Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process

Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process Xinjuan Li, Ao Li, Xiaoyu Tian, Chunna Lv, Weili Shang, Yahao Dong, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6242430/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Designing heterogeneous catalysts to mimic complicated biological processes and exploring methods to precisely modulate their chirality is crucial for asymmetric reactions. In this study, two chiral catalysts were immobilized on the non-helical C-C polymers, achieving amplification and reversible reversal of polymer chirality by altering the copolymer structure and solvent. Additionally, the copolymer undergoes a layered assembly process with solvent changes, resulting in reversible regulation of its superhelical fiber structure (P or M configuration). At high concentrations, it aggregates to form a knitting wool ball-like hyperhelical three-dimensional structure. A strong correlation has been established between the chirality and catalytic selectivity of the catalyst in the decarboxylative Mannich reaction/asymmetric transfer hydrogenation enantioselective cascade reaction. This bimetallic catalyst produces two chiral products in catalytic asymmetric cascade reactions with high catalytic activity and excellent enantioselectivity, achieving the "one stone, two birds" effect. It can be reused 10 times without significant losss of catalytic activity or stereoselectivity. This copolymerization synthesis strategy may contribute to the development of new polymer catalyst with controllable chirality and superhelical structure. Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Physical sciences/Chemistry/Polymer chemistry/Supramolecular polymers Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Homochirality is one of the most prominent characteristics of biomolecules 1 . Biopolymers express their chirality by twisting into single handed helices, such as the alpha helix of proteins and the double helix of DNA 2 . The application of chirality in biological systems, such as L-amino acids and D-sugars, leads to the adoption of ordered helical structures in biomolecules, such as the right-handed helix in proteins and the right-handed double helix in DNA 3 . The high efficiency and stereospecificity of enzyme catalysis depend on the chirality of biomacromolecules 4 . Inspired by the biological spirals, numerous artificial helical polymers have been developed 5-7 . These polymers exhibit significant optical activity due to excessive single-handed helicity 8 . Chiral catalysts immobilzied on helical polymers provide a model system for elucidating the origin of natural chirality and offer a pathway for developing chiral catalysts. The enantioselectivity can be adjusted by modifying the helicity of the polymer 9-23 . However, the regulation of polymer chirality is a challenging task. In addition, current research primarily focuses on immobilizing catalysts on helical polymers to form homochiral polymers, while immobilizing catalysts on non-helical C-C polymers to construct catalysts with controllable chirality remains challenging 9, 22 . Chiral structures can be formed at different length scales, from the molecular level to the hierarchical level 24-49 . Molecules that cannot be superimposed on their mirror image are referred to as having molecular chirality or conformational chirality 35 . With the introduction of symmetric chiral centers, polymer chains exhibit a helical shape due to intramolecular interactions, and the conformation has exclusive chirality (conformational chirality) 40 . The chiral stereocenter can be located on the main chain or side chain. For polymers without inherent chiral centers (achiral polymers), induced conformational chirality can be achieved by binding with chiral dopants, a behavior known as induced circular dichroism (ICD) 32-34 . Due to intermolecular interactions between chiral or achiral polymers and ICD self-assembly, the stacking of helical chains may lead to the formation of single-handed helical superstructures or layered chirality. The transfer of chiral information (chiral evolution) from molecular chirality to hierarchical chirality is crucial for molecular processes in nature, such as communication, replication, and enzyme catalysis, as well as for controlling the functionality and complexity of self-assembled structures 49 . The self-assembly of chiral polymers has become a powerful strategy for constructing chiral nanostructures, and the chirality of nanostructures can be regulated by the polymer structure 31, 34 . Although significant progress has been made in the self-assembly of chiral polymers, the chiral evolution from polymers to nanostructures, as well as the simultaneous observation of