Chiral organosilicon compounds are widely applied in frontier fields including synthetic chemistry, materials science, and pharmaceutical research. Thus, the design of green, operationally simple, and chemoselective strategies for the assembly of structurally sophisticated organosilicon frameworks is of paramount significance and continues to attract considerable attention. Silacyclobutanes (SCBs), a class of small-ring compounds with unique structural features, exhibit excellent reactivity due to their inherent ring strain. During the past decade, the transition-metal-catalyzed (Rh, Pd, Ni) regio- and enantioselective C-Si bond cleavage of silacyclobutanes has emerged as a powerful and complementary synthetic tool for accessing structurally diverse, functionalized chiral organosilanes. This review systematically surveys recent advances in transition-metal-catalyzed asymmetric cleavage of C-Si bonds in silacyclobutanes with various coupling partners, such as alkenes, alkynes, allenes, and carbonyls, for the construction of chiral functionalized organosilanes featuring carbon-centered, silicon-centered, or axially chiral stereogenic units. We also briefly discuss the associated reaction mechanisms, strategic modulation of reactivity and enantioselectivity, and prospective developments.

Chiral sulfur(IV) and sulfur(VI) compounds bearing S=N bonds are important structural units in drug discovery, materials science, and asymmetric catalysis. The presence of a stereogenic sulfur atom increases the three-dimensional complexity of molecules, allowing for the precise tuning of their physicochemical properties and biological target-binding affinities. However, the highly stereoselective construction of these high-valent sulfur centers has long been a significant synthetic challenge. This review summarizes recent progress, primarily covering literature from 2020 to 2026, in the catalytic asymmetric synthesis of chiral sulfur compounds bearing S=N bonds. For S(IV) motifs including sulfilimines, sulfinamidines, and sulfinimidate esters, we examine advances in transition-metal catalysis and organocatalysis, highlighting recent breakthroughs in radical cross-coupling and direct asymmetric amination. For S(VI) frameworks including sulfoximines, sulfonimidamides, sulfonimidate esters, and sulfonimidoyl fluorides, the discussion covers asymmetric C–H functionalization, dynamic kinetic asymmetric transformations (DyKAT), and stereospecific oxidative transfers from enantioenriched S(IV) precursors. We highlight stereocontrol strategies, reaction mechanisms, and substrate scopes. We also discuss current limitations and suggest possible directions for future work, with an emphasis on more sustainable catalytic methods and modular strategies for building new functional molecules.

Enantioselective assembly of chiral α-perfluoroalkylated organoboron compounds is a significant challenge in synthetic chemistry. Herein, a copper-catalyzed asymmetric B-H insertion reaction was employed to couple 2-arylpyridine-boranes with α-aryl-α-perfluoroalkyl diazomethanes, delivering over 40 novel chiral α-perfluoroalkylated organoboron compounds bearing boron/carbon vicinal stereogenic centers. This protocol accommodates a range of perfluoroalkyl substituents, including CF₃, C₂F₅, C₃F₇, and C₄F₉. The reaction affords products in up to 85% yield, 99% ee, and dr > 20:1 for longer-chain perfluoroalkyl substrates. Mechanistic insights are provided by deuterium-labeling and KIE experiments, together with reference to previous related precedents. The scalability and further transformations of the reaction products demonstrate their potential usefulness in the synthetic community.

