Recent advances in catalytic enantioselective construction of silicon-stereogenic silacarbocycles

Recent advances in catalytic enantioselective construction of silicon-stereogenic silacarbocycles | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 28 October 2025 V1 Latest version Share on Recent advances in catalytic enantioselective construction of silicon-stereogenic silacarbocycles Authors : Xiuping Yuan , Kehan Jiao , Jiaqiong Sun , Qian Zhang , and Tao Xiong 0000-0002-2516-084X [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.176163513.35413878/v1 183 views 100 downloads Contents Abstract Supplementary Material Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Silicon-stereogenic silacarbocycles represent a privileged class of organosilicon compounds with broad applications in asymmetric synthesis, functional materials, and medicinal chemistry. This review comprehensively summarizes recent advances in their catalytic enantioselective synthesis, a field address challenges stemming from unique stereoelectronic properties of silicon. We highlight the pivotal role of diverse catalytic systems, from transition metals to organocatalysts, in enabling key strategies such as desymmetrization, kinetic resolution, and dynamic kinetic asymmetric transformation for assembling these chiral frameworks. The discussion critically assesses the current state of the art, identifies persistent limitations, and outlines promising future research directions. Cite this paper: Chin. J. Chem. 2025 , 42 , XXX—XXX. DOI: 10.1002/cjoc.70XXX Recent advances in catalytic enantioselective construction of silicon-stereogenic silacarbocycles Xiuping Yuan, ‡, a Kehan Jiao, ‡, b Jiaqiong Sun,* , a Qian Zhang* , a,c and Tao Xiong* , a a Province Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, 5268 Renmin Street, Changchun 130024, China b School of Environment, Northeast Normal University, Changchun 130117, China c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China. asymmetric catalysis | Si-stereogenic silacarbocycles | organosilicon compounds | organic methodologies Comprehensive Summary Silicon-stereogenic silacarbocycles represent a privileged class of organosilicon compounds with broad applications in asymmetric synthesis, functional materials, and medicinal chemistry. This review comprehensively summarizes recent advances in their catalytic enantioselective synthesis, a field address challenges stemming from unique stereoelectronic properties of silicon. We highlight the pivotal role of diverse catalytic systems, from transition metals to organocatalysts, in enabling key strategies such as desymmetrization, kinetic resolution, and dynamic kinetic asymmetric transformation for assembling these chiral frameworks. The discussion critically assesses the current state of the art, identifies persistent limitations, and outlines promising future research directions. Key Scientists In 2011, Hayashi and Shintani reported a pioneering Pd-catalyzed asymmetric ring expansion of silacyclobutanes with alkynes, enabling the construction of cyclic tetraorganosilicon stereocenters and marking the inception of this field. Subsequently, Takai and coworkers developed a Rh-catalyzed asymmetric synthesis of chiral spirosilabifluorene through sequential Si–H and C–H bond activations. In 2015, Nozaki developed an efficient Rh-catalyzed [2+2+2] cycloaddition for the highly enantioselective synthesis of Si-stereogenic dibenzosiloles. In 2018, Xu and colleagues established a Pt-catalyzed tandem hydrosilylation/cyclization, and in 2022, the same group made further breakthroughs in the Rh-catalyzed dynamic kinetic asymmetric hydrosilylation to access Si-stereogenic benzosiloles. Meanwhile, the Song group developed a Rh-catalyzed ring expansion of silacyclobutanes with alkynes, expanding the methodologies for synthesizing axially chiral spirosilanes. In 2021, He et al. made a important contribution through Rh-catalyzed C–H silylation, enabling the enantioselective synthesis of Si-stereogenic monohydrosilanes and various heterocycles. Concurrently, the group of Wang conducted impressive studies on Rh-catalyzed asymmetric hydrosilylation and established a kinetic resolution strategy for the efficient synthesis of Si-stereogenic cyclic monohydrosilanes. More recently, Zhao reported a base-metal-catalyzed intramolecular ring expansion and an Ir-catalyzed enantioselective C–H silylation for constructing Si-stereogenic silacarbocycles, thereby further broadening the catalyst scope in this area. Numerous other researchers have also made important contributions; however, due to space constraints, a comprehensive acknowledgment of all achievements is not feasible within this review. Contents 1. Introduction 3 2. Pd-catalyzed construction of Si-stereogenic silacarbocycles 3 3. Rh-catalyzed construction of Si-stereogenic silacarbocycles 5 4. Base matal-catalyzed construction of Si-stereogenic silacarbocycles 11 5. Other metal-catalyzed construction of Si-stereogenic silacarbocycles 13 6. Organocatalytic construction of Si-stereogenic silacarbocycles 14 7. Conclusions and Perspectives 14 1. Introduction Si-stereogenic silacarbocycles exhibit significant application potential across various fields, including synthetic chemistry, materials science, and medicinal chemistry [1] (Figure 1A). For instance, they are frequently employed as chiral auxiliaries or probes; SPSiOL (spirosilabiindane diol) can be readily converted into a broad range of chiral ligands; spirobifluorenes have been utilized in organic light-emitting diodes (OLEDs); and (-)-sila-mesembrabol demonstrates enhanced in vivo antidepressant activity compared to the natural (-)-mesembrabol. Although silicon (Si) and carbon (C) belong to the same main group in the periodic table, their chemical behaviors differ substantially at the molecular level due to inherent differences in atomic size (rₛᵢ = 1.17 Å，r c = 0.77 Å) and electronegativity (χₛᵢ=1.8，χ c =2.5) [2] . In contrast to the rapid advancement in the synthesis of C-centered chiral compounds, the catalytic enantioselective construction of Si-stereogenic centers faces substantial synthetic challenges. The main obstacles include (Figure 1B): (1) The longer Si–C bonds typically lead to looser transition states in the chiral induction step, making it difficult to form ordered transition states [3] ; (2) The more diffuse 3p orbitals of Si, compared to carbon’s 2p orbitals, lead to reduced overlap efficiency, thereby resulting in limiting stability of Si–C or Si–heteroatom multiple bonds. Consequently, constructing chiral Si centers via asymmetric addition to Si=X double bonds (where X represents another atom) is not feasible [4] ; (3) The availability of low-lying 3d orbitals on Si atoms facilitates racemization of chiral Si centers via hypercoordinate intermeidates, such as pentacoordinated or hexacoordinated species [5] . Cyclic chiral Si molecules, as a distinct subclass of Si-stereogenic compounds, pose additional synthetic challenges beyond these general difficulties, primarily including: (1) High sensitivity