Cesium carbonate → HCID 71045661, compound

HRID 2374455Notes

Reaction equation

HRID 2374455 reaction equation
Br[C:2]1[S:3][C:4]([S:8]([NH:11][C:12]2[N:17]=[C:16]([NH:18][C:19](=[O:25])[O:20][C:21]([CH3:24])([CH3:23])[CH3:22])[CH:15]=[C:14]([CH3:26])[CH:13]=2)(=[O:10])=[O:9])=[C:5]([CH3:7])[N:6]=1.[C:27]([C:29]1[CH:34]=[CH:33][C:32](B(O)O)=[CH:31][CH:30]=1)#[N:28].C(=O)([O-])[O-].[Cs+].[Cs+]>C(COC)OC.O>[C:27]([C:29]1[CH:34]=[CH:33][C:32]([C:2]2[S:3][C:4]([S:8]([NH:11][C:12]3[N:17]=[C:16]([NH:18][C:19](=[O:25])[O:20][C:21]([CH3:24])([CH3:23])[CH3:22])[CH:15]=[C:14]([CH3:26])[CH:13]=3)(=[O:10])=[O:9])=[C:5]([CH3:7])[N:6]=2)=[CH:31][CH:30]=1)#[N:28]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 27343264-Cyanophenylboronic acidHCID 58838506HCID 58838506, compound

Product 1

HCID 71045661HCID 71045661, compoundYield 33.1%

Reagents, catalysts & solvents 1

HCID 18180031Water 1,2-dimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of tert-butyl (6-{[(2-bromo-4-methyl-1,3-thiazol-5-yl)sulfonyl]amino}-4-methylpyridin-2-yl)carbamate (0.96 g, 2.08 mmol, 1 equiv), 4-cyanophenylboronic acid (0.336 g, 2.29 mmol, 1.1 equiv), and cesium carbonate (2.03 g, 6.24 mmol, 3 equiv) in 2:1 dimethoxyethane/water (30 mL) was purged with nitrogen for 15 minutes. Dichloro[1,1′-bis(diphenylphosphine)ferrocene] palladium (II) chloride (0.068 g, 0.08 mmol, 0.04 equiv) was then added, and the resulting mixture was purged with nitrogen for another 15 minutes. The reaction was heated to 80° C. for 1 h. After cooling to 24° C., the solution was concentrated in vacuo (˜25 mm Hg). The resulting aqueous mixture was extracted ethyl acetate (60 mL). The collected organic was dried over anhydrous sodium sulfate, filtered, and concentrated. Purification by high performance flash chromatography (0→10% ethyl acetate in hexanes) provided the intermediate (0.334 g, 33%). 1H NMR (400 MHz, CDCl3), δ: 7.97 (d, J=8.3 Hz, 2H), 7.73 (d, J=8.3 Hz, 2H), 7.63 (br s, 1H), 7.43 (s, 1H), 6.90 (s, 1H), 2.65 (s, 3H), 2.32 (s, 3H), 1.50 (s, 9H); LRMS (ESI) m/z: 486.1.

Workup

  1. customthe resulting mixture was purged with nitrogen for another 15 minutes
  2. temperatureAfter cooling to 24° C.
  3. concentrationthe solution was concentrated in vacuo (˜25 mm Hg)
  4. extractionThe resulting aqueous mixture was extracted ethyl acetate (60 mL)
  5. dry with materialThe collected organic was dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by high performance flash chromatography (0→10% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-da21889c67954a239e08dae62b83bbfb
Source dataset
uspto-grants-2008_12
Patent number
US07462634B2

Reaction notes

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