Metal-Free Formal Oxidative C-C Coupling by In Situ Generation of an Enolonium Species

Much contemporary organic synthesis relies on transformations that are driven by the intrinsic, so-called natural, polarity of chemical bonds and reactive centers. The design of unconventionally polarized synthons is a highly desirable strategy, as it generally enables unprecedented retrosynthetic disconnections for the synthesis of complex substances. Whereas the umpolung of carbonyl centers is a well-known strategy, polarity reversal at the alpha-position of a carbonyl group is much rarer. Herein, we report the design of a novel electrophilic enolonium species and its application in efficient and chemoselective, metal-free oxidative C-C coupling.