to the steric hindrance imposed bysubstituents on the Si atom during cyclic formation [6] ; (2) Stringent requirements for catalytic system compatibility, necessitating carefully tailored ligands and metal precursors. Significant progress has been made in the construction of Si-stereogenic silacarbocycles over the past decades. The first major advancement was the Pd-catalyzed cyclobutane desymmetrization reaction reported by Shintani and Hayashi in 2011. Around the same time, Takai and colleagues described a Rh-catalyzed desymmetrization of phenylsilanes. In recent years, the groups of Xu and Wang have successfully developed methods for the synthesis of Si-stereogenic silacarbocycles from racemic compounds via dynamic kinetic asymmetric transformation (DYKAT) and kinetic resolution (KR) strategies under rhodium catalysis (Figure 1C). To improve cost-effectiveness, earth-abundant transition metals such as Co, Cu, and Ni have been successfully employed in the enantioselective construction of cyclic chiral Si centers through hydrosilylation of unsaturated hydrocarbons, intramolecular aryl transfer reactions, and intramolecular Si–O coupling. As complementary approaches, environmentally benign organocatalytic systems—including chiral phosphoric acid, imidodiphosphorimidate, enamine, N -heterocyclic carbene (NHC) catalysis—have recently emerged as viable alternatives. Although the synthesis of chiral Si compounds has been well reviewed in several publications [7][1e] , a focused discussion on the construction of specific Si-stereogenic silacarbocycles is still lacking. This review provides a comprehensive overview of major advances in the catalytic enantioselective synthesis of Si-stereogenic silacarbocycles over the past few decades. The content is organized according to catalytic systems (e.g., transition metal catalysis and organocatalysis), and includes detailed discussions on reaction mechanisms, substrate scope, factors influencing stereoselectivity, and subsequent transformations and applications of the resulting products. Figure 1 Applications, comparison of C and Si atoms, and catalytic asymmetric construction of Si-stereogenic silacarbocycles 2. Pd-catalyzed construction of Si-stereogenic silacarbocycles Over the past decades, Pd-catalyzed asymmetric reactions have become a powerful tool for constructing Si-stereogenic silacarbocycles. By leveraging desymmetrization strategies, this approach has enabled precise stereochemical control over Si-containing ring systems. The development of highly enantioselective methodologies has significantly broadened access to structurally diverse chiral silacycles with enhanced synthetic efficiency. Ligands play a crucial role in governing both reactivity and stereoselectivity in these processes. Collectively, these advances have established a robust platform for synthesizing functional chiral cyclic organosilicon molecules and enriched the field of organosilicon chemistry. Silacyclobutanes (SCBs) have emerged as pivotal four-membered synthons in organosilicon chemistry, primarily due to their substantial ring strain which facilitates selective Si–C bond cleavage. The desymmetrizing ring-expansion reactions of prochiral or meso-SCBs represent a powerful and efficient strategy for constructing Si-stereogenic SCBs. By engaging SCBs in transition-metal-catalyzed annulations with unsaturated partners like alkynes, alkenes, or allenoates, this approach enables the direct transformation of simple, symmetric precursors into complex chiral silacycles—often in a single step. In 2011, Hayashi and co-workers reported a Pd-catalyzed intramolecular enantioselective desymmetrization of alkyne-tethered SCBs 1 via ring expansion, affording silacycles 2 bearing tetraorganosilicon stereocenters (Scheme 1, top) [8] . A catalytic cycle involving oxidative addition, alkyne insertion, and reductive elimination was proposed, with ligand bulkiness identified as crucial for stereocontrol. The desymmetrizative oxidative addition step is likely the enantiodetermining step in this transformation. In 2012, the same group extended this methodology to an intermolecular variant using an analogous catalytic system (Scheme 1, bottom) [9] . The reaction between SCBs 3 and electron-deficient alkynes 4 provided Si-stereogenic 1-sila-2-cyclohexenes 5 in high yields and enantioselectivity (up to 92% ee). Mechanistic studies revealed that the pathway diverged from the initial system, proceeding via alkyne coordination (oxidative cyclization), transmetalation (σ-bond metathesis), and reductive elimination, with the enantioselective σ-bond metathesis effectively constructing the Si-stereogenic center. Song and Su groups reported an efficient approach for synthesizing chiral exo-cyclic enoate-substituted silacyclohexenes via Pd-catalyzed asymmetric ring expansion of silacyclobutanes with allenoates, addressing the limited structural diversity of silacycles (Scheme 2). [10] In the presence of Pd(OAc)₂ and a TADDOL-derived ligand L2 , the reaction exhibited excellent regioselectivity and good enantioselectivity. Scheme 1 Pd-catalyzed enantioselective desymmetrization of silacyclobutanes with alkynes toward chiral silacycles. Scheme 2 Pd-catalyzed asymmetric ring expansion of silacyclobutanes with allenoates to chiral silacyclohexenes. The desymmetric insertion of C–metal bonds into Si-containing cyclic olefins also offers a viable route for constructing chiral silacyclic compounds. In 2022, Zhao and Li reported a Pd-catalyzed asymmetric intramolecular Heck cyclization for the enantioselective construction of sila-bicyclo[3.2.1] scaffolds bearing both C- and Si-stereocenters (Scheme 3). [11] This transformation employed a desymmetrizative coupling of prochiral silacyclopentenes with aryl bromides 9 , delivering products in high yields (up to 98%) and excellent enantioselectivities (up to 99% ee) using a chiral ( R p , R )- t Bu-FOXAP ( L3 ) as the ligand. Mechanistic studies revealed that the steric and electronic properties of the ligand govern the enantiodetermining migratory insertion step. Furthermore, the synthetic utility of the products was demonstrated through a series of stereospecific downstream transformations, including reduction, bromination, and epoxidation. Scheme 3 Pd-catalyzed enantioselective intramolecular Heck cyclization for sila-bicyclo scaffolds. The desymmetric activation and intramolecular cyclization of diaryl-substituted prochiral silanes undoubtedly represent a powerful strategy for constructing chiral silacycles. In 2012, Shintani, Hayashi, and co-workers achieved a milestone in this area by reporting a Pd-catalyzed asymmetric synthesis of Si-stereogenic dibenzosiloles 12 via enantioselective intramolecular C–H bond functionalization and arylation of prochiral 2-(arylsilyl)aryl triflates 11 (Scheme 4). [12] Employing a Pd(OAc)₂/Josiphos-type ligand ( L4 ) catalyst system, the reaction achieved excellent chemo- and enantioselectivity (up to 98% ee) under mild conditions, representing the first catalytic asymmetric construction of Si stereocenters