Potassium Phosphate, Tribasic → 1,1-Dimethylethyl {[3'-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-5-(methyloxy)-3-biphenylyl]methyl}carbamate

HRID 564480Notes

Reaction equation

HRID 564480 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]([O:8][CH3:9])[CH:7]=1.C1(P(C2CCCCC2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2OC)CCCCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[CH3:62][C:63]([Si:66]([CH3:79])([CH3:78])[O:67][CH2:68][C:69]1[CH:70]=[C:71](B(O)O)[CH:72]=[CH:73][CH:74]=1)([CH3:65])[CH3:64]>O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:65][C:63]([Si:66]([CH3:79])([CH3:78])[O:67][CH2:68][C:69]1[CH:70]=[C:71]([C:2]2[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[C:4]([CH2:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH:3]=2)[CH:72]=[CH:73][CH:74]=1)([CH3:62])[CH3:64]

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 16079156(1R)-Dicyclohexyl(2'-methoxy-[1,1'-binaphthalen]-2-yl)phosphaneHCID 57813382[3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acidHCID 57813417Tert-butyl 3-bromo-5-methoxybenzylcarbamate

Product 1

HCID 578132741,1-Dimethylethyl {[3'-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-5-(methyloxy)-3-biphenylyl]methyl}carbamateYield 74%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
80 °C

Procedure

1,1-Dimethylethyl {[3-bromo-5-(methyloxy)phenyl]methyl}carbamate (1.4 g, 4.43 mmol), Pd(OAc)2 (70.0 mg, 0.14 mmol), dicyclohexyl[2′-(methyloxy)-1,1′-binaphthalen-2-yl]phosphane (84.0 mg, 0.175 mmol) and K3PO4 (1.2 g, 5.31 mmol) were dissolved in dioxane (30 mL). The mixture was heated at 80° C. for 30 min, and then [3-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid (1.5 g, 5.76 mmol) was added. The mixture reaction was stirred at reflux for two days. The solvent was removed under reduced pressure, then diluted with CH2Cl2 (100 mL). The organic layer was washed with water (20 mL), brine (20 mL), and dried over Na2SO4. The product 1,1-dimethylethyl[3′-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-5-(methyloxy)-3-biphenylyl]methyl}carbamate (1.5 g) was purified by flash column chromatography (PE:EA=15:1). Yield: 74%.

Workup

  1. customThe mixture reaction
  2. temperatureat reflux for two days
  3. customThe solvent was removed under reduced pressure
  4. additiondiluted with CH2Cl2 (100 mL)
  5. washThe organic layer was washed with water (20 mL), brine (20 mL)
  6. dry with materialdried over Na2SO4
  7. customThe product 1,1-dimethylethyl[3′-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-5-(methyloxy)-3-biphenylyl]methyl}carbamate (1.5 g) was purified by flash column chromatography (PE:EA=15:1)

Sources & evidence

ORD record
ord-dc48d8e0a6ae46979a58fd3ffafc305e
Source dataset
uspto-grants-2011_11
Patent number
US08067408B2

Reaction notes

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