Phosphoric Acid → [3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid

HRID 564471Notes

Reaction equation

HRID 564471 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH2:8][O:9][SiH:10]([CH3:12])[CH3:11])[CH:5]=[CH:6][CH:7]=1.C[C:14]([CH3:17])([CH3:16])[CH3:15].[Li]CCCC.[B:23](OCCCC)([O:29]CCCC)[O:24]CCCC.OP(O)(O)=O>C1COCC1>[CH3:15][C:14]([Si:10]([CH3:12])([CH3:11])[O:9][CH2:8][C:4]1[CH:3]=[C:2]([B:23]([OH:29])[OH:24])[CH:7]=[CH:6][CH:5]=1)([CH3:17])[CH3:16]

Participants

6

Reactant 4

HCID 1004Phosphoric AcidHCID 12712Tributyl borateHCID 137331256{[(3-Bromophenyl)methyl]oxy}(dimethyl)silane 2,2-dimethylpropaneHCID 178418339Butyllithium

Product 1

HCID 57813382[3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acidYield 74.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To the solution of {[(3-bromophenyl)methyl]oxy}(dimethyl)silane-2,2-dimethylpropane (1:1) (100.0 g, 331.9 mmol) in THF (500 mL), which was cooled to −78° C., n-BuLi (132.7 mL, 331.9 mmol) was added dropwise. The mixture was stirred for 1 h at −78° C., then B(OBu)3 (107.5 mL, 398.2 mmol) was added one portion. The reaction mixture was warmed to room temperature, and stirred over night. After cooled to 0° C., 5% H3PO4 was added to pH=4-5, the mixture was stirred 0.5 h, then was filtered. After removing THF, the residue was extracted with Et2O (200 mL×2), and the organic layer was dried over Na2SO4. After removing the solvent, the residue was added to water, and white solid was precipitated which was dried in vacuo. 65.7 g of [3-({[(1,1-dimethylethyl)-(dimethyl)silyl]oxy}methyl)phenyl]boronic acid was obtained (Yield: 74.5%). 1H NMR (400 MHz, CDCl3): δ 0.14 (s, 6 H), 0.98 (s 9 H), 4.88 (s, 2 H), 7.49-7.59 (m, 2 H), 8.14 (d, J=7.6 Hz, 1 H), 8.19 (s, 1 H).

Workup

  1. temperatureThe reaction mixture was warmed to room temperature
  2. stirringstirred over night
  3. temperatureAfter cooled to 0° C.
  4. stirringthe mixture was stirred 0.5 h
  5. filtrationwas filtered
  6. customAfter removing THF
  7. extractionthe residue was extracted with Et2O (200 mL×2)
  8. dry with materialthe organic layer was dried over Na2SO4
  9. customAfter removing the solvent
  10. additionthe residue was added to water, and white solid
  11. customwas precipitated which
  12. customwas dried in vacuo

Sources & evidence

ORD record
ord-4dadff922cfd494e8df0b7b32c1149dd
Source dataset
uspto-grants-2011_11
Patent number
US08067408B2

Reaction notes

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