Triethylamine → tert-Butyl 2-(diethoxymethyl)-1h-pyrrolo[3,2-c]pyridine-1-carboxylate

HRID 749507Notes

Reaction equation

HRID 749507 reaction equation
[CH3:1][C:2]([O:5][C:6](=[O:15])[NH:7][C:8]1[CH:13]=[CH:12][N:11]=[CH:10][C:9]=1I)([CH3:4])[CH3:3].[CH2:16]([O:18][CH:19]([O:22][CH2:23][CH3:24])[C:20]#[CH:21])[CH3:17].C(N(CC)CC)C.C1CCN2C(=NCCC2)CC1>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.CCOC(C)=O>[CH3:1][C:2]([O:5][C:6]([N:7]1[C:8]2[CH:13]=[CH:12][N:11]=[CH:10][C:9]=2[CH:21]=[C:20]1[CH:19]([O:22][CH2:23][CH3:24])[O:18][CH2:16][CH3:17])=[O:15])([CH3:4])[CH3:3]

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 662853,3-DiethoxypropyneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 10903275(3-Iodo-pyridin-4-yl)-carbamic acid tert-butyl ester

Product 1

HCID 68885234tert-Butyl 2-(diethoxymethyl)-1h-pyrrolo[3,2-c]pyridine-1-carboxylate

Reagents, catalysts & solvents 4

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

Heat a solution of (3-iodo-pyridin-4-yl)carbamic acid 1,1-dimethylethyl ester (13.3 g, 41.56 mmol, Darnbrough, Shelley; Mervic, Miljenko; Condon, Stephen M.; Burns, Christopher J. Synthetic Communications (2001) 31(21), 3273-3280), 3,3-diethoxy-1-propyne (5.96 ml, 41.56 mmole), triethylamine (23 ml, 166 mmol), dichlorobis(triphenyl-phospine)palladium(II) (1.46 g, 2.08 mmol) and copper iodide (237 mg, 1.25 mmol) in dry DMF under argon to 90° C. for 3 h. Allow the reaction mixture to cool to 70° C. and add DBU (12.5 ml, 83.12 mmol). Stir the reaction at 70° C. for 3 h and then stir at room temperature overnight. Pour the reaction mixture into EtOAc, wash with water (2×) and brine, dry over MgSO4, filter and concentrate to give the title compound as an oil. Purify the oil by flash chromatography (silica, elute with 10-20% EtOAc/n-heptane) to provide 9.8 g of the title compound as a clear oil, tlc (silica, 30% EtOAc/heptane, Rf=0.30).

Workup

  1. customthe reaction at 70° C. for 3 h
  2. stirringstir at room temperature overnight
  3. washwash with water (2×) and brine
  4. dry with materialdry over MgSO4
  5. filtrationfilter
  6. concentrationconcentrate

Sources & evidence

ORD record
ord-521e7cdfb7fd4dd698406759bd20e6dc
Source dataset
uspto-grants-2008_07
Patent number
US07402672B2

Reaction notes

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