Stereodivergent 1,3-Difunctionalization of Alkenes by Charge Relocation

Nuno Maulide used charge relocation for the stereodivergent 1,3-difunctionalization of alkenes.

Alkenes are one of the most basic, crucial and ubiquitous func-tional groups in organic synthesis and, as such, have long been of immense commercial importance, finding applications in, among other things, petrochemistry and the production of pharmaceuticals and fragrances. Among the many reaction modes accessible to alkenes (e.g., cycloaddition, oxidation, polymerization, metathesis, and others), alkene difunctionalization is arguably the most intuitive paradigm, serving as a textbook example of alkene reactivity in organic chemistry curricula around the world. Within the realm of alkene di-functionalization, 1,2-addition across the double bond and allylic functionalization are the most widely encountered reaction classes. In contrast, difunctionalization at positions remote from one another has been reported considerably less frequently.
Nuno Maulide and his group from the University of Vienna (Austria) developed an idea, as he explains, “out of a consideration of the limitations of classical methods for alkene transformation. While the ma-jority of known reactions only allow functionalization on the two alkene carbon atoms – or the allylic position – we sought to break this paradigm using the reactivity inherent to carbo-cationic species generated from the addition of electrophiles to alkenes.”

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