-heteroarenes. Through the rational design of activators (including alkyl, vinyl, benzyl, dinitrophenyl and Tf groups) and the incorporation of diverse nucleophiles (O-, C-, and N-based), we have established a modular system capable of generating a range of key open-chain intermediates such as Zincke aldehydes, azatrienes (including Zincke imines), streptocyanines, and vinamidinium salts. Strategic modification of these versatile intermediates using a wide range of electrophilic, amphiphilic, or dipolar reagents enables multiple editing paradigms, including efficient pyridine ring contractions to functionalized pyrroles, degenerate ring transformations of pyridines with concurrent core functionalization, and denitrogenative annulation of pyridine to arene dialdehydes or thiophene motifs. Moreover, it facilitates the transformation of pyrimidines into diverse nitrogen-containing heterocycles via vinamidinium salt intermediates. In this Account, we systematically summarize our work on skeletal editing using tunable Zincke intermediates generated via the ANRORC pathway, with particular emphasis on mechanistic understanding, substrate scope, and synthetic applications. By outlining prospective research directions, we anticipate this Account will set the stage for future exploration of the ANRORC strategy in skeletal editing of heterocycles, promote the discovery of novel reactivity patterns, and thereby contribute to further progress in this dynamic field.
Lv et al. (2026) studied this question.