Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids, Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides

Laboratory of Homogeneous Catalysis and Molecular Design at the Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łodź, Poland

Institute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznań, Poland

Institute of General and Ecological Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland

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Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen, Denmark

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Dipartimento di Chimica e Biologia “A. Zambelli” Università di Salerno, Via Giovanni Paolo II, 84084 Fisciano (SA), Italy

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Department of Chemistry, University of Helsinki, A.I. Virtasen aukio 1, 00014 Helsinki, Finland

Authors to whom correspondence should be addressed.

Academic Editor: Norio Shibata

Molecules 2021, 26(10), 2957; https://doi.org/10.3390/molecules26102957

Received: 30 April 2021 / Revised: 13 May 2021 / Accepted: 14 May 2021 / Published: 16 May 2021

(This article belongs to the Special Issue Organofluorine Chemistry and Beyond)

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Abstract

We describe a mechanism-guided discovery of a synthetic methodology that enables the preparation of aromatic amides from 2-bromo-2,2-difluoroacetamides utilizing a copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully introduced. A wide range of 2-bromo-2,2-difluoroacetamides as either aliphatic or aromatic secondary or tertiary amides were also reactive under the developed conditions. The described synthetic protocols displayed excellent efficiency and were successfully utilized for the expeditious preparation of diverse aromatic amides in good-to-excellent yields. The reactions were scaled up to gram quantities. View Full-Text

Keywords: fluorine; amides; copper; catalysis; C-C-coupling; boronic acids; aryl trialkoxysilanes; dimethyl-aryl-sulfonium salts

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MDPI and ACS Style

Mkrtchyan, S.; Jakubczyk, M.; Lanka, S.; Pittelkow, M.; Iaroshenko, V.O. Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids, Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides. Molecules 2021, 26, 2957. https://doi.org/10.3390/molecules26102957

AMA Style

Mkrtchyan S, Jakubczyk M, Lanka S, Pittelkow M, Iaroshenko VO. Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids, Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides. Molecules. 2021; 26(10):2957. https://doi.org/10.3390/molecules26102957

Chicago/Turabian Style

Mkrtchyan, Satenik, Michał Jakubczyk, Suneel Lanka, Michael Pittelkow, and Viktor O. Iaroshenko. 2021. "Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids, Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides" Molecules 26, no. 10: 2957. https://doi.org/10.3390/molecules26102957

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Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids, Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides

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