An Iodine-Promoted, Mild and Efficient Method for the Synthesis of Phenols from Arylboronic Acids

Abstract

A mild and efficient methodology for the ipso-hydroxylation of arylboronic acids to phenols has been developed using aqueous hydrogen peroxide as oxidizing agent and molecular iodine as catalyst. The reactions were performed at room temperature in short reaction time under metal-, ligand- and base-free conditions.

Key words

arylboronic acid - phenol - hydroxylation - hydrogen peroxide - iodine

References and Notes

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14

Hydroxylation of Arylboronic Acids; General Procedure: A 50 mL round-bottom flask was charged with arylboronic acid (1 mmol), 30% aqueous H₂O₂ (2 mL) and iodine (5 mol%) and the reaction mixture was stirred at room temperature. After completion of the reaction (TLC) the reaction mixture was diluted with water (20 mL) and extracted with diethyl ether (3 × 15 mL). The ether extract was washed with sodium thiosulfate solution (10 mL). The separated organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica gel (eluting with ethyl acetate/hexane or diethyl ether/hexane) or by crystallization. All compounds were characterized by ^¹H NMR, ^¹³C NMR, FT-IR and MS and by comparison with authentic samples. Analytical data of phenol (2a): colorless solid; mp 41-42 ˚C (Lit.^¹7 41-42 ˚C). ^¹H NMR (CDCl₃): δ = 7.25-7.19 (m, 2 H), 6.93-6.88 (m, 1 H), 6.81-6.78 (m, 2 H), 5.08 (s, 1 H); ^¹³C NMR (CDCl₃): δ = 153.0, 127.5 (2C), 120.0, 114.5 (2C)