| Control over the Chemoselectivity of Pd-Catalyzed Cyclization Reactions of (2-Iodoanilino)carbonyl Compounds. | |
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MedLine Citation:
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PMID: 22473709 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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The factors that control the chemoselectivity of palladium-catalyzed cyclization reactions of (2-iodoanilino)carbonyl compounds have been explored by an extensive experimental computational (DFT) study. It was found that the selectivity of the process, that is, the formation of fused six- versus five-membered rings, can be controlled by the proper selection of the initial reactant, reaction conditions, and additives. Thus, esters or amides produce ketones by a nucleophilic addition process, whereas the addition of PhO(-) ions leads to the formation of indolines by an α-arylation reaction. In contrast, the corresponding ketone reactants yield a mixture of both reaction products, the ratio of which depends on the base used, in the presence of phenol. The outcome of the processes can be explained by the formation of a common four-membered palladacycle intermediate from which the competitive nucleophilic addition and α-arylation reactions occur. The remarkable effect of phenol in the process, which makes the α-arylation reaction easier, favored the formation of enol complexes, which are stabilized by an intramolecular hydrogen bond between the hydroxy group of the enol moiety and the oxygen atom of the phenoxy ligand. Moreover, the chemoselectivy of the process can be also controlled by the addition of bidendate ligands that lead to the almost exclusive formation of indoles at expenses of the corresponding alcohols. |
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Authors:
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Daniel Solé; Israel Fernández; Miguel A Sierra |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-4-4 |
Journal Detail:
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Title: Chemistry (Weinheim an der Bergstrasse, Germany) Volume: - ISSN: 1521-3765 ISO Abbreviation: - Publication Date: 2012 Apr |
Date Detail:
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Created Date: 2012-4-4 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9513783 Medline TA: Chemistry Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Copyright Information:
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Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Affiliation:
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Laboratori de Química Orgànica, Facultat de Farmàcia, Universitat de Barcelona, Av. Joan XXIII s/n, 08028 Barcelona (Spain), Fax: (+34) 934024539. dsole@ub.edu. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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