Cesium carbonate → HCID 70097589, compound

HRID 467760Notes

Reaction equation

HRID 467760 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10](Br)=[CH:9][CH:8]=[C:7]([CH2:12][O:13][CH3:14])[N:6]=1)=[O:4].[C:15](=[O:22])([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[NH2:16].C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[C:18]([O:17][C:15]([NH:16][C:10]1[C:5]([C:3]([O:2][CH3:1])=[O:4])=[N:6][C:7]([CH2:12][O:13][CH3:14])=[CH:8][CH:9]=1)=[O:22])([CH3:21])([CH3:20])[CH3:19]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 67299913HCID 67299913, compound

Product 1

HCID 70097589HCID 70097589, compoundYield 56.2%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred solution of 3-bromo-6-methoxymethyl-pyridine-2-carboxylic acid methyl ester (933 mg, 3.59 mmol; intermediate A-3, step 6) and tert-butyl carbamate (504 mg, 4.3 mmol) at r.t. in dioxane (15 ml) under an argon atmosphere were added cesium carbonate (1.64 g, 5.02 mmol), Pd2(dba)3 (65.7 mg, 71.7 μmol) and Xantphos (62.3 mg, 108 μmol; CAS 161265-03-8). The mixture was degassed under vacuum and flushed with argon, then heated to 100° C. overnight. The mixture was cooled to r.t., diluted with CH2Cl2, and the solids were filtered off and washed with some CH2Cl2. The filtrate was concentrated. The crude product was purified by silica gel chromatography using a cyclohexane/EtOAc gradient to give the title compound (598 mg, 56%) as viscous light yellow oil.

Workup

  1. customThe mixture was degassed under vacuum
  2. customflushed with argon
  3. temperatureThe mixture was cooled to r.t.
  4. additiondiluted with CH2Cl2
  5. filtrationthe solids were filtered off
  6. washwashed with some CH2Cl2
  7. concentrationThe filtrate was concentrated
  8. customThe crude product was purified by silica gel chromatography

Sources & evidence

ORD record
ord-f69506ea03e34776adefa8400b21a5aa
Source dataset
uspto-grants-2014_01
Patent number
US08623866B2

Reaction notes

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