through C–H activation. Further demonstrating the versatility of desymmetrization approaches, Hayashi and Nozaki developed in 2017 a Pd-catalyzed asymmetric synthesis of Si-stereogenic dihydrophenazasilines via an enantioselective 1,5-Pd migration (Scheme 5). [13] This transformation constituted the first synthesis of Si-stereogenic compounds via a transition-metal-catalyzed C to C migration. Using a chiral ( R )-Binap derivative ( L5 ), the reaction achieved up to 98% ee under mild conditions with broad substrate scope. Mechanistic studies indicated that enantioselectivity is established during the Pd migration event, while deprotonation/reductive elimination is rate-limiting. Scheme 4 Pd-catalyzed enantioselective C–H arylation for Si-stereogenic dibenzosiloles. More recently, in 2023, Shintani and coworkers reported a Pd-catalyzed intramolecular Hiyama coupling for the synthesis of 4-sila-4H-benzo[ d ][1,3]oxazines (Scheme 6). [6a] The employment of a Josiphos-type chiral ligand ( L6 ) successfully afforded the Si-stereogenic product 16 with good enantioselectivity. Mechanistic investigations proposed a sequence involving: (i) oxidative addition, (ii) intramolecular transmetalation via a pentacoordinate Si species that facilitates chiral inversion, and (iii) reductive elimination to deliver the final product. In summary, Pd-catalyzed desymmetrization of prochiral Si compounds has provided elegant and vital synthetic pathways to chiral silacarbocycles. However, the current synthetic paradigm remains predominantly relay on structurally precise substrates, highlighting an area for future methodological expansion. Scheme 5 Pd-catalyzed asymmetric synthesis of Si-stereogenic dihydrophenazasilines via 1,5-palladium migration. Scheme 6 Pd-catalyzed intramolecular Hiyama coupling to 4-sila-4H-benzod 1,3-oxazines. 3. Rh-catalyzed construction of Si-stereogenic silacarbocycles In addition to Pd-based systems, Rh-catalysis has also been extensively developed for the synthesis of Si-stereogenic silacarbocycles. Rh-catalyzed reactions have grown into a robust platform for enantioselective formation of Si-stereogenic centers. Through strategic use of desymmetrization, kinetic resolution (KR), and dynamic kinetic asymmetric transformation (DYKAT), a variety of chiral organosilicon compounds, including benzosiloles, spirosilacycles, and silaheterocycles, have been conveniently synthesized. Not only do these methods exhibit operational simplicity and broad functional group compatibility, but they also provide critical chiral building blocks that facilitate advances in asymmetric synthesis, optoelectronic materials, and catalytic applications. In 2012, two independent studies significantly advanced the Rh-catalyzed synthesis of Si-stereogenic compounds. Chatani and co-workers reported a Rh-catalyzed coupling between silylphenylboronic acid and internal alkynes, providing access to 2,3-disubstituted benzosilole derivatives (Scheme 7). [14] Notably, employing the chiral ligand ( S,S )-QuinoxP ( L7 ) enabled the formation of Si-chiral benzosilole 19 with high enantioselectivity (98% ee). In the same year, Shintani and Hayashi described a Rh-catalyzed asymmetric synthesis of Si-stereogenic dibenzoxasilines through selective cleavage of one enantiotopic phenyl group on Si (Scheme 8). [15] Using ( S,S )-Me-Duphos ( L8 ) as the chiral ligand, the reaction achieved high enantioselectivities (up to 92% ee). This work introduced a novel ”enantioselective transmetalation” strategy, establishing its feasibility for constructing Si stereocenters. Further mechanistic insight was provided in 2019 by the Lan group, who employed density functional theory (DFT) calculations to elucidate the reaction pathway. [16] Their simulations revealed a four-step mechanism involving: (i) formation of an aryloxorhodium intermediate, (ii) Rh–Si exchange, (iii) oxidative addition, and (iv) reductive elimination, with enantioselectivity controlled by steric differentiation in the reductive elimination transition state. Scheme 7 Rh-catalyzed coupling between 2-trimethylsilylphenylboronic acid and internal alkynes for asymmetric synthesis of 2,3-disubstituted benzosilole Scheme 8 Rh-catalyzed asymmetric synthesis of Si-stereogenic dibenzoxasilines Scheme 9 Rh-catalyzed enantioselective synthesis of Si-stereogenic benzofuranylmethylidene-benzoxasiloles. In 2018, the Tanaka group reported an enantioselective synthesis of Si-stereogenic benzofuranylmethylidene-benzoxasiloles via the desymmetrization of bis(2-ethynylphenol)silanes catalyzed by a cationic Rh(I)/( S )-BINAP ( L9 ) complex (Scheme 9). [17] This transformation proceeds through a cascade of 1,2-Si, 1,3-C migrations and oxacyclization, enabling the construction of the stereogenic Si center with moderate enantioselectivity. Notably, the resulting compounds displayed remarkable fluorescence properties. Specifically, derivatives bearing electron-donating groups (e.g., methoxy, methyl, phenyl) exhibited high fluorescence quantum yields in solution, whereas the trifluoromethyl-substituted derivative, which features an electron-withdrawing group, demonstrated excellent fluorescence in the solid state. Dihydrosilanes serve as versatile building blocks in Si-stereogenic chemistry, leveraging their dual Si–H bonds for sequential functionalization and their inherent prochirality for direct access to chiral Si centers via desymmetrization. The strategic activation of one Si–H bond enables efficient, stereocontrolled construction of diverse silacarbocycles in a single operation. This approach transforms simple symmetric precursors into architecturally complex chiral frameworks with high atom economy, and has emerged as a pivotal method for assembling enantiomerically enriched Si-containing heterocycles, significantly advancing the field of asymmetric organosilicon chemistry. Despite the promising potential of chiral spirosilabiindane frameworks, their highly enantioselective synthesis remained largely underdeveloped. In 2013, Kuninobu, Takai, and co-workers achieved a breakthrough by reporting a Rh-catalyzed asymmetric synthesis of chiral spirosilabifluorene via dehydrogenative silylation of a C–H bond using 2-arylphenylsilanes, forming quaternary Si centers (Scheme 10). [18] Employing chiral phosphine ligand ( R )-BINAP ( L10 ), the reaction afforded high yields (up to 95%) with excellent enantioselectivity (up to 81% ee). A mechanism involving sequential Si–H and C–H bond activations, followed by reductive elimination, was proposed to account for the spirocyclic framework formation. Subsequent advances further expanded the toolbox for Si-stereogenic molecule synthesis. In 2020, the He group developed a Rh-catalyzed tandem enantioselective C–H silylation/alkene hydrosilylation strategy, enabling efficient construction of Si-stereogenic silanes (Scheme 11). [19] This process features SiH 2 -directed enantioselective intramolecular C–H activation followed by stereospecific intermolecular alkene hydrosilylation, delivering products in high yields (up to 95%) with excellent