Chiral carbon-rich molecules have attracted increasing attention because they integrate extended π-conjugation with stereochemical complexity, thereby giving rise to circularly polarized luminescence, chiral charge/spin transport, molecular recognition, and unconventional open-shell electronic structures. Among the structural elements available for their construction, five-membered carbon rings occupy a particularly important position. This review provides an overview of recent progress in chiral carbon-rich molecules incorporating five-membered carbocyclic motifs, including chiral fullerenes, nonbenzenoid and bowl-shaped nanographenes, helically distorted open-shell systems, and chiral polycyclic aromatic hydrocarbons (PAHs) with interrupted π-conjugation. We emphasize the dual and complementary roles of five-membered carbocycles. In fully conjugated frameworks, pentagons introduce curvature, non-benzenoid topology, perturbed aromaticity, and unusual spin/electronic distributions, thereby enabling diverse chiral fullerene and nanographene architectures with distinctive optical, magnetic, and supramolecular properties. In frameworks with interrupted π-conjugation, five-membered rings incorporated into spiro-, indane-, or cyclophane-type motifs can rigidify three-dimensional architectures, mediate chirality transfer, attenuate through-bond π-conjugation, and enhance through-space electronic coupling, thereby offering effective design strategies for high-performance chiroptical and optoelectronic systems. By comparing these two regimes, we highlight how five-membered carbocycles have emerged since 2019 as versatile design elements for modulating chirality, topology, and function in carbon-rich molecules, and we discuss current synthetic limitations, unresolved mechanistic questions, and potential future opportunities in photonic, spintronic, and molecular electronic applications.

The incorporation of multiple stereogenic elements into a single molecule can profoundly influence its biological and physical properties. However, the direct enantioselective synthesis of atropisomers bearing both axial and central chirality remains a significant challenge. Herein, we report an efficient kinetic resolution strategy based on a Michael addition/O-alkylation cascade between racemic bromonitroalkenes and 2-naphthols. This methodology enables the simultaneous synthesis of atropisomers featuring multiple stereogenic elements while recovering axially chiral bromonitroalkene building blocks with excellent stereoselectivities (up to 98% ee and > 20:1 dr, with a selectivity factor S up to 259). The reaction accommodates a broad range of electronic and steric substituents on both the nitroalkene and the naphthol components, as well as variation of the fused aromatic ring system. The synthetic utility of the approach was further demonstrated through gram-scale synthesis, parallel resolution, and the transformation of the recovered (aR)-bromonitroalkene into diverse atropisomeric architectures and the construction of various bis-axially chiral atropisomers via central-to-axial chirality transfer. A plausible transition-state model was proposed to rationalize both the stereochemical outcomes and the role of DABCO as a co-catalyst. This work provides a practical and versatile platform for accessing structurally complex molecules with multiple stereogenic elements and expands the synthetic toolbox for constructing chiral molecular architectures.

N-heterocyclic carbene (NHC) organocatalysis enables umpolung activation of enals to deliver chiral α,β-unsaturated acylazolium electrophiles, realizing a highly selective cascade Friedel-Crafts (F-C) alkylation/lactamization of 4-aminoindoles with regioselective C5-site functionalization and excellent enantioselectivity. Nevertheless, the underlying mechanism and origins of selectivities remain poorly understood. Herein, we report a comprehensive density functional theory (DFT) investigation to fully characterize the complete catalytic cycle of this cascade transformation. The computational results indicate that the electrophilic addition of 4-aminoindole to the α,β-unsaturated acylazolium intermediate governs the stereoselectivity and regioselectivity. Activation-strain model (ASM) and energy decomposition analysis (EDA) reveal that electrostatic interactions and dispersion forces constitute the dominant stabilizing factors for the energetically favorable S-configured transition state. For regioselectivity, projection of orbital coefficient vector (POCV) analysis quantifies intrinsic atomic reactivity of different indole carbon sites, verifying that higher atomic reactivity at C5 position accounts for the preferential C5-functionalization. This work establishes a full mechanistic map of NHC-catalyzed asymmetric F-C reaction of indole and provides quantitative theoretical tools (ASM, EDA, POCV) to predict and rationalize stereo- and regioselectivity, offering guidance for rational design of NHC catalytic systems for indole functionalization.

