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      DFT calculations on the mechanism of copper-catalysed tandem arylation–cyclisation reactions of alkynes and diaryliodonium salts

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          Abstract

          We present a computational mechanistic study on the copper(III)-catalysed carboarylation–ring closure reactions leading to the formation of functionalised heterocycles. We have performed DFT calculations along selected routes and compared their free energy profiles. The calculations considered two viable options for the underlying mechanism which differ in the order of the oxazoline ring formation and the aryl transfer steps. In our model transformation, it was found that the reaction generally features the aryl transfer–ring closing sequence and this sequence shows very limited sensitivity to the variation of the substituent of the reactants. On the basis of the mechanism the origin of the stereoselectivity is ascribed to the interaction of the Cu ion with the oxazoline oxygen driving the ring-closure step selectively.

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          Most cited references 41

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          A meta-selective copper-catalyzed C-H bond arylation.

          For over a century, chemical transformations of benzene derivatives have been guided by the high selectivity for electrophilic attack at the ortho/para positions in electron-rich substrates and at the meta position in electron-deficient molecules. We have developed a copper-catalyzed arylation reaction that, in contrast, selectively substitutes phenyl electrophiles at the aromatic carbon-hydrogen sites meta to an amido substituent. This previously elusive class of transformation is applicable to a broad range of aromatic compounds.
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            Diaryliodonium Salts: A Journey from Obscurity to Fame

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              Enantioselective α-arylation of aldehydes via the productive merger of iodonium salts and organocatalysis.

              The enantioselective α-arylation of aldehydes has been accomplished using diaryliodonium salts and a combination of copper and organic catalysts. These mild catalytic conditions provide a new strategy for the enantioselective construction and retention of enolizable α-formyl benzylic stereocenters, a valuable synthon for the production of medicinal agents. As one example, this new asymmetric protocol has been applied to the rapid synthesis of (S)-ketoprofen, a commercially successful oral and topical analgesic.
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                Author and article information

                Contributors
                Role: Guest Editor
                Journal
                Beilstein J Org Chem
                Beilstein J Org Chem
                Beilstein Journal of Organic Chemistry
                Beilstein-Institut (Trakehner Str. 7-9, 60487 Frankfurt am Main, Germany )
                1860-5397
                2018
                12 July 2018
                : 14
                : 1743-1749
                Affiliations
                [1 ]Török Ignác Secondary School, Gödöllő, Hungary, Present address: St Catharine’s College, Cambridge CB2 1RL, UK
                [2 ]ELTE "Lendület" Laboratory of Catalysis and Organic Synthesis, Eötvös Loránd University, Institute of Chemistry, Budapest, Hungary
                [3 ]Servier Research Institute of Medicinal Chemistry, Záhony utca 7, H-1031, Budapest, Hungary
                [4 ]Research Centre for Natural Sciences of the Hungarian Academy of Sciences, Institute of Organic Chemistry, Budapest, Hungary
                Article
                10.3762/bjoc.14.148
                6071690
                Copyright © 2018, Stenczel et al.; licensee Beilstein-Institut.

                This is an Open Access article under the terms of the Creative Commons Attribution License ( http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc)

                Categories
                Full Research Paper
                Chemistry
                Organic Chemistry

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