enantiocontrol (up to 99% ee). Mechanistic studies outlined a detailed catalytic cycle: oxidative addition of a Si–H bond to an in situ generated Rh–H species forms intermediate II ; dihydrogen reductive elimination gives silyl–Rh(I) complex III , which undergoes enantioselective C–H activation to afford IV ; reductive elimination forms the C–Si bond and regenerates a Rh–hydride that adds oxidatively to the second Si–H bond, ultimately leading, after alkene insertion and reductive elimination, to the product and catalyst regeneration. The operational simplicity, efficiency, and compatibility with a broad range of functional groups underscore its promise for applications in asymmetric synthesis, medicinal chemistry, and materials science. In 2021, He and co-workers reported a Rh-catalyzed asymmetric dehydrogenative intramolecular C–H silylation for synthesizing Si-stereogenic monohydrosilanes (Scheme 12). [20] Using a chiral Rh–diphosphine catalyst, a range of 1 H -benzosiloles and 1 H -benzosilolometallocenes were obtained with excellent chemo-, regio-, and stereoselectivity. These monohydrosilanes serve as versatile precursors to tetraorganosilanes and exhibit attractive photophysical properties, including bright blue fluorescence and circularly polarized luminescence (CPL). That same year, the group also described a Rh-catalyzed enantioselective synthesis of six- and seven-membered triorgano-substituted Si-stereogenic heterocycles via direct dehydrogenative C–H silylation (Scheme 13). [21] This method delivers diverse Si-centered chiral molecules in good to excellent yields and enantioselectivities (up to 99% ee) under mild conditions, with broad substrate scope—including indole and carbazole derivatives—and scalability to gram quantities without erosion of enantiopurity. The resulting Si-bridged heterocycles display bright blue fluorescence with tunable photophysical behavior and can be further functionalized stereospecifically, highlighting their potential in organic optoelectronics. Concurrently, the group devised a Rh-catalyzed intramolecular C(sp²)–H functionalization strategy for desymmetrizing dihydrosilanes 37 , providing efficient access to chiral monohydrosilanes 38 under mild conditions with excellent yields and enantioselectivity (Scheme 14). [22] This method features broad substrate compatibility, especially for alkyl-substituted Si stereocenters. The proposed mechanism involves the coordination of [Rh(cod)Cl] with ( R )-DTBM-Segphos L15 to generate a Rh(I)–H species, with product formation and catalyst regeneration occurring via two round of oxidative addition–reductive elimination sequences. Scheme 10 Rh-catalyzed asymmetric dehydrogenative silylation to chiral spirosilabifluorenes. Scheme 11 Rh-catalyzed tandem enantioselective C–H silylation/alkene hydrosilylation to Si-stereogenic silanes. Achieving asymmetric coupling between dihydrosilanes and alkyl C–H bonds presents considerable challenges. In 2015, Takai and Murai’s group addressed this by expanding the substrate scope to 2-alkylphenylsilanes, overcoming the inherent difficulties of low reactivity and poor selectivity associated with unactivated C(sp 3 )–H bonds (Scheme 15). [23] They accomplished unactivated C(sp 3 )–H silylation using the chiral phosphine ligand ( R )-H₈-BINAP ( L16 ) to synthesize chiral Si-stereogenic spirocyclic compounds. Notably, 1,1′-spirosilabiindane ( 40 ), which features axial chirality, was obtained via a two-fold dehydrogenative silylation process, although with moderate enantioselectivity (40% ee). Scheme 12 Rh-catalyzed asymmetric dehydrogenative C–H silylation to Si-stereogenic monohydrosilanes. Scheme 13 Rh-catalyzed enantioselective C–H silylation to six- and seven-membered Si-stereogenic heterocycles. In 2020, the He group reported a Rh(I)-catalyzed enantioselective silylation of aliphatic C–H bonds for the synthesis of Si-stereogenic dihydrobenzosiloles (Scheme 16). [24] This transformation involves an intramolecular C(sp³)–H silylation of dihydrosilanes with high enantioselectivity, followed by a stereospecific intermolecular alkene hydrosilylation to afford asymmetrically tetrasubstituted silanes. A wide variety of dihydrosilanes and alkenes bearing diverse functional groups were tolerated, delivering the target compounds in good to excellent yields and enantioselectivities (up to 97% ee). Mechanistic investigations revealed that the stereogenic Si center is established during the initial C–H activation step. In 2021, the same group developed a Rh-catalyzed asymmetric dehydrogenative C(sp 3 )–H silylation strategy for synthesizing Si-stereogenic dihydrodibenzosilines that incorporate both Si-centered and axial chiralities within a six-membered bridged biaryl framework (Scheme 17). [25] This method achieves excellent enantioselectivity (up to 96% ee) and exhibits broad substrate compatibility, accommodating diverse functional groups and substituents on the Si center. Single-crystal X-ray analysis uncovered a novel chirality relay phenomenon from Si-central to axial chirality, attributed to the elongated C–Si bond and steric effects of the tri-ortho-substituted biaryl scaffold. The resulting chiral silanes were further derivatized into functional materials, such as fluorescent pyrene derivatives exhibiting CPL, underscoring their potential in asymmetric catalysis and chiroptical applications. Scheme 14 Rh-catalyzed intramolecular C(sp 2 )–H functionalization of dihydrosilanes to chiral monohydrosilanes. Scheme 15 Rh-catalyzed enantioselective C(sp³)–H silylation to Si-stereogenic spirocycles. Scheme 16 Rh-catalyzed enantioselective aliphatic C–H silylation to dihydrobenzosiloles. The intramolecular hydrosilylation of alkenyl-dihydydrosilanes serves as a robust strategy for constructing enantiomerically enriched Si-stereogenic silacycles. As early as 1996, Tamao reported the first catalytic asymmetric synthesis of C₂-symmetric axially chiral spirosilanes via Rh-catalyzed intramolecular hydrosilylation of a bis(alkenyl)dihydrosilane. [26] Building on this early work, Wang and Li developed chiral spirosilabiindane scaffolds in 2020 through a Rh-catalyzed asymmetric double hydrosilylation, enabling efficient access to Si-centered spirocyclic structures (Scheme 18). [1b] This methodology allowed for the large-scale preparation (over 10 grams) of enantiopure SPSiOL (spirosilabiindane diol), a versatile chiral building block for ligand and catalyst design. Structural analyses revealed that the Si-centered spirocycle possesses a larger dihedral angle and a longer O–O distance compared to its carbon-centered analogues, imparting unique conformational constraints. The utility of SPSiOL [27] was further demonstrated by the synthesis of a series of monodentate phosphoramidite ligands (SPSiPhos), which showed superior performance in Rh-catalyzed hydrogenation and Pd-catalyzed intramolecular carbonamination, affording high enantioselectivities (up to 99.8% ee) and enhanced reactivity under milder conditions. Scheme 17 Rh-catalyzed asymmetric dehydrogenative C(sp³)–H silylation to