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Over the last ten years, the combination of organocatalysis with transition metal (TM) catalysis has become one of the most important toolboxes used for synthesizing optically pure compounds containing chiral quaternary centers, including spiro heterocyclic molecules. The dominant method in the enantioselective synthesis of spiro heterocyclic compounds based on synergistic catalysis includes chiral aminocatalysis and NHC catalysis, as already established covalent organocatalytic strategies. Another area of organocatalysis widely combined with TM catalysis producing enantiomerically enriched spiro heterocyclic compounds is non‐covalent catalysis, dominated by chiral phosphoric acids, thiourea, and squaramide derivatives. This review article aims to summarize enantioselective methods used for constructing spirocyclic heterocycles based on a combination of organocatalysis and transition metal catalysis. [ABSTRACT FROM AUTHOR]

An organocatalytic asymmetric domino Michael/α‐alkylation reaction between enals and non‐stabilized alkyl halides has been developed. Chiral secondary amine catalyzed cyclization reaction of 1‐bromo‐3‐nitropropane with α,β‐unsaturated aldehydes provides 1,2,3‐trisubstituted cyclopentane carbaldehydes with high diastereo‐ (dr up to 8 : 1) and enantioselectivities (ee up to 96 %). [ABSTRACT FROM AUTHOR]