Synlett
DOI: 10.1055/a-1290-8469
letter

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

Efstathios Tonis
a  Laboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece
,
Felix Stein
b  Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, Germany
,
Ioannis K. Stamatopoulos
a  Laboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece
,
Jessica Stubbe
b  Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, Germany
,
Athanasios Zarkadoulas
a  Laboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece
,
Biprajit Sarkar
b  Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, Germany
c  Chair of Inorganic Coordination Chemistry, Institute of Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
,
Georgios C. Vougioukalakis
a  Laboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece
› Author Affiliations
This work was supported by the Hellenic Foundation for Research and Innovation under the ‘First Call for H.F.R.I. Research Projects to support Faculty members and Researchers and the procurement of high-cost research equipment grant’ (H.F.R.I., Grant Number: 16 – Acronym: SUSTAIN). The contribution of the European Cooperation in Science and Technology (COST, Grant Number CA15106; C–H Activation in Organic Synthesis – CHAOS) is also gratefully acknowledged. Financial support from a joint DAAD-IKY project (funded by DAAD through funds from the Bundesministerium für Bildung und Forschung - BMBF) is also acknowledged.


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.

Supporting Information



Publication History

Received: 20 September 2020

Accepted after revision: 15 October 2020

Publication Date:
15 October 2020 (online)

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
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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.