dihydrodibenzosilines. Shortly thereafter, the Wang group reported a highly efficient Rh-catalyzed intramolecular hydrosilylation for the enantioselective synthesis of Si-stereogenic cyclic monohydrosilanes (Scheme 19). [28] Using a catalytic system comprising [Rh(1,5-hexadiene)Cl] 2 and the chiral ligand ( R )-QuinoxP ( L17 ), this method constructed five- and six-membered silacycles with excellent diastereoselectivity (>98:2 dr), complete regioselectivity, and high enantioselectivity (up to >99% ee). Notable advantages include short reaction times (often 5 minutes), low catalyst loading (0.1 mol%), broad functional group tolerance, and versatility across various Si and aromatic substituents. Mechanistic studies involving deuterium labeling and DFT calculations support a Chalk–Harrod mechanism, with Si–H oxidative addition to rhodium as the enantiodetermining step. In 2023, the Li group described a Rh-catalyzed enantioselective formal [4+1] cyclization between readily available benzyl alcohols 55 and secondary silanes 56 , providing efficient access to Si-stereogenic cyclic silyl ethers 57 (Scheme 20). [29] This transformation exhibits a broad substrate scope and high chemo- and enantioselectivity. Mechanistic studies uncovered a dual role for the Rh–H catalyst: it first mediates an enantiodetermining dehydrogenative O–H silylation to establish a chiral Si–O bond, followed by an intramolecular C–H silylation directed by the remaining Si–H group. Combined experimental and DFT analyses identified Si–O reductive elimination from a Rh(III) intermediate as the stereocontrolling step. Alternatively, in 2015, Nishiyama and Naganawa groups reported a Rh-catalyzed enantioselective desymmetrizing intramolecular hydrosilylation of symmetrically disubstituted hydrosilanes, affording five-membered cyclic organosilanes with chiral Si centers (Scheme 21). [30] A novel axially chiral phenanthroline ligand, ( S )-BinThro L20 , was designed and demonstrated to be highly effective, achieving enantioselectivities of up to 91% ee. It is worth noting that the efficient chiral environment originates from N,N,O -tridentate coordination to the Rh(I) catalyst. Scheme 18 Rh-catalyzed asymmetric double hydrosilylation to Si-centered spirosilabiindanes. Scheme 19 Rh-catalyzed enantioselective intramolecular hydrosilylation to Si-stereogenic cyclic monohydrosilanes. Scheme 20 Rh-catalyzed enantioselective [4+1] cyclization of benzyl alcohols and silanes to Si-stereogenic heterocycles. In 2020, the Xu group developed a highly enantioselective Rh-catalyzed trans-selective hydrosilylation of Si-tethered bisalkynes, enabling the efficient synthesis of Si-stereogenic benzosiloles (Scheme 22). [31] The reaction proceeds under mild conditions using a chiral Ar-BINMOL-Phos ligand ( L21 ), achieving excellent enantioselectivity (up to >99% ee) and broad functional group compatibility. Notably, key additives such as KO t Bu were found to play a critical role in ensuring high stereocontrol. The resulting chiral benzosiloles display aggregation-induced emission (AIE) and circularly polarized luminescence (CPL) activity, underscoring their potential as advanced optoelectronic materials. Mechanistic investigations reveal that the catalytic process is mediated by a mononuclear Rh(I) species. Scheme 21 Rh-catalyzed enantioselective intramolecular hydrosilylation to five-membered Si-stereogenic cyclosilanes. In 2015, Nozaki and Shintani group described the first intermolecular asymmetric synthesis of Si-stereogenic dibenzosiloles through a Rh-catalyzed [2+2+2] cycloaddition of Si-containing prochiral triynes 62 with internal alkynes 63 (Scheme 23, top left). [32] This reaction employs an axially chiral monophosphine ligand L22 , achieving high yields and excellent enantioselectivities. When prochiral dialkynylsilanes 64 of the same type react with isocyanates under identical reaction conditions, regio- and enantioselective synthesis of Si-stereogenic Si-bridged arylpyridinones is enabled (Scheme 23, top right). [33] The reaction demonstrates complete regioselectivity, and mechanistic studies suggest a catalytic cycle involving rapid oxidative cyclization followed by turnover-limiting intramolecular alkyne insertion or reductive elimination. Scheme 22 Rh-catalyzed asymmetric trans-hydrosilylation of Si-tethered bisalkynes to Si-stereogenic benzosiloles. In 2017, the Rh-catalyzed [2+2+2] cycloaddition strategy was employed to achieve Si-centered axially chiral spirocyclic by the same group (Scheme 23, bottom). [34] The Si-containing tetrayne reacted with nitriles and isocyanates, leading to the formation of spirosilacycles 68 via asymmetric cycloaddition. Scheme 23 Rh catalysts asymmetric [2+2+2] cycloaddition reactions for the synthesis of Si-stereogenic chiral cyclosilicon Chiral Rh catalysts have proven highly effective in promoting the desymmetric ring-opening or ring-expansion reactions of SCBs, enabling efficient construction of Si-stereogenic heterocycles. In 2017, the He group reported a Rh-catalyzed asymmetric synthesis of chiral dibenzosiloles bearing quaternary Si centers through a tandem desymmetrization of SCBs and intermolecular dehydrogenative silylation with (hetero)arenes (Scheme 24). [35] Employing ( R )-TMS-Segphos ( L25 ) as the chiral ligand, the reaction achieved high yields (up to 88%) and excellent enantioselectivities (up to 93% ee). Mechanistic studies suggest the transformation proceeds through a stereodetermining SCB opening/intramolecular C–H silylation step, followed by stereospecific intermolecular dehydrogenative coupling. Following this, the Song group reported in 2019 the first Rh-catalyzed intermolecular asymmetric ring-expansion between SCBs 72 and unactivated terminal alkynes 73 , affording silacyclohexenes 74 with high yields and excellent enantioselectivity (Scheme 25, top). [36] Subsequently, Xu and co-workers (2021) further advanced this strategy by developing a Rh/Cu bimetallic system for the asymmetric ring expansion between SCBs and arylpropiolate-type internal alkynes 75 , using the multifunctional Ar-BINMOL-Phos ligand L27 (Scheme 25, middle). [37] This [4+2] annulation achieved high chemoselectivity and moderate-to-good yields of diverse monoester-functionalized 1-sila-2-cyclohexenes 76 , while accommodating various substituents on both SCBs and alkynes. Silaffluorene, the heavier homologue of fluorene, ranks among the most significant silacyclic backbones extensively present in functional materials. Recently, the Song group reported a Rh-catalyzed asymmetric ring expansion of 4/5-spirosilafluorenes 77 with terminal alkynes 73 , enabling the enantioselective synthesis of axially chiral 6/5-spirosilafluorenes 78 (Scheme 25, bottom). [38] This was achieved through the use of a sterically demanding ( R )-binaphthyl phosphoramidite ligand L28 , which facilitated high enantioselectivity. The key to success lies in monosubstitution at the ortho-positions of the prochiral Si center in the silafluorene ring, allowing for effective desymmetrization of the enantiotopic Si–C bonds in