both homochirality and chirality, has not been well-defined 2, 39, 48 . The formation mechanism of superhelical chirality is complex, especially for assembly systems containing multiple chiral components 51-53 . Revealing the contribution of each chiral component to superhelical chirality remains a challenge. The use of two chiral catalysts to achieve excellent catalytic results in a one pot multi catalytic reaction has attracted widespread attention 52-58 . Although there have been some studies on the synergistic catalytic mechanism of the two catalysts, the research on the combination mechanism of this dual handed catalyst is not deep enough 52 . In addition, there is a lack of research on the chiral synergy mechanism, assembly, and catalytic mechanism of introducing two different chiral catalysts into polymer structures simultaneously. Inspired by this, we developed a series of polymer-supported chiral catalysts by immobilizing two chiral metal catalysts on a non-helical C-C polymer. The correlation between the chirality and copolymer structure of bimetallic catalysts in different solvents was systematically studied. We found that the copolymer structure significantly impacts chirality. Introducing another chiral structure into the side chain of a chiral polymer results in significant chiral amplification and reversal effects. Compared to block copolymers, random copolymers exhibit more pronounced chiral amplification and reversal effects. By studying assembly in different solvents, a clear correlation between superhelical chirality and solvent polarity was established. Additionally, the concentration of the polymer solution significantly affects the superhelical structures of polymers. A close correlation has been established between the chirality and catalytic selectivity of the cocatalyst in the DMR/ATH cascade reaction. We effectively achieved chiral amplification and reversal of the catalyst by adjusting the copolymer structure and solvent, resulting in two chiral products produced by a single catalyst in a cascade reaction, achieving the "one stone, two birds" effect. Moreover, the catalyst exhibits superior catalytic stability. Results and discussion Synthesis and characterization of chiral copolymers Figure 1 illustrates the synthesis of copolymers through RAFT copolymerization using monomers (1R, 2R) A-Ru and S-B-Cu. The RAFT reagent employed 4-cyanopentanoic acid dithiobenzoate (CPADB), polymerized in DMF at 70 ℃ for 24 h. The ratios of monomer to CPADB and AIBN were 35:3:1, with the mole ratios of the two monomers detailed in Table 1. The polymerization reaction yielded both random and block copolymers with high molar mass (Mn) and low dispersion indices. Supplementary information (SI) provides additional details (Figures S1-11). Size exclusion chromatography (SEC) measurement revealed that the dispersions (Mw/Mn) of bimetallic copolymers was relatively narrow, less than 1.29, indicating a low distribution index. Notably, the copolymer Poly(A-Ru 1 )-r-(B-Cu 0 ), synthesized S-B without Cu complex and A-Ru, exhibited a relatively higher molecular weight distribution index of 2.03. Table. 1 Yield, molecular weight, and molecular weight distribution of each polymer run Monomer mole ratios (S-B-Cu/(1R, 2R)A-Ru) Polymers d Yield b M n a M w /M n a 1 1:2 c Poly(A-Ru 1 )-r-(B-Cu 0 ) e 26.0% 888464 2.03 2 1:2 Poly(A-Ru 1 )-b-(B-Cu 2.2 ) 72.0% 905523 1.21 3 1:2 Poly(A-Ru 1 )-r-(B-Cu 1.5 ) 30.0% 752316 1.04 4 1:3 Poly(A-Ru 1 )-b-(B-Cu 2.6 ) 4.8% 705277 1.21 5 2:1 Poly(A-Ru 1 )-b-(B-Cu 5 ) 61.0% 69049 1.36 6 2.5:1 Poly(A-Ru 1 )-r-(B-Cu 5.6 ) 69.0% 39329 1.15 7 3:1 Poly(A-Ru 1 )-r-(B-Cu 8 ) 42.5% 31513 1.09 8 S-B-Cu Ρ-[Cu-pyox( i Pr)] 82.5% 76618 1.29 9 (1R, 2R) A-Ru Ρ-[V-TsDPEN-Ru] 14.7% 241273 1.07 a The M n and M w/ M n were determined by SEC with equivalent to polystyrene standards. b The isolated yields of the polymerization, c represent monomer (S-B:(1R, 2R)A-Ru 1:2), d represent the ratio of (1R, 2R)A-Ru:S-B-Cu:B in copolymer e represent (1R, 2R)A-Ru:B=1：1.3 in Poly(A-Ru 1 )-r-(B-Cu 0 ). We initially examined the changes in circular dichroism (CD) signals of various copolymers in different solvents. In DMF, the CD signal of the Ru homopolymer at 445 nm differed from the monomer, indicating the chirality of the polymer main chain (Figure S12). Upon copolymerization with another chiral molecule (oxazoline monomer S-B), the CD signal for copolymer Poly(A-Ru 1 )-r-(B-Cu 0 ) at 445 nm significantly enhanced, demonstrating chiral amplification (Figure S13a). This exemplifies the “sergeant-and-soldiers” principle, where a secondary chirality induces amplification of the primary chiral peak signal 56 . We further investigated the effect of adding Cu to oxazoline chiral molecule on the polymer’s chirality. Both block and random