The development of asymmetric catalytic methods using CO₂ as a C1 synthon is an important strategy for constructing chiral carboxylic acids and heterocyclic compounds. In recent years, through the design of innovative catalytic systems, efficient and highly selective syntheses of chiral carboxylic acids, spanning central to axial chirality, have been achieved from diverse substrates, including alkenes, alkynes, and organic electrophiles. Concurrently, significant progress has also been made in the synthesis of chiral heterocycles, particularly 2-oxazolidinones and cyclic carbonates. This review systematically summarizes key advances in this field from 2021 to mid-2026. Organized by target product structure, the discussion first addresses chiral carboxylic acids, categorized by substrate type (carbon-carbon unsaturated bonds and organic electrophiles). Key strategies, including carbo-carboxylation, boracarboxylation, hydrocarboxylation, dicarboxylation, and electroreductive carboxylation, are elaborated in detail, along with their stereoselectivity control mechanisms. The discussion then covers chiral heterocycles, summarizing the catalytic asymmetric construction of chiral 2-oxazolidinones and chiral cyclic carbonates. Finally, the major challenges and future directions in this field are discussed.

We report an organocatalytic enantioselective desymmetrization of 2-aminophenyl malonates enabled by intramolecular ester aminolysis. This protocol efficiently delivers C3-disubstituted oxindole derivatives bearing quaternary stereocenters under mild conditions with excellent chemo- and enantioselectivities. Notably, this reaction follows an acid-promoted dehydration pathway instead of an alcohol elimination pathway, which differs from conventional ester aminolysis reactions reported previously. Gram-scale synthesis and further derivatization of the resulting products demonstrate the synthetic utility of this transformation.

Owing to their stable axial chirality, atropisomeric biaryl compounds have found widespread applications in medicinal chemistry, natural product chemistry, and agricultural chemistry. Up to now, two principal strategies have been established for the synthesis of axially chiral biaryls: the enantioselective construction of the aryl-aryl axis via asymmetric coupling reactions, and the stereoselective modification of a pre-existing axis, which includes asymmetric construction of one aromatic ring, desymmetrization of prochiral substrates, and dynamic kinetic resolution (DKR) of biaryl skeletons. Among these strategies, enantioselective C−H functionalization avoids the use of pre-functionalized substrates and installs sterically demanding groups that enhance rotational barriers, thereby serving as an ideal DKR tool for the construction of atropisomeric biaryls directly from biaryl substrates with low rotational barriers. In this review, based on the nature of the directing groups, we summarize three distinct strategies for enantioselective C−H functionalization of biaryls with free axial rotation: directing group (DG)-mediated, transient DG-enabled, and DG-free approaches. The mechanisms and substrate scopes of selected representative reactions are also briefly discussed.

Although significant progress has been made in constructing three-dimensional, C(sp³)-rich bioisosteres for pyridines, the development of catalytic enantioselective approaches to access chiral nitrogen-containing bridged scaffolds remains limited and challenging. Herein, we report a chiral Brønsted acid-catalyzed enantioselective reduction of imines harnessing Hantzsch ester as the hydrogen source under mild conditions, delivering structurally diverse chiral 3-azabicyclo[3.1.1]heptanes (27 examples) in generally good yields with high enantiocontrol (up to 93% yield, 97% ee). The reaction can be scaled up to 2 mmol with full preservation of the excellent outcomes. These saturated heterocycles serve as versatile precursors, as demonstrated by conversion to bicyclo[2.1.1]hexanes via a facile nitrogen-deletion strategy with complete retention of enantiopurity. Notably, the enantioenriched 3-aza-BCHep can serve as a secondary amine organocatalyst, promoting the asymmetric Friedel–Crafts alkylation of indole with an α,β-unsaturated aldehyde in excellent yield and promising stereoinduction. This work establishes a practical route to access enantiopure saturated heterocyclic scaffolds, offering new three-dimensional candidates as potential pyridine isosteres in drug discovery and asymmetric catalysis.

