Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides

Marc Magre and Josep Cornella*

*Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, 45470, Germany, Email: cornellakofo.mpg.de

M. Magre, J. Cornella, J. Am. Chem. Soc., 2021, 143, 21497-21502.

DOI: 10.1021/jacs.1c11463

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Abstract

An organobismuth(III) complex bearing a bis-aryl sulfone ligand backbone catalyzes a synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids in the presence of SO₂ and Selectfluor. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.

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proposed mechanism

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General procedure for aryl sulfonyl fluorides

A pressure Schlenk equipped with a stirring bar was charged with aryl boronic acid (0.2 mmol), diarylbismuth tetrafluoroborate (5 mol%, 5.9 mg), K₃PO₄ (3.0 equiv., 0.6 mmol, 128 mg) and Selectfluor® (1.5 equiv., 106 mg), 4Å molecular sieves (50 mg) and dry CHCl₃:CH₃CN (5:1, 3 mL). The Schlenk was pressurized with SO₂ (1.5 bar) and left stirring for 16 h at 70 °C. After the reaction time, the reaction was cooled to 25 °C and filtered, the solid was washed with CH₂Cl₂ (2 × 3 mL) and the volatiles evaporated under vacuum. The crude material was purified by flash chromatography (SiO₂, pentane:CH₂Cl₂ as eluent system).

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Key Words

sulfonyl fluorides, Selectfluor

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ID: J48-Y2021