Potassium Carbonate → HCID 178425614, compound

HRID 662052Notes

Reaction equation

HRID 662052 reaction equation
C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[K+].[K+].Br[C:27]1[CH:28]=[C:29]([CH2:35][NH:36][C:37](=[O:43])[O:38][C:39]([CH3:42])([CH3:41])[CH3:40])[CH:30]=[CH:31][C:32]=1[C:33]#N.[OH:44][CH2:45][C:46]1[CH:47]=[C:48](B(O)O)[CH:49]=[CH:50][CH:51]=1.[CH3:55][C:56]([Si:59](C)(C)[CH3:60])([CH3:58])[CH3:57]>O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:55][C:56]([SiH:59]([CH3:60])[O:44][CH2:45][C:46]1[CH:47]=[C:48]([C:27]2[C:32]([CH3:33])=[CH:31][CH:30]=[C:29]([CH2:35][NH:36][C:37](=[O:43])[O:38][C:39]([CH3:42])([CH3:41])[CH3:40])[CH:28]=2)[CH:49]=[CH:50][CH:51]=1)([CH3:58])[CH3:57]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 57813462HCID 57813462, compoundHCID 67006324HCID 67006324, compound

Product 1

HCID 178425614HCID 178425614, compoundYield 72.4%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

Pd(OAc)2 (56.3 mg, 0.25 mmol), PPh3 (263.0 mg, 1.0 mmol), K2CO3 (1.7 g, 12.5 mmol) and 1,1-dimethylethyl [(3-bromo-4-cyanophenyl)methyl]carbamate (2.6 g, 8.4 mmol) were suspended in 1,4-dioxane (30 mL). After the mixture was heated to 80° C. for 15 min, [3-(hydroxymethyl)phenyl]boronic acid-(1,1-dimethylethyl)(trimethyl)silane (2.7 g, 10.0 mmol) was added. Then the reaction mixture was stirred over night at 100° C. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was dissolved in CH2Cl2 (50 mL), washed with water (20 mL), brine (20 mL), and dried over Na2SO4. After the solvent was removed, the crude product was purified on Al2O3 column chomatography, eluting with CH2Cl2 to yield the captioned product (2.6 g, yield: 60%). 1H NMR (400 MHz, CDCl3) δ 0.12 (s, 6H), 0.95 (s 9H), 1.46 (s, 9H), 4.41-4.42 (m, 2H), 4.81 (s, 2H), 7.37-7.47 (m, 6H), 7.71 (d, J=8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ −5.3, 18.4, 25.9, 28.3, 44.2, 64.7, 80.0, 109.9, 118.6, 126.1, 126.2, 126.4, 127.3, 128.6, 134.0, 137.9, 142.0, 144.5, 145.8, 155.8; HPLC: retention time: 9.500 min; purity: 95.2% (HPLC).

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe solvent was removed under reduced pressure
  3. dissolutionThe residue was dissolved in CH2Cl2 (50 mL)
  4. washwashed with water (20 mL), brine (20 mL)
  5. dry with materialdried over Na2SO4
  6. customAfter the solvent was removed
  7. customthe crude product was purified on Al2O3 column chomatography
  8. washeluting with CH2Cl2

Sources & evidence

ORD record
ord-482b9d91321e4b7794c858335bef85fa
Source dataset
uspto-grants-2011_12
Patent number
US08084449B2

Reaction notes

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