A Palladium-Free Sonogashira Coupling Protocol Employing an In Situ Prepared Copper/Chelating 1,2,3-Triazolylidene System

Efstathios Tonis; Felix Stein; Ioannis K. Stamatopoulos; Jessica Stubbe; Athanasios Zarkadoulas; Biprajit Sarkar; Georgios C. Vougioukalakis

doi:10.1055/a-1290-8469

Synlett, Table of Contents

Synlett 2021; 32(06): 616-620
DOI: 10.1055/a-1290-8469

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A Palladium-Free Sonogashira Coupling Protocol Employing an In Situ Prepared Copper/Chelating 1,2,3-Triazolylidene System

Efstathios Tonis

^aLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece

,

Felix Stein

^bInstitut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, Germany

,

Ioannis K. Stamatopoulos

^aLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece

,

Jessica Stubbe

^bInstitut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, Germany

,

Athanasios Zarkadoulas

^aLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece

,

Biprajit Sarkar∗

^bInstitut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, Germany

^cChair of Inorganic Coordination Chemistry, Institute of Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany

,

Georgios C. Vougioukalakis∗

^aLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece

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Abstract

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Abstract

A new, palladium-free Sonogashira coupling reaction protocol using a catalytic system that comprises a simple, cheap, widely available copper salt and a chelating 1,2,3-triazolylidene ligand precursor is reported. This protocol provides the desired coupling products in moderate to very good yields.

Key words

Sonogashira coupling - palladium-free - copper - sustainability - 1,2,3-triazolylidenes

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References

References and Notes
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32 General Catalytic Protocol Procedure A dry Schlenk tube equipped with a magnetic stirrer is loaded under argon with Cu(OAc)₂ (10 mol%, 0.0167 mmol), ligand L (5 mol%, 0.0084 mmol), K₂CO₃ (0,33 mmol), the aryl halide (0.167 mmol), and DMF (1 mL). The above mixture is degassed with a slow bubbling flow of argon for 20 min. The terminal alkyne (0.2 mmol) is then added, and the reaction mixture is sealed under an argon atmosphere. The Schlenk tube is transferred in a preheated oil bath (130 °C), and the reaction mixture is stirred for 8 h. Then, the reaction is cooled to room temperature and transferred in a 100 mL separating funnel with 20 mL of H₂O. The mixture is extracted with ethyl acetate (3 × 10 mL). The organic layers are combined, washed with brine (15 mL), and dried over MgSO₄. The dry organic layer is filtered, and the solvent is removed in a rotary evaporator. Products are separated with gradient column chromatography using CH₂Cl₂/petroleum ether. 1-Nitro-4-(phenylethynyl)benzene (3a) Prepared according to the general procedure and obtained as a yellow solid in 80% yield (30 mg, 0.134 mmol). ¹H NMR (200 MHz, CDCl₃): δ = 8.23 (d, J = 9.0 Hz, 2 H), 7.67 (d, J = 9.0 Hz, 2 H), 7.61–7.52 (m, 2 H), 7.44–7.34 (m, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 147.14, 132.43, 132.00, 130.43, 129.43, 128.69, 123.80, 122.26, 94.86, 87.70.

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