Accounts of Chemical Research, Год журнала: 2025, Номер unknown
Опубликована: Апрель 2, 2025
ConspectusAromatic rings are fundamental structural motifs found in natural products, synthetic intermediates, pharmaceuticals, agrochemicals, and functional materials. While transformations at the periphery of these well-established, modifying their core frameworks has remained an underexplored frontier. Our group pioneered concept, termed "aromatic metamorphosis", enabling skeletal aromatic by replacing endocyclic atom with a different or inserting into rings, which leads to novel strategies diverse molecular architectures.The concept metamorphosis was first demonstrated stepwise conversion dibenzothiophenes dibenzofurans triphenylenes. These transformations, facilitated palladium nickel catalysts, involve strategic activation robust C-S C-O bonds as key steps. Next, approach extended two-step conversions carbazoles, dibenzophospholes, fluorenes, etc., oxidation corresponding sulfones subsequent sequential inter- intramolecular nucleophilic substitution reactions. new routes have provided efficient access optoelectronic Especially, SNAr-based construction heterohelicene library systematic variation atoms. This strategy revolutionized way libraries constructed enables rapid discovery molecules.In addition substitutions, ring-expanding through insertion also been explored. We developed nickel-catalyzed boron benzofurans, generating benzoxaborins, important scaffolds for medicinal chemistry. catalytic transformation successfully scaled industrial synthesis companies, demonstrates practical utility metamorphosis. Furthermore, manganese-catalyzed lithium-metal-promoted methodologies expanded ranges heteroatoms inserted cleaved, providing methods heterocycles diversity element compositions.Reductive dilithiation thiophenes efficiently yields 1,4-dilithiobutadienes, react variety electrophiles produce series nonbiogenic heteroles, such boroles, phospholes, siloles. In principle, this method should allow sulfur readily available be replaced any is therefore considered ideal example terms chemical spaces elements.Aromatic proposes many synthons retrosynthetic disconnections that defy conventional wisdom organic synthesis. By making full use metamorphosing skeleton, can directly minimal effort time investment. Its applications span from pharmaceuticals materials science, paving paradigm design well strategy.
Язык: Английский