3-Pyridinylboronic acid → HCID 68615877, compound

HRID 1431977Notes

Reaction equation

HRID 1431977 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:14]2[CH:19]=[C:18]([O:20][CH3:21])[C:17]([O:22][CH3:23])=[C:16]([O:24][CH3:25])[CH:15]=2)[N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH:6]=1.[N:26]1[CH:31]=[CH:30][CH:29]=[C:28](B(O)O)[CH:27]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:10]([O:9][C:7]([N:5]1[CH:6]=[C:2]([C:28]2[CH:27]=[N:26][CH:31]=[CH:30][CH:29]=2)[CH:3]=[C:4]1[C:14]1[CH:19]=[C:18]([O:20][CH3:21])[C:17]([O:22][CH3:23])=[C:16]([O:24][CH3:25])[CH:15]=1)=[O:8])([CH3:13])([CH3:12])[CH3:11]

Participants

4

Reactant 2

HCID 27343783-Pyridinylboronic acidHCID 68615727HCID 68615727, compound

Product 1

HCID 68615877HCID 68615877, compoundYield 13.6%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Procedure

A mixture of 4-bromo-1-tert-butoxycarbonyl-2-(3,4,5-trimethoxyphenyl)-pyrrole (2.0 g, 5.0 mmol, Example 76b), Pd(PPh3)4 (290 mg, 0.25 mmol) and pyridine-3-boronic acid (614 mg, 5.0 mmol) are evacuated for 10 min and set under argon atmosphere, followed by addition of degassed dimethoxyethane (DME, 10 ml) and 2 M aqueous Na2CO3 solution (10 ml). The reaction mixture is heated for 20 h to 80° C., cooled to room temperature and diluted with water and ethyl acetate. The organic layer is dried (MgSO4), filtered and the solvents are evaporated. The residue is chromatographed with ethyl acetate/hexane (1:1) to yield first 1-tert-butoxycarbonyl-4-(3-pyridyl)-2-(3,4,5-trimethoxy-phenyl)-pyrrole (280 mg, 12%) as a yellowish amorphous solid and then the title compound (700 mg, 45%) as a yellowish solid, 1H-NMR (300 MHz, DMSO-d6): 11.52 (br.s, 1H); 7.88 (br. s, 1H); 8.33 (br.d; J=6.0, 1H); 8.0-7.95 (m, 1H); 7.48 (br.s, 1H); 7.35-7.3 (m, 1H); 7.07 (br.s, 1H); 7.02 (s, 2H); 3.85 (s, 2MeO); 3.67 (s, MeO).

Workup

  1. customare evacuated for 10 min
  2. additionfollowed by addition of degassed dimethoxyethane (DME, 10 ml) and 2 M aqueous Na2CO3 solution (10 ml)
  3. temperatureThe reaction mixture is heated for 20 h to 80° C.
  4. additiondiluted with water and ethyl acetate
  5. dry with materialThe organic layer is dried (MgSO4)
  6. filtrationfiltered
  7. customthe solvents are evaporated
  8. customThe residue is chromatographed with ethyl acetate/hexane (1:1)

Sources & evidence

ORD record
ord-a672f3078bc14e7389037ae43f89c682
Source dataset
uspto-grants-2009_11
Patent number
US07612064B2

Reaction notes

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