Аннотация:The review summarizes the chemistry of nitrones and nitronates in the context of the C‐H reactivity of their α‐carbon atom. Electrophilic, nucleophilic and radical reactions leading to functionalization of the α‐position are described. Examples of the application of these processes in total synthesis are outlined. 1. Introduction 2. An overview of the α‐C‐H reactivity of nitrones and nitronates 3. Tautomerization of nitrones and nitronates 4. Nitrones and nitronates as α‐C‐nucleophilic synthons 4.1 Reaction of nitrones with С‐electrophiles 4.2 Halogenation and nitrosation of nitrones 4.3. Addition of electrophiles to N‐siloxyenamines 4.4 Reaction of nitronates with electrophiles 4.5. Addition of electrophiles to N,N‐bis(oxy)enamines 5. Nitrones and nitronates as α‐C‐radical synthons 5.1 Oxidative dimerization of nitrones 5.2 Addition reactions of N‐vinyl nitroxyl radicals 5.3 Radical reactions of N‐(oxy)enamines and N,N‐bis(oxy)enamines 5.4. Oxidation of the α‐position in nitrones 6. Nitrones and nitronates as α‐C‐electrophilic synthons 6.1 Reaction of N‐oxyenamines with nucleophiles 6.2 Introduction of nucleophiles into the α‐position of nitronates via N,N‐bis(oxy)enamines 7. Functionalization of the α‐carbon atom in nitrones and nitronates using [n,3]‐migrations and related processes 7.1 [1,3]‐Migrations in N,N‐bis(oxy)enamines 7.2 [3,3]‐Sigmatropic rearrangements in N‐oxyenamines 8. Applications in target‐oriented organic synthesis 9. Conclusions