Reactivity of Arynes for Arene Dearomatization
journal contributionposted on 14.01.2019 by Rajdip Karmakar, Anh Le, Peipei Xie, Yuanzhi Xia, Daesung Lee
Any type of content formally published in an academic journal, usually following a peer-review process.
An unprecedented aryne-mediated dearomatization reaction is described. An aryne intermediate generated from arenesulfonyl ynamide-tethered tri- and tetraynes reacts with both the π-systems of a tethered alkene and the arenesulfonyl group to generate cyclohexa-1,3-diene-containing penta- and hexacyclic frameworks. 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