Potassium Carbonate → HCID 86633198, compound

HRID 662063Notes

Reaction equation

HRID 662063 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH2:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH:5]=[C:6]([C:8]#[N:9])[CH:7]=1.[CH:19]1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=C[CH:20]=1.C([O-])([O-])=O.[K+].[K+].[CH3:44][C:45]([Si:48]([CH3:61])([CH3:60])[O:49][CH2:50][C:51]1[CH:52]=[C:53](B(O)O)[CH:54]=[CH:55][CH:56]=1)(C)[CH3:46]>O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:8]([C:6]1[CH:5]=[C:4]([CH2:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH:3]=[C:2]([C:53]2[CH:54]=[CH:55][CH:56]=[C:51]([CH2:50][O:49][Si:48]([CH3:60])([CH3:61])[CH:45]([CH3:44])[CH3:46])[CH:52]=2)[CH:7]=1)#[N:9].[CH3:19][CH3:20]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 57813278HCID 57813278, compoundHCID 57813382[3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid

Product 1

HCID 86633198HCID 86633198, compoundYield 72%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
70 °C

Procedure

1,1-Dimethylethyl [(3-bromo-5-cyanophenyl)methyl]carbamate (1.90 g, 6.11 mmol), Pd(OAc)2 (76 mg), PPh3 (228 mg) and K2CO3 (1.27 g, 9.16 mmol) were dissolved in dioxane (50 mL). The mixture was heated at 70° C. for 30 min, and then [3-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid (2.11 g, 7.94 mmol) was added. The mixture reaction was stirred at reflux overnight. The solvent was removed under reduced pressure, then the residue diluted with CH2Cl2 (100 mL). The organic layer was washed with water (30 mL) and brine (30 mL), and dried over Na2SO4. The product, 1,1-dimethylethyl {[5-cyano-3′-({[dimethyl(1-methylethyl)silyl]oxy}methyl)-3-biphenylyl]methyl}carbamate-ethane was purified by flash column chomatography (2.0 g, yield: 72%). 1H NMR (400 MHz, CDCl3) δ 0.12 (s, 6H), 0.96 (s, 9H), 1.47 (s, 9H), 4.41 (d, J=6 Hz, 2H), 4.81 (s, 2H), 7.38-7.44 (m, 3H), 7.50 (s, 1H), 7.55 (s, 1H), 7.70 (s, 1H), 7.75 (s, 1H); 13C NMR (100 MHz, CDCl3) δ −5.2, 18.4, 25.9, 28.3, 43.4, 64.7, 80.1, 113.1, 118.7, 124.7, 125.6, 126.1, 129.0, 129.2, 129.6, 130.4, 133.4, 134.8, 138.6, 141.2, 142.5, 142.9, 155.9; HPLC: retention time: 4.670 min; purity: 94.4%; MS m/z 453 (M+, 32), 339 (M+-TBS, 100).

Workup

  1. customThe mixture reaction
  2. temperatureat reflux overnight
  3. customThe solvent was removed under reduced pressure
  4. additionthe residue diluted with CH2Cl2 (100 mL)
  5. washThe organic layer was washed with water (30 mL) and brine (30 mL)
  6. dry with materialdried over Na2SO4
  7. customThe product, 1,1-dimethylethyl {[5-cyano-3′-({[dimethyl(1-methylethyl)silyl]oxy}methyl)-3-biphenylyl]methyl}carbamate-ethane was purified by flash column chomatography (2.0 g, yield: 72%)

Sources & evidence

ORD record
ord-6c763ce83a1a47e5b2f0c32e7fdbc781
Source dataset
uspto-grants-2011_12
Patent number
US08084449B2

Reaction notes

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