Recent Advances in Catalytic Atroposelective Synthesis of Seven‐ and Eight‐Membered Rings with Inherent Chirality

Inherently chiral seven‐ and eight‐membered cyclic frameworks constitute privileged structural motifs in natural products and bioactive compounds. While remarkable achievements have been made in enantioselective synthesis of centrally and axially chiral seven‐ and eight‐membered rings, the catalytic atroposelective construction of inherent chiral systems remains a significant challenge in modern organic synthesis. Current methodologies predominantly focus on calix[n]arene assemblies, particularly enantioenriched calix[4]arenes, whose success in materials science applications has been well‐documented in recent reviews. This review systematically summarizes emerging strategies for catalytic asymmetric access to seven‐ and eight‐membered rings, encompassing both direct asymmetric functionalization of preformed rings and de novo ring‐forming approaches. Particular emphasis is placed on catalytic asymmetric annulation methodologies and stereoselective functional group transformations that induce inherent chirality. By critically analyzing the current state‐of‐the‐art and existing limitations, this review aims to inspire innovative catalytic systems and unconventional disconnection strategies for constructing these biologically relevant yet synthetically challenging architectures.