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Reactivity of Arynes for Arene Dearomatization
Rajdip Karmakar1, Anh Le1, Peipei Xie2
1Department of Chemistry , University of Illinois at Chicago , 845 West Taylor Street , Chicago , Illinois 60607 , United States.
Abstract:
An unprecedented aryne-mediated dearomatization reaction is described. An aryne intermediate generated from arenesulfonyl ynamide-tethered triynes and tetraynes reacts with both the π-systems of a tethered alkene and the arenesulfonyl group to generate cyclohexa-1,3-diene-containing pentacyclic and hexacyclic frameworks. Density functional theory (DFT) calculations show a nucleophilic dearomatization mechanism involving a zwitterionic intermediate derived from an aryne. A novel halogen effect on the efficiency of the dearomatization and deterrence of aromatization of the cyclohexa-1,3-diene moiety was also observed.
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