Lithium aluminum hydride → [3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methanol

HRID 1502419Notes

Reaction equation

HRID 1502419 reaction equation
[AlH4-].[Li+].C[C:4]1[CH:12]=[CH:11][C:7]([C:8](O)=[O:9])=[CH:6][C:5]=1[B:13]1[O:17][C:16]([CH3:19])([CH3:18])[C:15]([CH3:21])([CH3:20])[O:14]1>O1CCCC1>[CH3:18][C:16]1([CH3:19])[C:15]([CH3:20])([CH3:21])[O:14][B:13]([C:5]2[CH:6]=[C:7]([CH2:8][OH:9])[CH:11]=[CH:12][CH:4]=2)[O:17]1

Participants

4

Reactant 2

HCID 28112Lithium aluminum hydrideHCID 160860864-Methyl-3-(tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid

Product 1

HCID 44118236[3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methanolYield 78.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Lithium tetrahydroaluminate (1.0M solution in tetrahydrofuran, 6.1 mL, 6.0 mmol) was added dropwise to a solution of 4-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid (0.4 g, 1.5 mmol) in tetrahydrofuran (6 mL) cooled at 0° C. The reaction mixture was warmed to room temperature, stirred for 2 hours, and then quenched via dropwise addition of saturated aqueous ammonium chloride solution (1 mL). The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (50 mL). The organic layer was separated, dried over sodium sulfate, filtered, and evaporated in vacuo to afford a residue that was purified by flash chromatography (silica, 12 g, ISCO, 0-100% ethyl acetate in heptane) to afford the title compound as a white solid (276 mg, 61%). 1H NMR (400 MHz, CDCl3) δ 7.73 (d, J=1.3 Hz, 1H), 7.32 (dd, J=7.8, 1.8 Hz, 1H), 7.16 (d, J=7.8 Hz, 1H), 4.63 (s, 2H), 3.01 (s, 1H), 2.52 (s, 3H), 1.34 (s, 12H).

Workup

  1. temperatureThe reaction mixture was warmed to room temperature
  2. customquenched via dropwise addition of saturated aqueous ammonium chloride solution (1 mL)
  3. additionThe reaction mixture was diluted with ethyl acetate (50 mL)
  4. washwashed with water (50 mL)
  5. customThe organic layer was separated
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customto afford a residue that
  10. customwas purified by flash chromatography (silica, 12 g, ISCO, 0-100% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-77392b751e8b46c8ae44ac30d3e28ad2
Source dataset
uspto-grants-2015_12
Patent number
US09206175B2

Reaction notes

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