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Polyhalogenated nitrobutadienic building blocks (PNBBs) represent an important class of reactive species and useful synthetic intermediates or synthons.In the early days, the availability of these kinds of compounds was rather limited, which significantly constrained their synthetic applications.Over the past two decades, several facile and practical synthetic approaches have been developed towards aromatic compounds such as thiophenes, pyrimidines, thereby allowing the exhaustive investigations on their chemical characteristics.