Li Luyang, Yu Tongyan, Du Kemeng, Xu Pan
School of Chemistry and Chemical Engineering, Southeast University, Nanjing, China.
Nat Commun. 2025 Aug 6;16(1):7251. doi: 10.1038/s41467-025-62585-1.
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)-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)-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.
在保持分子结构完整性的同时，实现官能团向分子内未活化的C-H位点的直接迁移，是有机合成领域面临的一项重大挑战。在此，我们报道基于光催化奎宁环的自由基阳离子催化能够实现选择性的1,4-氰基迁移至烯基C(sp)-H位点，而不会引入任何额外的修饰。该方法利用以N为中心的自由基阳离子作为催化剂，促进自由基迁移和离子消除，从而恢复双键并实现CN基团与C(sp)-H键之间的位置交换。这导致形成烯基腈，这是一种通用的关键中间体，它可以很容易地与多种亲核试剂发生取代反应，进而实现烯烃的多种双官能化。因此，这种CN迁移方法补充了现有的通过官能团迁移进行自由基诱导的烯烃1,2-双官能化的先进方法。
