Get access

The Ketene-Surrogate Coupling: Catalytic Conversion of Aryl Iodides into Aryl Ketenes through Ynol Ethers


  • Funding provided by the NIH (R01GM102403) and the Welch Foundation (I-1612). We thank Dr. Karen S. MacMillan (UT Southwestern) for preliminary experiments related to the synthesis of anilides and Jibao Xia (UT Southwestern) for independently repeating the synthesis of 10 g, and Prof. Gary Sulikowski for suggesting the Fries rearrangement to synthesize the ketone 18.


tert-Butoxyacetylene is shown to undergo Sonogashira coupling with aryl iodides to yield aryl-substituted tert-butyl ynol ethers. These intermediates participate in a [1,5]-hydride shift, which results in the extrusion of isobutylene and the generation of aryl ketenes. The ketenes are trapped in situ with multiple nucleophiles or undergo electrocyclic ring closure to yield hydroxynaphthalenes and quinolines.