The CuH-catalyzed regio-, diastereo-, and enantioselective reduction of vinyl-substituted 1,2-diketones has been achieved, efficiently affording a range of vinyl-substituted syn-1,2-diols, motifs that are ubiquitous in bioactive molecules and serve as valuable building blocks in organic synthesis. Totally 24 diol products were obtained smoothly (up to 91% yield) with a high level of stereoselectivity control (up to 99% ee and > 20:1 dr). The protocol tolerates both aryl and alkyl substrates, and the products facilitate a range of further transformations. The work represents a new choice that addresses the limitations of known methods.

Precisely controlling the supramolecular chirality of polymer assemblies remains a persistent challenge. Herein, we report the synthesis of various main-chain chiral azopolyesters with side azobenzenegroups through the regioselctive ring-opening copolymerization of cyclic anhydrides and enantiopure epoxides with different spacer lengths between the chiral stereocenter and the azobenzene chromophore. The influences of both the spacer length and main-chain backbone structure on the supramolecular chirality of the resulting azopolyester assemblies are investigated in detail. The slight change in main-chain structure or/and the flexible spacer allows successful control over chiral consistency or chirality inversion in the assemblies, leading to two distinct odd-even effects. This effect is also reflected in the liquid crystalline properties of the azopolyesters. These findings provide a novel strategy for modulating supramolecular chirality in polymer assemblies.

Axially chiral biaryls exhibit broad applications across diverse disciplines, and thus the development of conceptually new methods for accessing this structural motif remains highly desirable. Herein, we report the successful implementation of atroposelective de novo benzene formation via asymmetric [2+4] annulation in the enantioselective synthesis of axially chiral 1,2'-binaphthyls using β-substituted α-naphthylalkynes and o-iodostyrenes as C-4 and C-2 synthons, respectively. This nickel/PyrOX-catalyzed annulation reaction features a broad substrate scope (43 examples), excellent regiocontrol, exclusive 6-endo cyclization, and good to high enantioselectivity (up to 92% ee). Furthermore, the synthetic utility of the products is demonstrated through their efficient derivatizations into a range of potential bidentate ligands and bifunctional organocatalysts.

Due to the conformational rigidity, the bridged-cyclic chiral phosphorus compounds have been demonstrated to show enantioinducing ability generally superior to conformationally flexible chiral phosphorus compounds as ligands or organocatalysts in catalytic asymmetric reactions. However, investigations into the bridged-cyclic chiral phosphorus compounds are relatively much rarer than the non-bridged-cyclic phosphorus compounds resulting from the paucity of efficient synthetic methods. In order to draw the attention of researchers who are interested in asymmetric synthesis and catalysis to this issue, in this review, we intend to summarize the progress in the synthesis of bridged-cyclic chiral phosphorus compounds and their applications in catalytic asymmetric reactions. We wish this review article could serve as a useful guide and stimulate, to some extent, the interests of asymmetric catalysis scholars to devote to this challenging but greatly important field.

Chiral nickel complexes of bis(oxazoline)s serve as highly active catalysts for an enantioselective reductive alkenylation of N-sulfonyl and N-sulfamoyl aldimines, using readily available alkenyl bromides and triflates as reagents. The new method is readily scalable with low loadings of nickel catalysts, as low as 0.2 mol%. The reaction condition is almost neutral and tolerated polar groups of esters, thioethers, carbamates, heterocyclic pyridine and quinoline, and weakly acidic alcohols. Mechanistically, density functional theory (DFT) calculations reveal that alkenyl transfer to N-sulfonyl imines occurs on nickel catalysts via a classical 1,2-migratory insertion.

