationconcentrated in vacuo
  20. concentrationThe product was further concentrated from DCM and MTBE
  21. customdried in hi-vac oven at 45° C. overnight
  22. customThe title compound was collected as a white solid (38 mg, 30%)

Sources & evidence

ORD record
ord-11577be56c654c54b6c7e28664db5677
Source dataset
uspto-grants-2014_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08846935B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes