Анотація
1-Substituted-2,2,2-trifluoroethylamines have emerged as structurally distinct and pharmacologically potent motifs in modern drug design, contributing to enhanced metabolic stability, target selectivity, and bioactivity across various therapeutic classes. This review provides a comprehensive account of their catalytic enantioselective synthesis, encompassing chiral auxiliary-based methods and a wide array of asymmetric catalytic strategies — including hydrogenation, [1,3]-proton shift reactions, nucleophilic additions, and cycloadditions. Emphasis is placed on the stereochemical outcomes achieved with ruthenium, palladium, phosphoric acid, borane, and squaramide-based catalysts, many of which routinely deliver an enantiomeric excess (ee) exceeding 90–99%. Despite these advances, the phenomenon of self-disproportionation of enantiomers (SDE) remains critically underreported, casting doubt on the veracity of ee values in the literature. This review highlights the pronounced SDE behavior of fluorinated amines and underscores the need for rigorous stereochemical validation. By integrating synthetic innovation with epistemic scrutiny, this work aims to guide future research toward more reliable, efficient, and stereochemically sound methodologies for the synthesis of fluorinated amine derivatives.
Посилання
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