the silacyclobutane moiety. The resulting ( S )-configured 6/5-silaspirane framework constitutes a novel and promising scaffold for the development of advanced functional materials. Scheme 24 Rh-catalyzed desymmetrization of SCBs and dehydrogenative silylation with arenes to dibenzosiloles. Scheme 25 Rh-catalyzed enantioselective [4+2] annulation of SCBs with alkynes to silacyclohexenes. Axially chiral spiranes featuring a spiro-Si center—referred to as silaspiranes—serve as a class of highly promising cyclic frameworks, which can be applied to synthesize novel spiro analogs with excellent properties. In 2022, the Song group reported a Rh-catalyzed asymmetric dual ring expansion of spirosilabicyclobutanes 79 with alkynes 73 , enabling the synthesis of axially chiral 6/6-silaspiranes 80 (spirosilabicyclohexenes) with yields of up to 98% and enantioselectivities of up to 98% ee (Scheme 26). [39] This was achieved through the use of a sterically demanding binaphthyl phosphoramidite ligand L29 , which facilitated high enantioselectivity. Additionally, they developed a stepwise process that could be further applied for the construction of hetero-disubstituted spirosilabicyclohexenes from two different alkynes 82 . DFT calculations revealed that migratory insertion (not oxidative addition) is the enantioselectivity-determining step, with the bulky 3,3’-aryl substituents of L29 playing a critical role in stereocontrol. Scheme 26 Rh-catalyzed asymmetric dual ring expansion of spirosilabicyclobutanes with alkynes to silaspiranes. In 2024, Ming and co-workers elucidated an unusual C–Si switch effect during the enantioselective construction of Si-stereogenic centers from silacyclohexadienones (Scheme 27). [40] Both Rh-catalyzed asymmetric conjugate addition (Condition A) and oxidative Heck reactions (Condition B) successfully mediated the desymmetrization of the substrates, thereby affording enantioenriched Si-stereogenic silacycles with high chemo-, diastereo-, and enantioselectivity. DFT calculations revealed that this unexpected C–Si switch originates from silicon’s distinctive stereoelectronic properties, including elongated C–Si bonds, inherent structural distortion, and σ–π conjugation involving its vacant 3d orbitals. In 2024, the Wang group reported a highly efficient Rh-catalyzed kinetic resolution (KR) of racemic monohydrosilanes 87 for the enantioselective construction of Si-stereogenic organosilanes 88 (Scheme 28). [41] By employing ( R,R )-Et-DuPhos L18 as the optimal ligand and [Rh(cod)Cl]₂ as the catalyst, the intramolecular hydrosilylation reaction achieves excellent selectivity factors under mild conditions. Mechanistic investigations suggest that the reaction proceeds via a modified Chalk-Harrod mechanism, which is distinct from those observed in dihydrosilane-based hydrosilylations. This catalytic KR strategy successfully overcomes previous limitations and provides a practical and scalable route to diverse Si-chiral building blocks. The catalytic synthesis of Si-stereogenic silacarbocycles has generally focused on the desymmetrization of prochiral or symmetric substrates. However, strategies involving dynamic kinetic asymmetric transformation (DYKAT) of racemic silanes, which would significantly broaden access to Si-stereogenic molecules, have been underdeveloped, primarily due to the lack of efficient methods for deracemization at the Si center. In 2022, the Xu group reported the first case of dynamic kinetic asymmetric transformation (DYKAT), with excellent enantioselectivities (up to 92% ee) (Scheme 29). [42] This was achieved through the use of a novel non-diastereopure mixed phosphine-phosphoramidite ligand (SiMOS-Phos L31 ), which features axial chirality and multiple stereocenters. DFT calculations reveal a unique mechanism involving ligand-assisted chiral inversion at the Si center, where the amide moiety promotes an S N 2-type substitution of chloride to enable stereochemical interconversion. Scheme 27 C–Si switch in the enantioselective construction of Si-stereogenic silacycles from silacyclohexadienones. Scheme 28 Rh-catalyzed kinetic resolution of racemic monohydrosilanes via intramolecular hydrosilylation. Scheme 29 Rh-catalyzed dynamic kinetic asymmetric hydrosilylation construction of Si-stereogenic benzosiloles. 4. Base matel catalyzed construction of Si-stereogenic silacarbocycles Earth-abundant base metals have emerged as powerful catalysts for constructing Si-stereogenic silacarbocycles, enhancing both economic and synthetic efficiency. These metals promote diverse key transformations—intramolecular aryl transfers, ring-expansion reactions, stepwise hydrosilylations, and Si–O couplings—to afford various valuable scaffolds such as benzooxasiloles, cyclic benzosiloles, and silolanes. Notably, these low-cost catalytic systems are robust and versatile, delivering high enantioselectivity and diastereoselectivity across a broad range of substrates. Scheme 30 Ni(0)-catalyzed enantio- and diastereoselective synthesis of benzoxasiloles. In 2015, Ogoshi reported a Ni(0)-catalyzed intramolecular aryl transfer reaction for synthesizing chiral benzoxasiloles 92 using chiral NHC ligand L32 (Scheme 30). [43] This method simultaneously forms C- and Si-stereogenic centers with excellent enantioselectivity and diastereoselectivity (dr = 99:1) via diastereotopic aryl transfer from prochiral silanes to aldehydes through enantioselective addition. In 2021, the Zhao group developed an Ni(0) catalyzed asymmetric intramolecular ring expansion strategy for synthesizing enantioenriched Si-stereogenic benzosiloles 94 bearing tetraorganosilicon stereocenters (Scheme 31). [44] This method utilizes silacyclobutanes 93 as substrates and employs a Ni(0)/ L33 catalytic system, delivering excellent yields (up to 94%) and high enantioselectivities (up to 99% ee). Additionally, this protocol was successfully extended to construct Si-stereogenic bis-silicon-bridged π-extended systems, which exhibited fluorescence emission, cotton effects, and circularly polarized luminescence (CPL) activity. Three years later, the Xu group conducted DFT calculations on this reaction. [45] Mechanistically, Alkene insertion is rate-determining, and enantioselectivity stems from C−H··· π noncovalent interactions stabilizing the major enantiomer’s transition state. The study guides efficient synthesis of Si-stereogenic compounds. In 2022, the Meng group reported a Co-catalyzed sequential site- and stereoselective hydrosilylation of 1,3-enynes 95 , enabling the synthesis of enantioenriched cyclic alkenylsilanes 97 with simultaneous formation of C- and Si-stereogenic centers (Scheme 32). [46] This transformation proceeds via a cascade process wherein primary silanes initially undergo hydrosilylation of the alkyne moiety, followed by an enantioselective Co−H addition to the 1,1-disubstituted alkene ( IV ), which subsequently undergoes intramolecular diastereoselective metathesis with the prochiral Si−H bond to yield the cyclic alkenylsilane 97 while regenerating the catalyst. The method exhibits broad substrate