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Gold for the Generation and Control of Fluxional Barbaralyl Cations

Authors

  • Dr. Paul R. McGonigal,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • Claudia de León,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • Yahui Wang,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • Anna Homs,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • César R. Solorio-Alvarado,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • Prof. Antonio M. Echavarren

    Corresponding author
    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
    2. Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo s/n, 43007 Tarragona (Spain)
    • Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • We thank the MICINN (CTQ2010-16088/BQU and FPI fellowship to A.H.), the AGAUR (2009 SGR 47), AtMol (Contract No. ICT-270028), and the ICIQ Foundation for financial support. We also thank the ICIQ X-ray diffraction unit for the solid-state structures of 16/16′, 17, 18, and 7 v.

Abstract

original image

The frog prince with his two identities pales in comparison with the shape-shifting barbaralyl cation, which exists as a mixture of 181 400 degenerate forms. Gold-catalyzed cycloisomerizations of 7-alkynyl cyclohepta-1,3,5-trienes were found to proceed via fluxional barbaralyl intermediates (see scheme). The evolution of the intermediates into 1- or 2-substituted indenes could be controlled by the choice of gold complex.

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