Thallium hydroxide → HCID 69082823, compound

HRID 2362408Notes

Reaction equation

HRID 2362408 reaction equation
[F:1][C:2]1[CH:12]=[CH:11][C:5](/[CH:6]=[CH:7]/B(O)O)=[CH:4][CH:3]=1.Br[C:14]1[CH:19]=[C:18]([Br:20])[CH:17]=[CH:16][N:15]=1.[OH-].[Tl+]>O1CCCC1.O.ClCCl.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>[Br:20][C:18]1[CH:17]=[CH:16][N:15]=[C:14](/[CH:7]=[CH:6]/[C:5]2[CH:11]=[CH:12][C:2]([F:1])=[CH:3][CH:4]=2)[CH:19]=1

Participants

8

Reactant 3

HCID 160963Thallium hydroxideHCID 8171042,4-DibromopyridineHCID 5706776trans-2-(4-Fluorophenyl)vinylboronic acid

Product 1

HCID 69082823HCID 69082823, compound

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of (E)-4-fluorostyrylboronic acid (5 g, 30.1 mmol) and 2,4-dibromopyridine (6.49 g, 27.4 mmol) in tetrahydrofuran (150 mL) was purged with nitrogen for 20 min. To this was added Pd(Ph3P)4 (2.37 g, 2.05 mmol) and a 10% w/w solution of thallium(I) hydroxide (137 g, 62 mmol) in water. The reaction was stirred under nitrogen at room temperature. After 3 h, the gray suspension was diluted with dichloromethane and filtered through celite. The organics were washed with water, dried over magnesium sulfate, and concentrated. The resulting residue was purified by column chromatography (5%→13% EtOAc/Hex) to give 2.65 g (33%). 1H NMR (CDCl3) Shift: 8.43 (d, J=5.2 Hz, 1H), 7.64 (d, J=15.9 Hz, 1H), 7.50-7.59 (m, 3H), 7.34 (dd, J=5.3, 1.7 Hz, 1H), 7.10 (t, J=8.7 Hz, 2H), 7.02 (d, J=16.2 Hz, 1H). 13C NMR (CDCl3) Shift: 163.1, 157.0, 150.4, 133.3, 133.2, 132.5, 129.0, 126.4, 125.3, 116.0. 19F NMR (CDCl3) Shift: −112.69 (bs, 1F). Mass spec.: 278.2 (MH)+.

Workup

  1. filtrationfiltered through celite
  2. washThe organics were washed with water
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. customThe resulting residue was purified by column chromatography (5%→13% EtOAc/Hex)
  6. customto give 2.65 g (33%)

Sources & evidence

ORD record
ord-8f3cf4511f184a62babe2d9c3ab4e68b
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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