Amino acids are typical naturally occurring chiral compounds, whose enantiomeric pairs show distinct biological functions and markedly different application prospects. The precise chiral recognition of amino acid enantiomers is of great significance in diverse fields including life sciences, medical diagnosis, and pharmaceutical development. Over the past decade, chiral fluorescent probes toward amino acids have gained considerable attention for enantiomer recognition. Among these probes, Schiff base chiral fluorescent probes have emerged as a powerful class of sensors for achieving high enantioselective recognition of amino acids, owing to their advantages of facile synthesis, tunable structure, facile functionalization, and excellent photophysical and coordination properties. This review systematically summarizes the research progress of such probes in the enantiomer recognition of different types of amino acids, including acidic, basic, non-polar, and polar amino acids. It focuses on discussing probe design strategies, enantioselective recognition, interaction mechanisms, and application developments. In addition, this paper also highlights and outlines the major challenges existing in this field and the difficult issues that need to be addressed in the future.

Over the past few decades, transition-metal-free chiral Brønsted acid or Lewis acid-catalyzed asymmetric reactions between diazo nucleophiles and imines have emerged as a pivotal strategy for constructing chiral aziridines or β-amino α-diazo derivatives, achieving remarkable synthetic progress. This review summarizes the research advances in asymmetric aza-Darzens reactions and asymmetric Mannich-type reactions of diazo nucleophiles with imines. It encompasses diverse catalytic systems, including chiral boroxinates, chiral dicarboxylic acids, chiral phosphoric acids, chiral N-triflylphosphoramides, and chiral Lewis acids, with an emphasis on the effects of substrate and catalyst on chemoselectivity. Remaining challenges and future perspectives are presented in this review.

Chiral saturated (hetero)cyclic scaffolds constitute privileged structural motifs in natural products, pharmaceuticals, and bioactive molecules, where their three-dimensional architectures often confer superior physicochemical and pharmacological properties compared to planar aromatic systems. Despite their importance, general and modular strategies for the enantioselective synthesis of these C(sp³)-rich frameworks remain limited. In recent years, enantioselective radical cross-coupling (RCC) has emerged as a transformative strategy that addresses these limitations by enabling the direct coupling of abundant radical precursors, including alkenes, carboxylic acids, alkyl halides, and C(sp³)–H bonds, in a largely functional-group-agnostic manner. By leveraging transition-metal catalysis with chiral ligands, these methods achieve exquisite stereocontrol while providing modular access to structurally diverse saturated (hetero)cycles under mild conditions. This review comprehensively surveys recent advances in the catalytic enantioselective construction of saturated (hetero)cycles via RCC, organized into three major strategic classes: enantioconvergent cross-coupling of racemic substrates, enantioselective hydrofunctionalization of (hetero)cyclic alkenes, and direct enantioselective C(sp³)–H RCC. We critically analyze synthetic achievements, mechanistic insights, and substrate scope encompassing diverse ring sizes (from three-membered to bridged polycyclic systems) and heteroatom incorporation (N, O, S, P, Si, Ge), and discuss persistent challenges including macrocycle synthesis, C(sp³)–C(sp³) bond formation, multicomponent couplings, catalyst diversification beyond nickel and cobalt, expansion of C(sp³)–H functionalization scope, and mechanistic elucidation. This review provides a comprehensive understanding of the current state of the field and highlights promising directions for future development in accessing enantioenriched (hetero)cyclic architectures with broad applications in pharmaceutical discovery, materials science, and chemical biology.

Chiral ligands play a crucial role in enantioselective transition-metal catalysis, not only by coordinating to metal centers and modulating their electronic properties, but also by providing the essential chiral environment for efficient enantiodiscrimination. For a given reaction, high enantioselectivities can often be achieved with different chiral ligands, offering valuable enantioinduction models, even when these ligands possess distinct structures and chiral environments. Herein, we report that a class of conformationally flexible C₁-symmetric axially chiral phenanthroline ligands enables the formation of chiral copper catalysts capable of promoting the highly enantioselective ring-opening acyloxylation of cyclic biaryliodonium salts. Using this approach, a range of valuable axially chiral biaryl compounds bearing an ester group and a carbon–iodine bond were synthesized in good to excellent yield (up to 99%), with good to excellent enantioselectivity (up to 99.5:0.5 er).

