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.

An organocatalytic asymmetric multicomponent tandem cycloaddition has been established for the construction of C–N axially chiral 5-pyrazolyl indole frameworks, which represent a novel class of five-five-membered indole scaffolds. Utilizing 5-aminopyrazoles, cyclohexanediones, and 2,3-diketoester precursors, this methodology constructs the indole ring de novo in a single step, demonstrating high atom- and step-economy with water as the exclusive byproduct. The protocol enabled the efficient and high-enantioselective synthesis of structurally diverse C–N axially chiral 5-pyrazolyl indoles. This achievement not only introduces a new member to the family of axially chiral pyrazolyl indoles but also provides an efficient and novel strategy for their construction.

We report a highly enantioselective N-heterocyclic carbene (NHC)/copper-catalyzed intermolecular dearomative cyclopropanation of indoles with diazo esters. This protocol enables the efficient construction of cyclopropane-fused indolines featuring quaternary stereogenic centers under mild conditions. A broad range of substituted indoles and diazo esters is tolerated, delivering the corresponding products in high yields with enantioselectivities of up to 90% ee. Notably, the employment of a bulky chiral NHC ligand is crucial for achieving effective stereocontrol over the challenging quasi-linear copper–carbenoid intermediate. Furthermore, gram-scale reactions and downstream transformations demonstrate the synthetic utility of this methodology. Mechanistic investigations, including kinetic isotope effect and Hammett studies, support a reaction pathway involving nucleophilic attack of the indole on a copper–carbenoid species. This earth-abundant copper catalytic system serves as a sustainable alternative to traditional noble-metal-based asymmetric carbene-transfer reactions.

A Pd(II)-catalyzed C–H olefination strategy has been established for the enantioselective synthesis of [n]metacyclophanes. The method demonstrates excellent functional group tolerance across a series of olefins and metacyclophane precursors with varying ansa-chain lengths, achieving high stereocontrol through kinetic or dynamic kinetic resolution. Racemization experiments were conducted to investigate the relationship between molecular structure and conformational stability. Furthermore, the synthetic utility of this approach was demonstrated through gram-scale synthesis and the application of a resulting bifunctional thiourea catalyst in asymmetric Michael additions, highlighting its potential in asymmetric synthesis.

The asymmetric construction of nitrogen stereocenters is notoriously difficult due to rapid nitrogen inversion. Zhang and co-workers now showcase a Pd-catalyzed enantioselective C-H activation strategy that turns this inversion into an advantage, delivering stable chiral azepines with high enantioselectivity. Coincidentally, almost at the same time, Shi and co-workers reported a similar C-H alkylation reaction. Beyond methodology, the products serve as promising scaffolds for asymmetric catalysis and chiroptical materials, bridging synthesis and function. This Perspective discusses how their works not only provide a powerful synthetic method but also open a new avenue for constructing heteroatom stereocenters by harnessing, rather than suppressing, molecular dynamics. Here, nitrogen inversion is deliberately exploited as a dynamic feature that enables enantioselective C-H functionalization, rather than being suppressed as a stereochemical liability.

P-Stereogenic centers are important structural motifs prevalent in natural products, bioactive molecules, and high-performance ligands. Their presence confers significant value across medicinal chemistry, materials science, and asymmetric catalysis. In recent years, catalytic asymmetric hydrophosphination has emerged as a powerful and efficient strategy for constructing such P-stereogenic compounds. Distinguished by high atom economy, broad substrate compatibility, and excellent stereocontrol under mild conditions, these transformations align closely with the principles of sustainable and green synthesis. This review summarizes recent advances in the catalytic asymmetric hydrophosphination of unsaturated C–C bonds for the synthesis of P-stereogenic centers. It covers substrates including alkenes bearing electron-withdrawing groups, alkynes, as well as specialized systems such as enynes, allenes, and conjugated dienes. Emphasis is placed on the design of catalytic systems, encompassing transition-metal catalysts (e.g., Pd, Ni, Cu, Co, Mn) and organocatalysts, along with their mechanisms. Current challenges, such as the low reactivity of unactivated or sterically hindered substrates and difficulties in achieving stereochemical differentiation between phosphorus substituents, are also discussed. This review aims to provide a reference for further innovation and methodological development in the synthesis of P-stereogenic molecules.

Chiral organogermanes hold great potential as bioisosteres in medicinal chemistry and functional materials, yet their development has long been hindered by a scarcity of efficient synthetic strategies. This review offers a comprehensive overview of recent advances in the catalytic asymmetric synthesis of chiral organogermanes, highlighting a shift from traditional resolution methods toward asymmetric catalytic approaches. The content is organized into three main categories: (i) synthesis of C-stereogenic germanes, (ii) synthesis of Ge-stereogenic germanes, and (iii) synthesis of other chiral germanes, including planar, inherent, and axially chiral types. Key synthetic methodologies are systematically examined, such as enantioselective alkene hydrofunctionalization, carbene insertion, coupling reactions, and [2+2+2] cycloaddition, utilizing a variety of catalytic systems ranging from transition metals (Rh, Cu, Ni, Co) and Lewis acids to engineered metalloenzymes. Particular emphasis is placed on the mechanistic insights and ligand design principles that enable stereochemical control in these transformations. We hope this review will inspire chemists working in related areas and contribute to the future advancement of this field.

