Efficient approaches to the gram‐scale synthesis of fluorinated pyrazoles and pyrimidines bearing saturated (hetero)cyclic substituents are described. The methods rely on the heterocyclizations of sp3‐enriched β‐bromo‐α,α‐difluoroketones and fluorinated enaminones (in turn prepared from saturated heterocyclic α‐fluoroketones), respectively; these compounds themselves are useful synthetic intermediates that have been prepared on multigram scale for the first time. LogP and aqueous solubility measurements, as well as lead‐likeness assessment using the Nelson's LLAMA tool show that the 19 synthesized sp3‐enriched fluorinated building blocks meet the lead‐oriented synthesis criteria.

The Front Cover shows examples of fluoro‐substituted pyrazoles and pyrimidines with saturated heterocyclic substituents – advanced building blocks for organic and medicinal chemistry synthesized by a group of chemists from Kyiv, Ukraine. An efficient approach to the multigram preparation of sp3‐enriched fluorinated building blocks bearing protected azetidine, pyrrolidine, piperidine, or cyclohexanone moieties and transformations of these useful intermediates into the nitrogen heterocycles mentioned above are described. The authors thank Mr. Andriy Yakymenko for the photo of rapeseed fields used as a background, Mr. Bohdan Vaschenko and Ms. Vladyslava Prykhodko for their help with picture preparation. More information can be found in the Research Article by O. O. Grygorenko et al.