Electrochemical cascade migratory versus ortho-cyclization of 2-alkynylbenzenesulfonamides
Zhaojiang Shi1, Shicheng Dong2, Ting Liu1
1Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University Fuzhou 350108 China kyye@fzu.edu.cn.
Abstract:
Efficient control over several possible reaction pathways of free radicals is the chemical basis of their highly selective transformations. Among various competing reaction pathways, sulfonimidyl radicals generated from the electrolysis of 2-alkynylbenzenesulfonamides undergo cascade migratory or ortho-cyclization cyclization selectively. It is found that the incorporation of an extra 2-methyl substituent biases the selective migration of the acyl- over vinyl-linker of the key spirocyclic cation intermediate and thus serves as an enabling handle to achieve the synthetically interesting yet under-investigated cascade migratory cyclization of spirocyclic cations.
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