Cyano group translocation to alkenyl C(sp<sup>2</sup>)-H site by radical cation catalysis.
basic_science · Level V
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- Record sourced from PubMed, PMID 40769981.
- Also identified by DOI 10.1038/s41467-025-62585-1 and PMC identifier 12328622.
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Abstract
Achieving the direct translocation of a functional group to unactivated C-H sites within a molecule, while maintaining its structural integrity, presents a notable challenge in the realm of organic synthesis. Here, we report that photocatalytic quinuclidine-based radical cation catalysis can enable selective 1,4-cyano translocation to alkenyl C(sp<sup>2</sup>)-H sites without imparting any extraneous modifications. The approach leverages N-centered radical cations as catalysts to facilitate both radical translocation and ionic elimination, thereby restoring the double bond and enabling positional exchange between a CN group and a C(sp<sup>2</sup>)-H bond. This results in the formation of alkenyl cyanide, a versatile linchpin that can easily undergo substitution reactions with a wide range of nucleophiles then lead to diverse difunctionalizations of alkenes. Consequently, this CN translocation approach complements the existing state-of-the-art method of radical-induced alkene 1,2-difunctionalization via functional group translocation.