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  A Comparative Mechanistic Study of Cu-Catalyzed Oxidative Coupling Reactions with N-Phenyltetrahydroisoquinoline

Boess, E., Schmitz, C., & Klussmann, M. (2012). A Comparative Mechanistic Study of Cu-Catalyzed Oxidative Coupling Reactions with N-Phenyltetrahydroisoquinoline. Journal of the American Chemical Society, 134(11), 5317-5325. doi:10.1021/ja211697s.

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 Creators:
Boess, Esther1, Author              
Schmitz, Corinna1, Author              
Klussmann, Martin1, Author              
Affiliations:
1Research Group Klußmann, Max-Planck-Institut für Kohlenforschung, Max Planck Society, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, DE, ou_1445608              

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 Abstract: A comparative mechanistic study of Cu-catalyzed oxidative coupling reactions of N-phenyltetrahydroisoquinoline with different nucleophiles was conducted. Two previously reported combinations of catalyst and oxidant were studied, CuCl2·2H2O/O2 and CuBr/tert-butyl hydroperoxide (TBHP). On the basis of a synthetic study with different nucleophiles, the electrophilicity of the intermediate iminium ion was estimated and differences between the two methods were revealed. The key intermediate in the aerobic method is shown to be an iminium ion, formed through oxidation by copper(II), which can react with any nucleophile of sufficient reactivity. The role of oxygen is the reoxidation of the reduced catalyst. In the CuBr/TBHP system, an α-amino peroxide is proposed as a true intermediate within the catalytic cycle, formed from the amine and TBHP by a Cu-catalyzed radical reaction pathway and acting as a precursor to the iminium ion intermediate.

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Language(s): eng - English
 Dates: 2015-12-152012-03-072012-03-21
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja211697s
 Degree: -

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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 134 (11) Sequence Number: - Start / End Page: 5317 - 5325 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870