Developing mild and sustainable strategies for the synthesis of complex molecules is a pivotal yet challenging goal in modern synthesis. While cobalt catalysis offers a sustainable alternative to noble metals, achieving such transformations at room temperature remains elusive. Herein, we report a cobalt-catalyzed aerobic oxidative asymmetric formal cycloaddition involving C(sp²)–H bond activation of benzamides with unactivated alkynes at room temperature using air as the oxidant. For challenging low-activity substrates, reaction efficiency is enhanced via a photoinduced catalytic cycle. Mechanistic and substrate scope studies indicate that substrate reactivity is influenced by electronic and steric effects.

Asymmetric hydrogenation is an efficient tool for rapid synthesis of a diverse range of chiral compounds with high yields and excellent enantioselectivities. Chiral 2-methyl-1,2,3,4-tetrahydro-quinoline is a valuable building block for organic synthesis and has been widely used in the synthesis of bioactive molecules and chiral ligands. Herein, we report an improved iridium-catalyzed asymmetric hydrogenation of 2-methylquinoline on a hundred-gram scale for efficient synthesis of chiral 2-methyl-1,2,3,4-tetrahydroquinoline with up to 91.4% ee value and an 80,000 turnover number. Optically pure 2-methyl-1,2,3,4-tetrahydroquinoline could be obtained in high yields through recrystallization or chemical resolution with the tartaric acid derivative (L)-DMTA.

Cholesteric liquid crystal polymer network (CLCN) patterns composed of oppositely handed helical structures are attractive for anti-counterfeiting. Different areas can be observed under the circularly polarized light with opposite handedness. However, achieving precise control over the reflection band wavelengths of CLCN patterns using photochromic cholesteric liquid crystals (CLCs) remains a significant challenge. Herein, we synthesized a chiral cyanostilbene derivative that demonstrated significant modulation of its helical twisting power upon 365 nm ultraviolet (UV) irradiation. When incorporated into CLC mixtures, this additive enabled precise control over both the handedness and reflection wavelength of the resulting CLCN patterns within seconds under UV exposure. The system allowed for the preparation of colorful CLCN patterns through in-situ photopolymerization. These findings demonstrate that the developed CLC mixtures are well-suited for high-throughput fabrication of CLCN patterns on industrial coating lines.

O-Silylated hemiaminals are utilized as elegant imine precursors in the formal asymmetric [4+2] annulation of indoles for the first time, wherein chiral phosphoric acid (CPA) acts (1) as a Brønsted acid catalyst to facilitate methanimine formation under mild conditions and then (2) as an anion-binding catalyst for dearomative annulation. This methodology exhibits a broad substrate scope with remarkable functional group tolerance and enantioselectivity (up to 97% yield and 99% ee), providing straightforward access to the challenging indoline-fused tetrahydroquinolines bearing multiple stereogenic centers. Mechanistic studies reveal the critical role of PhNHCO- groups in enhancing both reactivity and enantioselectivity, probably due to non-covalent interactions with CPA. The kinetic isotope effects experiment and negative linear Hammett correlation suggest a concerted process.

Transition metal-catalyzed asymmetric C–H activation is vital for chiral molecule synthesis but faces challenges in remote C–H functionalization due to traditional metallacycle constraints and difficulties in long-range chiral recognition. This review summarizes three core strategies to address these issues: template-assisted chiral ligand control, norbornene-mediated palladium catalysis, and bifunctional catalyst control. These strategies achieve high enantioselectivity for diverse chiral architectures. Future directions include expanding to para-C–H bonds of arenes and aliphatic C–H bonds, developing robust chiral mediators/ligands, and applying the methodology to natural products and complex materials.

The synthesis of biaryl axially chiral amides and their derivatives—compounds that have shown promise as additives or catalysts in asymmetric catalysis—has traditionally relied on transition-metal catalysts. Herein, we report an NHC-catalyzed organocatalytic atropoenantioselective amidation between axially prochiral biaryl dialdehydes and amides that efficiently affords axially chiral imides. This method operates under metal-free and mild conditions, exhibits broad functional group tolerance and substrate scope, and delivers products with excellent enantioselectivities. Furthermore, a wide variety of axially chiral imides, amides, and related derivatives can be accessed through enantio-retentive transformations, offering a versatile and attractive strategy for their synthesis.