On the Gold-Catalyzed Generation of Vinyl Cations from 1,5-Diynes
M. Sc. Thomas Wurm
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
These authors contributed equally.
Search for more papers by this authorM. Sc. Janina Bucher
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
These authors contributed equally.
Search for more papers by this authorSarah B. Duckworth
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Matthias Rudolph
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Frank Rominger
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Crystallographic investigation.
Search for more papers by this authorCorresponding Author
Prof. Dr. A. Stephen K. Hashmi
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589 Saudi Arabia
Search for more papers by this authorM. Sc. Thomas Wurm
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
These authors contributed equally.
Search for more papers by this authorM. Sc. Janina Bucher
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
These authors contributed equally.
Search for more papers by this authorSarah B. Duckworth
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Matthias Rudolph
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Frank Rominger
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Crystallographic investigation.
Search for more papers by this authorCorresponding Author
Prof. Dr. A. Stephen K. Hashmi
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589 Saudi Arabia
Search for more papers by this authorGraphical Abstract
Positive intermediates: The combination of non-terminal 1,5-diynes with cationic gold complexes enables the generation of highly reactive vinyl cations that can be used for the synthesis of unsymmetrically substituted dibenzopentalenes. Quantum-chemical calculations indicate a fast valence tautomer equilibrium between a gold alkyne complex and the vinyl cation.
Abstract
Conjugated 1,5-diynes bearing two aromatic units at the alkyne termini were converted in the presence of a gold catalyst. Under mild conditions, aryl-substituted dibenzopentalenes were generated. Calculations predict that aurated vinyl cations are key intermediates of the reaction. A bidirectional approach provided selective access to the angular annulated product in high yield, which was explained by calculations.
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