scope, high efficiency, and excellent selectivity, providing access to a diverse array of chiral building blocks. Mechanistic investigations elucidate key steps, including Ojima-Crabtree isomerization and intramolecular hydrosilylation. Two years later, the Xiong group reported a Cu-catalyzed sequential hydrosilylation of arylmethylenecyclopropanes (MCPs) 98 with primary silanes providing an efficient and practical route to chiral silacyclopentanes bearing consecutive Si- and C-stereogenic centers in high yields (up to 99%) with excellent enantio- and diastereoselectivities (generally 98% ee, >25 :1 dr) (Scheme 33). [47] Mechanistically, the catalytic cycle starts with in situ formation of LCuH catalyst ( I ) from Cu(OAc)₂, silane, and bisphosphine ligand ( R )-DTBM-Segphos L15 . Regioselective insertion of MCP’s C=C bond then generates intermediate II , whose β-alkyl migration produces a Z/E mixture of homoallylcuprate III . III undergoes σ-bond metathesis with aryl silane to release homoallylic silane IV and regenerate LCuH. In subsequent enantioselective intramolecular hydrosilylation, IV reacts with LCuH to form chiral benzyl cuprate V . Finally, intramolecular σ-bond metathesis between Cu-C and H-Si bonds forms silacyclopentane 99 and regenerates LCuH, completing the cycle. Scheme 31 Ni-catalyzed intramolecular ring expansion for enantioselective synthesis of Si-stereogenic cyclic benzosiloles. Scheme 32 Co-catalyzed sequential hydrosilylation of 1,3-enynes synthesis of chiral cyclic alkenylsilanes. Concurrently, the He group reported a related Cu-catalyzed asymmetric cascade hydrosilylation of MCPs with hydrosilanes (Scheme 34). [48] A key distinction was the use of dihydrosilane 100 , expanding the silane scope to afford C-stereogenic silacyclopentanes 101 . When employing primary silanes 96 , the method similarly yielded chiral silacyclopentanes with consecutive Si and C stereocenters 102 . These products proved amenable to stereospecific transformations, enabling diversification. Mechanistic analysis identified a two-step cascade comprising intermolecular hydrosilylation followed by intramolecular cyclization, with the cyclization step governing enantioselectivity. Scheme 33 Cu-catalyzed sequential asymmetric hydrosilylation of MCPs with primary silanes Scheme 34 Cu-catalyzed sequential asymmetric hydrosilylation of MCPs with hydrosilanes 2024, Xu group reported a Cu-catalyzed asymmetric synthesis of Si-stereogenic benzoxasiloles via intramolecular Si–O coupling of [2-(hydroxymethyl)phenyl]silanes (Scheme 35). [49] Cu(I)/difluorphos L36 proved efficient for enantioselective Si–C cleavage and Si–O formation, giving high yields and excellent ee (up to 90% ee). Cu(I)/PyrOx L37 enabled KR of racemic substrates 105 to afford C- and Si-stereogenic products 106 . Mechanistic investigations, including DFT calculations, revealed that the reaction proceeds through a pentacoordinated silicate intermediate, with stereoselectivity being governed by ligand-substrate interactions. Scheme 35 Cu-catalyzed asymmetric synthesis of Si-stereogenic benzoxasiloles via intramolecular si–o coupling. 5. Other matel catalyzed construction of Si-stereogenic silacarbocycles Besides the precious metals Pd, Rh and the base metals Ni, Cu, and Co, there are also sporadic reports on the use of other metals for the synthesis of Si-stereogenic silacarbocycles. Examples of such metals include Pt, Sc, and Ir. Through hydrosilylation, desymmetrization, and C-H silylation, a series of structurally diverse Si-stereogenic silacarbocycles can be obtained, such as six-membered silacyclic compounds, α-trifluoromethyl silacycloheptanones, cyclic siloxanes, and so forth. Scheme 36 Pt-catalyzed hydrosilylation/cyclization of hydroxy-tethered internal alkynes with dihydrosilanes for synthesis of silacycles. In 2018, the Xu group reported a Pt-catalyzed tandem hydrosilylation/cyclization reaction of OH-containing internal alkynes with dihydrosilanes (Scheme 36). [50] This method enabled the efficient synthesis of six-membered silacyclic compounds 109 , including silyloxycycles and cyclic siloxanes, in high yields and good stereoselectivity. Additionally, they explored the enantioselective version of this reaction using chiral diphosphine ligands ( L38 ), achieving modest enantioselectivity with up to 32% ee. Organometallic rare-earth metal complexes are widely recognized for their role as active catalysts in the hydrosilylation of alkenes using primary silanes. In 2018, Hou reported an enantioselective hydrosilylation of alkenes with dihydrosilanes by using a new chiral half-sandwich scandium catalyst (Scheme 37). [51] This transformation is characterized by a wide substrate range, excellent yields, and superior enantioselectivity. Additionally, certain chiral tertiary silane products were further converted into valuable derivatives, including chiral silanols, quaternary silanes, and benzosilole derivatives. Mechanistic studies revealed the high enantioselectivity is induced through s-bond metathesis between a Si–H bond in a prochiral dihydrosilane and a Sc–alkyl bond. Scheme 37 Sc-catalyzed intermolecular alkene hydrosilylation. Scheme 38 Sc-catalyzed asymmetric trifluoromethylation of cyclic ketones for the synthesis of α-trifluoromethyl silacycloheptanones. In 2022, the Wang group reported a Sc(III)/chiral bisoxazoline-catalyzed homologation asymmetric trifluoromethylation of cyclic ketones using 2,2,2-trifluorodiazoethane (CF₃CHN₂, 114 ) as the CF₃ source, affording α-trifluoromethyl silacycloheptanones 115 in moderate to high yields with excellent enantio- and diastereoselectivities (Scheme 38). [52] The reaction accomplishes desymmetrization to form two stereocenters in a single step, enabling enantioselective Csp³–CF₃ bond and Si-stereogenic centers formation. Utilizing this method, a wide range of γ -substituted silacyclohexanones was successfully obtained. In 2021, Zhao and co-workers reported an intramolecular Ir-catalyzed enantioselective C–H silylation of prochiral diarylsilanols, enabling the synthesis of cyclic siloxanes 118 with a chiral Si-stereogenic center (Scheme 39). [53] These compounds could be further transformed into non- C 2-symmetric phenolic silanols (PSiOL), which served as scaffolds for the development of the first ligand featuring both Si- and P-stereocenters. Scheme 39 Ir-catalyzed enantioselective C–H silylation toward chiral Si-stereogenic cyclic siloxanes from prochiral diarylsilanols. 