copolymers exhibited a gradual decrease in CD signal with increasing Cu chiral content (Figure S13b). However, compared to Ru homopolymers, the CD signal still increases, indicating a chiral amplification effect. Surprisingly, in the random copolymerization Poly(A-Ru 1 )-r-(B-Cu 1.5 ), the CD signal at 445 nm nearly disappeared, and the signal shifted from positive to negative Conton effect. Simultaneously, the oxazoline Cu signal at 290 nm underwent a complete reversal, resulting in a single-configuration copolymer. Further investigations into the chirality of copolymers in non-polar solvent THF revealed less clear correlations (Figure S14). However, upon adding a small amount of water (THF/H 2 O v/v 4:1), the chirality correlation mirrored that in polar solvents (Figure 2a). The random copolymer Poly(A-Ru 1 )-r-(B-Cu 8 ) exhibited a clear CD signal at 438 nm, showing significant chiral amplification compared to Ru chiral homopolymers. A decrease in Cu chiral content reduced the CD signal. Random copolymerization demonstrating a more pronounced amplification effect than block copolymerization (Figure 2b and 2c). The CD variation trend of Poly(A-Ru 1 )-r-(B-Cu 1.5 ) with varying water content was also studied (Figure 2d). As the water ratio increased, the CD signal became negative at a water volume fraction of f=0.14, reaching maximum negativity at f=0.20. Further increases in water content shifted the signal from negative to positive Cotton effect at f=0.67, with maximum positivity at f=0.80, equivalent to the signal strength in THF (Figure 2d). Significant polymer precipitation occurred at f>0.80. These CD results indicated that bimetallic copolymers exhibit signal amplification and inversion in polar solvents. The chiral signal of Ru is transferred to the copolymer main chain, with the two chiral centers establishing a correlation, achieving amplification and inversion of the polymer main chain unpon introducing Cu chirality (Figure 3) 53, 55 . To further elucidate the correlation between chirality and copolymer structure, we studied the CD of blended chiral homopolymers, finding that blending did not establish effective correlation with a weak signal at 438 nm. Even at a 2:1 molar ratio of Cu chiral homopolymer to Ru polymer, the CD signal at 438 nm remained weak, indicating that the structural correlation between chirality and copolymers is crucial (Figure S14). The coexistence of two chiral structures synergistically regulates copolymer chirality, exhibiting amplification and reversal. Transmission electron microscopy (TEM) was used to study polymer assembly in different solvents. In THF/H 2 O v/v 8:1, Poly(A-Ru 1 )-r-(B-Cu 8 ), which exhibited the most significant chiral amplification in bimetallic system can observe a super-helical fiber structure (Figure S15), while other block copolymers assembled into different spherical micelle morphologies (Figure S16). Atomic force microscopy (AFM) revealed that the dominant structure in the super helical fiber of Poly(A-Ru 1 )-r-(B-Cu 8 ) was the P helix, with a small amount of M helix coexisting (Figure 4a). Similarly, Poly(A-Ru 1 )-r-(B-Cu 1.5 ) exhibited a super-helix fiber structure in THF/H 2 O v/v 8:1 (Figure 4b). In THF/H 2 O v/v 4:1, the copolymer Poly(A-Ru 1 )-r-(B-Cu 1.5 ) formed a cross-shaped nanowire assembly structure, with AFM revealing nanowires dominated by M-helice. Interestingly, in THF/H 2 O v/v 1:4, the copolymer’s chirality reversed, forming a helical structure dominated by the P configuration. The molecular chirality and super-helical structure of the copolymer underwent reversible changes with varying water content, consistent with CD results. The copolymer with a positive Cotton signal formed a super-helical structure with P as the dominant configuration. Poly(A-Ru 1 )-r-(B-Cu 1.5 ) formed two types of super-helical structures, predominantly P or M, in different solvents. The M configuration dominated in THF/H 2 O v/v 4:1, while the P configuration dominated in THF/H 2 O v/v 1:4 (Figure 4d and 4e). This fascinating phenomenon of reversible helical structure reversal with water content change has not been previously reported. The chirality of helical structures is influenced by both copolymer structures and solvents. Increasing the concentration of Poly(A-Ru 1 )-r-(B-Cu 1.5 ) in THF/H 2 O v/v 4:1 from 1.54×10 -3 mmol/L to 1.54×10 -2 mmol/L resulted in polymer chain entanglement, forming a knitting wool ball-like structure observed in AFM as an M-shaped helical structure winding into a 3D super-helix (Figure 4f). The phenomenon of forming a super helical 3D structure with increasing concentration was also observed in the assembly of the copolymer Poly(A-Ru 1 )-r-(B-Cu 8 ), except that two types of helices, P and M, coexisted in the structure (Figure 4c). To