Room-Temperature Ionic Liquids (RTILs) as Green Media for Metal- and Base-Free ipso-Hydroxylation of Arylboronic Acids

Abstract

The oxidative hydroxylation of arylboronic acids to the corresponding phenolic compounds under metal- and base-free aerobic conditions is successfully demonstrated on a greener media. Hydrogen peroxide, as an eco-friendly oxidant, is compatible with green mediates room-temperature ionic liquids (RTIL)s, providing hydroxylation products of arylboronic acids in an efficient manner. The RTIL support is particularly interesting for its reusability.

Key words

room-temperature ionic liquid - ipso-hydroxylation - arylboronic acid - phenol - hydrogen peroxide

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• 28 Typical Procedure for the ipso-HydroxylationA flask was charged with phenylboronic acid (3.0 mmol), [bmim]Cl (52.0 mg), and H₂O₂ (aq 30 wt%, 0.24 mL). Then, the mixture was stirred at room temperature in open air for 15 min. The reaction mixture was extracted with EtOAc (3 × 10 mL). The combined organic layers were washed with water, then dried with anhydrous Na₂SO₄, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes/EtOAc).Phenol (2a)96%, colorless oily liquid. ¹H NMR (400 MHz, CDCl₃): δ = 7.28 (t,  J = 8.4 Hz, 2 H), 6.99–6.95 (m, 1 H), 6.89–6.85 (m, 2 H), 4.80 (br s, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 155.4, 129.7, 120.9, 115.3 ppm.