Microwave-Promoted TBAF-Catalyzed S_NAr Reaction of Aryl Fluorides and ArSTMS: An Efficient Synthesis of Unsymmetrical Diaryl Thioethers

Abstract

Microwave irradiation was found to promote tetrabutyl­ammonium fluoride catalyzed nucleophilic aromatic substitution of aryl fluorides and arylthiotrimethylsilanes, affording high yields of unsymmetrical diaryl thioethers efficiently under mild, transition-metal- and base-free conditions. Microwave showed unusual improvement on the reaction in not only the conditions and reaction rate, but also in selectivity and substrate scope.

Key words

microwave irradiation - tetrabutylammonium fluoride - aryl halides - arylthiotrimethylsilane - nucleophilic aromatic substitution

References and Notes

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• 20a

  Typical Procedure for Microwave-Promoted TBAF-Catalyzed S _N Ar Reaction of ArSTMS and Aryl Fluorides: The mixture of phenylthiotrimethylsilane (1a; 0.218 g, 1.2 mmol, 1.2 equiv), p-nitrophenyl fluoride (2a; 0.141 g, 1.0 mmol), and TBAF (2.61 mg, 1 mol%) in MeCN (2 mL) was placed in a microwave oven flask under air and then stirred at r.t. (ca. 25 ˚C) under microwave irradiation (600 w) for 5 h and the reaction was monitored by TLC and/or GC-MS. The solvent was then evaporated under reduced pressure and the residue was purified by flash column chromatography on silica gel to give 97% yield of 3aa. An XH-100A microwave synthesis/extraction instrument, made by Beijing Xiang Hu Science and Technology Development Co. Ltd., was employed in above microwave irradiation reactions.
  (4-Nitrophenyl)phenylthioether (3aa): ^¹H NMR (300 MHz, CDCl₃): δ = 8.05 (d, J = 7.0 Hz, 2 H), 7.53-7.56 (m, 2 H), 7.45-7.48 (m, 3 H), 7.17 (d, J = 7.0 Hz, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 148.5, 145.4, 134.7, 130.4, 130.0, 129.7, 126.7, 124.0.

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24

It was observed other TBAX salts (X = Cl, Br, I) did not show any catalytic activity at all in the present reactions.