Triethylamine → HCID 90389297, compound

HRID 1526620Notes

Reaction equation

HRID 1526620 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([C:8]([O:10][CH3:11])=[O:9])=[N:6][CH:7]=1.[CH2:12]([Si:14]([C:19]#[CH:20])([CH2:17][CH3:18])[CH2:15][CH3:16])[CH3:13].C(N(CC)CC)C>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I>[CH2:15]([Si:14]([C:12]#[C:13][C:2]1[CH:3]=[CH:4][C:5]([C:8]([O:10][CH3:11])=[O:9])=[N:6][CH:7]=1)([CH2:19][CH3:20])[CH2:17][CH3:18])[CH3:16]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 637947(Triethylsilyl)acetyleneHCID 7016458Methyl 5-bromopyridine-2-carboxylate

Product 1

HCID 90389297HCID 90389297, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Conditions

Temperature
70 °C

Procedure

A glass microwave reaction vessel was charged with methyl 5-bromopyridine-2-carboxylate (0.95 ml, 6.94 mmol, Alfa Aesar), (triethylsilyl) acetylene (3.73 ml, 20.81 mmol, Sigma-Aldrich), tetrakis(triphenylphosphine) palladium (0.61 g, 0.527 mmol, Strem Chemicals), triethylamine (4.82 ml, 34.7 mmol, Sigma-Aldrich Chemical), and copper (I) iodide (0.04 ml, 1.040 mmol, Sigma-Aldrich). The reaction mixture was stirred and heated in a Biotage Initiator microwave reactor at 70° C. for 30 min. The reaction mixture was filtered through celite and concentrated. The reaction mixture was diluted with saturated NH4Cl and extracted with EtOAc. The organic extract was washed with water and brine, dried over MgSO4, filtered and concentrated in vacuo. The crude product was adsorbed onto a plug of silica gel and chromatographed through a silica gel column, eluting with a gradient of 0% to 40% EtOAc in hexane, to provide methyl 5-((triethylsilyl)ethynyl)picolinate (1.68 g, 6.09 mmol, 88% yield). MS m/z [M+H]+=276.0. Calculated from C15H21NO2Si: 275.418

Workup

  1. customA glass microwave reaction vessel
  2. filtrationThe reaction mixture was filtered through celite
  3. concentrationconcentrated
  4. additionThe reaction mixture was diluted with saturated NH4Cl
  5. extractionextracted with EtOAc
  6. extractionThe organic extract
  7. washwas washed with water and brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customchromatographed through a silica gel column
  12. washeluting with a gradient of 0% to 40% EtOAc in hexane

Sources & evidence

ORD record
ord-a2528f7c01ab484ea3622c55bfd82562
Source dataset
uspto-grants-2015_07
Patent number
US09085576B2

Reaction notes

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