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AbstractMuch 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 α‐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.