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)
    Search for more papers by this author
  • Claudia de León,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
    Search for more papers by this author
  • Yahui Wang,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
    Search for more papers by this author
  • Anna Homs,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
    Search for more papers by this author
  • César R. Solorio-Alvarado,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
    Search for more papers by this author
  • 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)
    Search for more papers by this author

  • 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

Das „formwandlerische“ Barbaralyl-Kation existiert als Gemisch von 181 400 entarteten Formen. Es ergab sich, dass Gold-katalysierte Cycloisomerisierungen von 7-Alkinylcyclohepta-1,3,5-trienen über fluxionale Barbaralyl-Zwischenstufen verlaufen (siehe Schema). Die Evolution der Zwischenstufen in 1- oder 2-substituierte Indene ließ sich durch die Wahl des Goldkomplexes steuern.

Ancillary