Cesium carbonate → 5-Methoxy-3-((triethylsilyl)ethynyl)picolinonitrile

HRID 930480Notes

Reaction equation

HRID 930480 reaction equation
[C:1](=[O:4])([O-])[O-].[Cs+].[Cs+].Cl[C:8]1[C:9]2[N:17]=[CH:16][C:15](Cl)=[CH:14][C:10]=2N=C[N:13]=1.[CH2:19]([Si:21]([CH2:26][CH3:27])([CH2:24][CH3:25])[C:22]#[CH:23])[CH3:20]>CC#N.CC#N.Cl[Pd]Cl.C(#N)C>[CH3:1][O:4][C:15]1[CH:14]=[C:10]([C:20]#[C:19][Si:21]([CH2:26][CH3:27])([CH2:24][CH3:25])[CH2:22][CH3:23])[C:9]([C:8]#[N:13])=[N:17][CH:16]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 637947(Triethylsilyl)acetyleneHCID 714284454,7-Dichloropyrido[3,2-d]pyrimidine

Product 1

HCID 867322855-Methoxy-3-((triethylsilyl)ethynyl)picolinonitrile

Reagents, catalysts & solvents 2

HCID 6093782Bis(acetonitrile)dichloropalladiumCatalystHCID 6342AcetonitrileSolvent

Procedure

A sealable vessel was charged with bis(acetonitrile)palladium (II) chloride (0.154 g, 0.593 mmol), dicyclohexyl(2′,4′,6′-triisopropyl-[1′,1′-biphenyl]-2-yl)phosphine (0.848 g, 1.780 mmol), cesium carbonate (25.1 g, 77 mmol), the product of Intermediate 9, step 1 (5 g, 29.7 mmol), and ACN (60 mL). The vessel was flushed with argon, sealed, and stirred at RT for 25 minutes. To the reaction was added triethyl(ethynyl)silane (5.41 g, 38.6 mmol), and the vessel was resealed and stirred at 90° C. for 3 hours. The solution was concentrated, and the residue was purified via silica gel chromatography, eluting with 0-50% ethyl acetate in heptanes, to afford the title compound (3.8 g, 13.9 mmol). MS m/z=273 (M+H).

Workup

  1. customThe vessel was flushed with argon
  2. customsealed
  3. stirringstirred at 90° C. for 3 hours
  4. concentrationThe solution was concentrated
  5. customthe residue was purified via silica gel chromatography
  6. washeluting with 0-50% ethyl acetate in heptanes

Sources & evidence

ORD record
ord-fd564755e9af4be9b2856be807f7b99d
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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