Owing to its intrinsic chirality, programmability and structural diversity, DNA functions as an effective chiral ligand for asymmetric catalysis in water. DNA hybrid catalysts are constructed by anchoring metal species into DNA scaffolds through covalent or noncovalent strategies. These DNA-based catalytic systems exhibit potent reactivity and high enantioselectivity in various C–C, C–N, C–O, and C–F bond formation reactions in aqueous media. Importantly, their catalytic activity and product stereochemistry can be precisely directed by modulating DNA sequences, tertiary structures, metal species, and host-guest interaction. This review highlights recent advances in DNA-mediated asymmetric catalysis and discusses future prospects toward tailored stereocontrol under aqueous conditions.

L-amino acids are ubiquitous in biology, yet the origin of their homochirality is an enduring mystery. Prebiotic chiral selection process of amino acids could significantly influence subsequent molecular evolution and the emergence of life. However, the distribution of chirality of amino acids remains convoluted, which poses obstacles to the in-depth study of prebiotic chiral selection of amino acids. Here, we propose that minerals in the prebiotic environment might have hindered the absolute selection of L-amino acids to induce a random distribution of L- and D-amino acids during the early stages of life’s evolution. Pyrite, abundant in the prebiotic world, predominantly selected D-amino acids in the photocatalytic reductive amination of α-keto acids, resisting the enantioselectivity of chiral driving forces like chiral structures, magnetic fields, circularly polarized light, and chiral molecules. This resistance is due to the wavy atomic arrangement of pyrite surfaces, which causes larger reaction energy differences between enantiomers. Our findings provide evidence to assess the validity of prebiotic chiral selection scenarios for biomolecules, an important step in understanding the origin of life.

Axially chiral binaphthyl scaffolds provide a robust platform for encoding permanent stereochemistry into conjugated polymer backbones while promoting nonplanar organization and higher-order aggregation. Building on our group’s earlier development of multilayer 3D folding polymers and related achiral/chiral multilayer polymer series, we designed and synthesized the first enantiopure chiral multilayer polymers from enantiopure binaphthyl-derived monomers via CuI-assisted, Pd-catalyzed Sonogashira polycondensation. To probe structure–property relationships, the monomer library was designed to contrast flexible alkoxy-substituted systems with a conformationally constrained tethered analogue. The resulting polymers were obtained in moderate yields, with number-average molecular weights on the order of 10³-10⁴ g mol^-1 and relatively narrow dispersities. UV–visible spectra showed the expected aromatic π-π^* absorptions. Photoluminescence measurements in tetrahydrofuran (THF)/H₂O mixtures displayed a nonmonotonic solvent-composition dependence, with emission enhancement at intermediate water fractions followed by quenching in more water-rich mixtures. Dynamic light scattering indicated the presence of light-scattering dispersed aggregates in CHCl₃ under the tested conditions, while scanning electron microscopy revealed hierarchical agglomerates in the dried state, in which submicrometer particulates coalesced into micrometer-scale clusters. Together, these results show that axial stereochemistry and aggregation/packing behavior cooperatively influence radiative and nonradiative decay pathways in chiral multilayer backbones, providing useful design guidance for aggregation-responsive emissive polymer materials.

We report the first Ir(I)-catalyzed enantioselective intramolecular C–H silylation of ferrocenes for the efficient construction of planar-chiral 5- and 6-membered ferrocenyl silacycles. This method overcomes key limitations of existing Rh(I)-based systems, offering superior reactivity, enhanced cost-effectiveness, and broader substrate scope, including challenging C3- and C6-substituted derivatives, as well as excellent enantiocontrol under mild conditions without requiring exogenous H₂ acceptors. The utility of the obtained planar-chiral scaffolds is preliminarily demonstrated through the synthesis of novel monophosphine ligands, which exhibit promising activity in asymmetric catalysis.