6. Organocatalytic construction of Si-stereogenic silacarbocycles While metal catalysis long served as the primary tool for synthesizing Si-stereogenic organosilicon compounds, metal-free organocatalytic methods have now emerged as a powerful and sustainable alternative, overcoming earlier limitations in catalyst and substrate design. This paradigm shift is marked by the successful application of diverse chiral catalysts, including NHCs, enamine systems, chiral phosphoric acids (CPAs), and confined imidodiphosphorimidates (IDPi). These organocatalysts enable highly enantioselective desymmetrizations to yield functional silacycles—thus serve as valuable, modular platforms for drug modification and complex molecule synthesis. Scheme 40 N-heterocyclic carbene catalyzed desymmetrization for asymmetric synthesis of si-stereogenic silacycles In 2022, the Xu group reports for the organocatalytic desymmetrization strategy for the asymmetric synthesis of Si-stereogenic silacycles using chiral NHC catalysts (Scheme 40). [54] This method successfully realized stereoselective intramolecular benzoin reactions of Si-centered diaromatic aldehydes, yielding enantioenriched dibenzo[ b,f ]silepin-10-ones 120 with well-defined 1,4-C- and Si-stereogenic centers. This approach exhibited a broad substrate scope, delivering products in good yields with moderate to excellent diastereoselectivities and enantioselectivities. In 2022, Yang and Xue employed spirocyclic chiral phosphoric acid (CPA) as an organocatalyst for achieving asymmetric remote enantioselective desymmetrization of 9,9-disubstituted 9,10-dihydroacridines 121 via asymmetric electrophilic aromatic amination with azodicarboxylates 122 (Scheme 41). [55] It yielded diverse chiral dihydroacridines with 9,9-aryl/alkyl or dialkyl substitutions 123 (up to >99% ee). DFT calculations linked CPA’s structure to selectivity, and gram-scale synthesis/derivatizations proved its utility. Scheme 41 Chiral phosphoric acid-catalyzed asymmetric remote desymmetrization to access Si-stereogenic centers. Next year, the Yu group reported a highly enantioselective construction of Si-stereocenters via asymmetric enamine catalysis (Scheme 42). [56] This method involves an intramolecular aldolization of prochiral siladials 124 , leading to the formation of multifunctional Si-stereogenic silacycles 126 with excellent enantioselectivity. By addressing challenges of remote asymmetric induction and potential racemization, this approach provides a versatile platform for the synthesis of diverse Si-stereogenic compounds, including fluoroalkyl-substituted derivatives that are difficult to access through traditional metal-catalyzed methods. Notably, the resulting products feature reactive enal moieties, which facilitate further transformations for applications in drug modification and complex molecule synthesis. Scheme 42 Asymmetric enamine catalysis enabled intramolecular aldolization of prochiral siladials. Scheme 43 Strongly acidic and confined IDPi-catalyzed asymmetric synthesis of Si‑stereogenic silacycles. In 2024, List and co-workers reported an organocatalytic asymmetric synthesis of Si-stereogenic silacycles using a strongly acidic and confined imidodiphosphorimidate (IDPi) catalyst Cat. 5 (Scheme 43). [57] This reaction involves the enantioselective cyclization of bis(methallyl)silanes, achieving excellent enantioselectivities of up to 93% ee. A key discovery was the role of acetic acid as an additive: it promotes the decomposition of these adducts to regenerate free catalyst, thereby enabling efficient catalyst turnover. Mechanistic studies revealed that protonation is formally the enantiodetermining step, but its contribution to enantioselectivity is negligible due to a small energy difference (0.2 kcal/mol) between transition states; the overall high enantioselectivity is further enhanced by subsequent parallel kinetic resolution (PKR). The method exhibits broad substrate compatibility and enables access to biologically relevant Si-stereogenic compounds, addressing a critical gap in synthetic methodologies for Si-centered stereogenicity. 7. Conclusions and Perspectives This review comprehensively summarizes the significant advances in the catalytic enantioselective construction of Si-stereogenic silacarbocycles over the past few decades. By leveraging efficient and powerful methodologies such as transition metal catalysis and organocatalysis, a great deal of chiral Si-stereogenic silacarbocycles featuring diverse and intriguing architectures have been successfully synthesized, primarily through desymmetrization of prochiral Si-containing molecules. Furthermore, strategies enabling simultaneous control of multiple chiral elements with high stereoselectivity have also been well established, facilitating access to structurally more complex compounds. These rapidly developed methods are expected to further stimulate the applications of these chiral silacarbocycles in the territories of synthetic chemistry, medicinal chemistry, and materials science. Despite remarkable progress in this territory, the area remains in its infancy and offers substantial opportunities for further development. For instance, although a wide range of Si-stereogenic silacarbocycles have been synthesized efficiently and concisely with excellent enantioselectivity, the prochiral starting materials typically required tedious synthetical sequences, which immensely compromise the process economy along with considerable chemical waste production. The development of efficient methodologies utilizing readily accessible prochiral substrates thus remains a highly desirable goal in synthetic chemistry. Moreover, most of the precedents in this domain have relied heavily on the transition metal catalysts, particularly precious metals in earlier research. Developing sustainable alternatives—such as base-metal catalysis, organocatalysis, and biocatalysis—for constructing Si-stereogenic silacarbocycles would significantly expand the scope and sustainability of this research area. Besides, the integration of emerging synthetical tools including photocatalysis, electrocatalysis or synergistic catalytic system, is expected to enable novel reaction pathways and open new avenues for innovation in this field. From the perspective of reaction mechanism, the synthetic methods reported to date have mainly focused on the desymmetrization of prochiral compounds; while alternative approaches—such as DYKAT directly using readily available racemic substrates—together with profound understanding of the mechanism, could offer more elegant and efficient strategies for constructing Si-stereogenic silacarbocycles. 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Keywords asymmetric catalysis organic methodologies organosilicon compounds si-stereogenic silacarbocycles Authors Affiliations Xiuping Yuan Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Kehan Jiao Northeast Normal University School of Environment View all articles by this author Jiaqiong Sun Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Qian Zhang Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Tao Xiong 0000-0002-2516-084X [email protected] Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Metrics & Citations Metrics Article Usage 183 views 100 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Xiuping Yuan, Kehan Jiao, Jiaqiong Sun, et al. Recent advances in catalytic enantioselective construction of silicon-stereogenic silacarbocycles. Authorea . 28 October 2025. DOI: https://doi.org/10.22541/au.176163513.35413878/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . 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