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Intramolecular hydroarylation of alkynes catalyzed by platinum or gold: mechanism and endo selectivity



Intramolecular hydroarylation of alkynes catalyzed by platinum or gold: mechanism and endo selectivity



Chemistry 11(10): 3155-3164



The cyclization of differently substituted aryl alkynes with PtII or AuI catalysts proceeds by endo-dig pathways. When AgI was used to generate reactive cationic AuI catalysts, 2H-chromenes dimerize to form cyclobutane derivatives by a AgI-catalyzed process. A DFT study on the cyclization mechanism shows a kinetic and thermodynamic preference for 6-endo-dig versus 5-exo-dig cyclizations in PtII-catalyzed processes. Calculations indicate that although Friedel-Crafts and the cyclopropanation processes via metal cyclopropyl carbenes show very similar activation energies, platinum cyclopropyl carbenes are the stationary points with the lowest energy.

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Accession: 049392503

Download citation: RISBibTeXText

PMID: 15779093

DOI: 10.1002/chem.200401069


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