Palladium-Catalyzed Carbonylative Homocoupling of 2-Iodophenols for the Synthesis of Symmetrical Xanthones

Abstract

Herein, we report the palladium-catalyzed carbonylative synthesis of symmetrical xanthones from functionalized 2-iodophenols in a one-pot manner. The protocol involves homocoupling of 2-iodophenols using Pd catalyst, Cs₂CO₃ as base, with gaseous CO as C1 building block. The simple, ligand- and additive-free strategy provides moderate to good yields of symmetrical xanthones. The reaction was also examined with the combination of 2-hydroxyphenyl boronic acid as another coupling partner. Additionally, this protocol was extended for the synthesis of aryl and alkyl salicylate derivatives by varying the reaction conditions.

Key words

carbonylation - homocoupling - palladium - xanthones - 2-iodophenols

Publication History

Received: 18 May 2023

Accepted after revision: 05 July 2023

Accepted Manuscript online:
05 July 2023

Article published online:
04 September 2023

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• 18 9H-Xanthen-9-one (2a); Typical Procedure: To a 100 mL stainless-steel reactor, 2-iodophenol (0.5 mmol), catalyst (5 mol%), base (2.5 equiv), and solvent (10 mL) were added. The autoclave was closed tightly and then pressurized with 3 atm of CO at room temperature ( Caution! CO gas is toxic and should be handled with care), then heated at 100 °C, and the reaction mixture was stirred with a mechanical stirrer for 16 h. After the reaction, the reactor was cooled to room temperature and the residual CO pressure was vented carefully. The reaction mixture was extracted with ethyl acetate and washed with saturated aqueous NaCl solution. The combined organic layer was dried over sodium sulfate and concentrated with a rotary evaporator. The residue obtained was purified by column chromatography (ethyl acetate/petroleum ether) and the obtained products were analyzed by GCMS and by ¹H and ¹³C NMR spectroscopic techniques. ¹H NMR (400 MHz, CDCl₃): δ = 8.33 (dd, J = 8.0, 1.5 Hz, 2 H), 7.71 (ddd, J = 8.7, 7.2, 1.7 Hz, 2 H), 7.48 (d, J = 8.4 Hz, 2 H), 7.39–7.33 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 177.18, 156.15, 134.76, 126.70, 123.86, 121.83, 117.93.