Dichloromethane → 4-cyano-5-ethyl-1-methyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrrole-2-carboxylic acid ethyl ester

HRID 1865054Notes

Reaction equation

HRID 1865054 reaction equation
[CH3:1][C:2]1([CH3:9])[C:6]([CH3:8])([CH3:7])[O:5][BH:4][O:3]1.[CH2:10]([O:12][C:13]([C:15]1[N:16]([CH3:25])[C:17]([CH2:23][CH3:24])=[C:18]([C:21]#[N:22])[C:19]=1I)=[O:14])[CH3:11].C(Cl)Cl.C(N(CC)CC)C>C(#N)C.O>[CH2:10]([O:12][C:13]([C:15]1[N:16]([CH3:25])[C:17]([CH2:23][CH3:24])=[C:18]([C:21]#[N:22])[C:19]=1[B:4]1[O:5][C:6]([CH3:8])([CH3:7])[C:2]([CH3:9])([CH3:1])[O:3]1)=[O:14])[CH3:11]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 57975348HCID 57975348, compound

Product 1

HCID 579748024-cyano-5-ethyl-1-methyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrrole-2-carboxylic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

Add 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.87 mL, 6.0 mmol) to 4-cyano-5-ethyl-3-iodo-1-methyl-1H-pyrrole-2-carboxylic acid ethyl ester (1.0 g, 3.0 mmol, prepared in prepared in Preparation 38), [1,1′-bis(diphenylphosphino)ferrocene]dichloro-palladium(II) complex with methylene chloride (1:1) (0.122 g, 0.15 mmol), and triethylamine (1.25 mL, 9.0 mmol) in acetonitrile and heat to reflux. After 3 hours, cool and pour into water. Extract with ethyl acetate. Wash the combined organics with water and brine, dry over magnesium sulfate, filter and concentrate under reduced pressure. Purify the residue by flash chromatography (silica gel), eluting with ethyl acetate:hexanes to provide the title compound. 1H NMR (400 MHz, CDCl3) δ 4.33 (q, 2H), 3.84 (s, 3H), 2.80 (q, 2H), 1.40 (s, 12H), 1.46 (t, 3H), 1.22 (t, 3H).

Workup

  1. temperatureheat to reflux
  2. temperaturecool
  3. extractionExtract with ethyl acetate
  4. washWash the combined organics with water and brine
  5. dry with materialdry over magnesium sulfate
  6. filtrationfilter
  7. concentrationconcentrate under reduced pressure
  8. customPurify the residue by flash chromatography (silica gel)
  9. washeluting with ethyl acetate

Sources & evidence

ORD record
ord-5f4c73361e964e13987ed25e8e5423eb
Source dataset
uspto-grants-2009_12
Patent number
US07625932B2

Reaction notes

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