Dearomatization_re-revised 2.pdf (737.01 kB)
Reactivity of Arynes for Arene Dearomatization
journal contribution
posted on 2019-01-14, 00:00 authored by Rajdip Karmakar, Anh Le, Peipei Xie, Yuanzhi Xia, Daesung LeeAn 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
Funding
We are grateful to NSF (CHE 1361620, D.L.) and the NSFC (21372178 and 21572163, Y.X.) for financial support. The Mass Spectrometry Laboratory at UIUC is greatly acknowledged
History
Publisher Statement
Copyright @ American Chemical SocietyCitation
Karmakar, R., Le, A., Xie, P., Xia, Y., & Lee, D. (2018). Reactivity of Arynes for Arene Dearomatization. Organic Letters, 20(14), 4168-4172. doi:10.1021/acs.orglett.8b01466Publisher
American Chemical SocietyLanguage
- en_US