4,4,5,5-Tetramethyl[1,3,2]dioxaborolane → 2-(2-(Butyloxy)-5-(methyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

HRID 2101748Notes

Reaction equation

HRID 2101748 reaction equation
Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[CH:4][C:3]=1[O:10][CH2:11][CH2:12][CH2:13][CH3:14].O(C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1)C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:54][C:55]1([CH3:62])[C:59]([CH3:61])([CH3:60])[O:58][BH:57][O:56]1>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:11]([O:10][C:3]1[CH:4]=[CH:5][C:6]([O:8][CH3:9])=[CH:7][C:2]=1[B:57]1[O:58][C:59]([CH3:61])([CH3:60])[C:55]([CH3:62])([CH3:54])[O:56]1)[CH2:12][CH2:13][CH3:14]

Participants

6

Reactant 3

HCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 578018162-Bromo-1-butoxy-4-methoxybenzene

Product 1

HCID 576724442-(2-(Butyloxy)-5-(methyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneYield 41%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
95 °C

Procedure

A mixture of 2-bromo-1-butoxy-4-methoxybenzene (1.2 g, 4.7 mmol), TEA (2.6 mL, 19 mmol), (oxydi-2,1-phenylene)bis(diphenylphosphine) (0.51 g, 0.95 mmol) (Aldrich, CAS# 166330-10-5), palladium(II) acetate (0.11 g, 0.47 mmol), and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.1 mL, 14 mmol) (Aldrich, CAS# 25015-63-8) in 1,4-dioxane (5.0 mL) was stirred overnight at 95° C. The mixture was cooled to room temperature, quenched with saturated aqueous ammonium chloride, and extracted with ether. The combined organic layers were dried over MgSO4 and concentrated. The crude product was purified by silica gel flash chromatography (0-10% EtOAc/hexane) to afford compound C.3 (0.60 g, 41% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.16 (d, J=3.1 Hz, 1H), 6.91 (dd, J=3.1, 9.0 Hz, 1H), 6.79 (d, J=9.0 Hz, 1H), 3.91 (t, J=6.3 Hz, 2H), 3.78 (s, 3H), 1.75 (m, 2H), 1.54 (m, 2H), 1.34 (s, 12H), 0.96 (t, J=7.4, 3H).

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. customquenched with saturated aqueous ammonium chloride
  3. extractionextracted with ether
  4. dry with materialThe combined organic layers were dried over MgSO4
  5. concentrationconcentrated
  6. customThe crude product was purified by silica gel flash chromatography (0-10% EtOAc/hexane)
  7. customto afford compound C.3 (0.60 g, 41% yield) as a colorless oil

Sources & evidence

ORD record
ord-e64b106892d4477aba7d7786c397c676
Source dataset
uspto-grants-2009_08
Patent number
US07572934B2

Reaction notes

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