Chiral poly(hetero)cyclic compounds are extensively found in numerous bioactive molecules, natural products, and even func-tional materials. Synthesis of this class of molecules follows tedious classical synthetic procedures in general. Recent advancement of the transition-metal-catalyzed directed C-H bond activation fol-lowed by an intra-/intermolecular cyclization reaction provides an upfront approach to the construction of numerous poly(hetero)cy-clic compounds. However, synthesis of chiral annulated products remains challenging. In general, chiral annulated products are syn-thesized by a conventional organocatalytic pathway employing suitable chiral ligand systems. Lack of suitable chiral ligands and dif-ficulties in the design and synthesis of appropriate ligands constrain the exploration of the chemistry. Remarkably, recent advances on chiral transition-metal catalysis and chiral ligand-controlled asym-metric C(sp2)-H bond functionalization chemistry demonstrate a way forward to access chiral annulated products. This review provides an overview of recent advancements in chiral CpxM(III)-catalyzed asymmetric annulation reactions, emphasizing the mecha-nistic understanding of the developed protocols.
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