Sodium Carbonate → (E)-6-chloro-3-(3-methoxyprop-1-en-1-yl)-1-trityl-1H-pyrazolo[4,3-c]pyridine

HRID 571386Notes

Reaction equation

HRID 571386 reaction equation
[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[C:8](I)=[N:9][N:10]([C:11]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:4]=2[CH:3]=1.[CH3:31][O:32][CH2:33]/[CH:34]=[CH:35]/B1OC(C)(C)C(C)(C)O1.C([O-])([O-])=O.[Na+].[Na+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.O1CCOCC1>[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[C:8](/[CH:35]=[CH:34]/[CH2:33][O:32][CH3:31])=[N:9][N:10]([C:11]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 162174432-[(1E)-3-methoxyprop-1-en-1-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 895258586-Chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine2×

Product 1

HCID 89525849(E)-6-chloro-3-(3-methoxyprop-1-en-1-yl)-1-trityl-1H-pyrazolo[4,3-c]pyridineYield 82.2%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

6-chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine (Intermediate 2a, 200 mg, 0.383 mmol), PdCl2(dppf)-CH2Cl2 adduct (47.0 mg, 0.057 mmol), 1-4-dioxane (1 mL), trans-3-methoxy-1-propenylboronic acid pinacol ester (0.15 mL, 0.707 mmol) and Na2CO3 (0.48 mL, 0.960 mmol, 2M) were charged in a vial. The mixture was evacuated and purged with nitrogen six times and heated at 80° C. for 35 min. The mixture was diluted with EtOAc and the organic phase was washed with water, brine, dried (Na2SO4) and concentrated in vacuo to afford a residue, which was purified by column chromatography on silica gel (10 g, EtOAc in hexane, 0-10%, 10 CV; 10-20%, 20CV) to afford (E)-6-chloro-3-(3-methoxyprop-1-en-1-yl)-1-trityl-1H-pyrazolo[4,3-c]pyridine (147 mg, 0.315 mmol, 82% yield) as a light yellow solid. MS ESI calc'd. for C29H25ClN3O [M+H]+ 466, found 466.

Workup

  1. customThe mixture was evacuated
  2. custompurged with nitrogen six times
  3. additionThe mixture was diluted with EtOAc
  4. washthe organic phase was washed with water, brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customto afford a residue, which
  8. customwas purified by column chromatography on silica gel (10 g, EtOAc in hexane, 0-10%, 10 CV; 10-20%, 20CV)

Sources & evidence

ORD record
ord-870d403d72144015a1f1a3c2889c9247
Source dataset
uspto-grants-2015_05
Patent number
US09023865B2

Reaction notes

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