Chiral Nanoporous Covalent Organic Frameworks in Asymmetric Catalysis: A Review on Synthetic Strategies and Catalytic Performance

Abstract

Chiral covalent organic frameworks (CCOFs) have emerged as a transformative platform for asymmetric catalysis, uniquely combining molecular-level stereocontrol with the practical advantages of heterogeneous materials. This review systematically examines the strategic design and synthesis of CCOFs through three primary approaches─direct synthesis, postsynthetic modification, and chiral induction─each with distinct advantages and limitations. We highlight their groundbreaking catalytic applications across thermal catalysis, photocatalysis, and the emerging field of electrocatalysis. The central focus is the nanoscale confinement effect, wherein pore size, shape, and chemical microenvironment collectively govern substrate enrichment, transition-state stabilization, and enantioselectivity. However, achieving precise structural control at the atomic level, elucidating catalytic mechanisms within confined nanospaces, and developing scalable synthesis remain formidable challenges. By integrating recent achievements with critical insights into these challenges, this review provides a rational framework for designing next-generation CCOF catalysts, paving the way toward more sustainable and efficient asymmetric synthesis.