further elucidate the configuration reversal process of copolymers, 1 H NMR analysis was conducted. The NMR results showed that with a slight increase in water content, the NMR signal in copolymer Poly (A-Ru 1 )-r-(B-Cu 1.5 ) significantly enhanced (Figure S17). The solubility of the copolymer also significantly increased with the addition of a small amount of water in THF. New NMR signals appeared at 5.30-6.20 ppm compared with Poly(A-Ru 1 )-r-(B 1.3 ), indicating possible ligand exchange between ligands and metals 60, 61 . As the water content increases, the peaks of the copolymer at 6.35 ppm and 8.17 ppm shift towards lower fields, and the signal peak of D 2 O also shifts towards lower fields, indicating a significant interaction between the hydrogen of water molecules and chiral ligand groups. Based on these results, we propose that the assembly structure changes of Poly(A-Ru 1 )-r-(B-Cu 1.5 ) follow a layered assembly process (Figure 5). Initially, chiral copolymers form secondary chiral structures containing right-handed helices (P-helicity). As water content increases, loose and twisted copolymer chains lead to left-handed stacking (M-helicity). With further concentration increases, left-handed chains aggregate to form a super-helical 3D yarn ball structure. The TEM results also confirmed the process of forming a 3D yarn ball structure by entanglement of polymer fibers with increasing concentration (Figure S15). Significant increases in water content return the structure to right-handed, possibly due to further twisting and driving of the polymer chains after helix release. At a deeper level, super-helix formation results from two natural combination effects: weak interactions caused by rapid exchange of different functional chiral ligands due to chain mismatches, and hydrogen bonding between water and chiral ligands. This super-helix formation process follows a "chain twist growth" mechanism of bimetallic materials 59 . Lower energy conformations were screened from UFF optimize molecule simulation established conformations for Poly(A-Ru 1 )-r-(B-Cu 1.5 ) consisting of 10 monomer units. Simulation results (Figure 5b) show that the asymmetric arrangement of polymer side chains induces P and M configurations in Poly(A-Ru 1 )-r-(B-Cu 1.5 ). When the copolymer forms a stable P configuration, the chiral side chains are in a loose and stretched state. When the M configuration is formed, the chiral side chains are in a relatively contracted and tightly packed state. This is consistent with the previous CD and AFM results, and water also affects the dissolution and binding state of the polymer side chains, ultimately determining the distortion of the copolymer main chain and forming two different helical structures. Meanwhile, from the simulation results, it can also be seen that, Cu chirality, closer to the polymer main chain than Ru chirality, plays a crucial role in the polymer main chain configuration, following the “sergeant-and-soldiers” principle. Catalytic performance of catalysts in DMR/ATH cascade reaction To further investigate the catalytic advantages of this dual metal catalyst, we applied it to catalyze the DMR/ATH cascade reaction. The reaction was conducted out at -20 ℃ for 5 hours, followed by heating to 60 ℃ for 18 hours. The raw materials were completely converted for all catalysts in THF/H 2 O v/v 8:1 (Table 2, Entry 1-15). The dr value of the catalyst obtained by blending small molecule Cu pyox (iPr) and V-TsDPEN-Ru in a 1:1 ratio was 56:44. Although the ee values of both diastereomers were high (95%/97%), the stereoselectivity was not ideal. In the Ru-Cu copolymerization catalytic system, the random copolymer Poly(A-Ru 1 )-r-(B-Cu 8 ) exhibited superior catalytic performance compared to the monomer, affording (R,R)-1c with a dr value of 97:3 and an ee value of 98%. Poly(A-Ru 1 )-r-(B-Cu 1.5 ) had good ee value (99%/77%), but poorer dr values (43:57) (Table 2, Entry 8). Mixing the two chiral homopolymers in different proportions resulted in complete reaction conversion, with good dr values (98:2 or 99:1), but poor ee values (Table 2, Entry 10-12). Poly(A-Ru 1 )-r-(B-Cu 0 ), with two chiral centers but no metal Cu, had a dr value of 38/62 and ee values of 96%/97% (Table 2, Entry 1), highlighting the importance of Cu in controlling stereoselectivity. These results indicate that Cu synergizes with Ru to control chiral reaction selectivity, with the chiral amplification effect induced by copolymerization enhancing catalyst enantioselectivity. Random copolymerization of bimetallic materials is more advantageous for synergistic catalysis, yielding excellent products. The structural ratio of the two chiral metals in the Ru/Cu bimetallic catalytic system significantly impacts the catalytic reaction, consistent with CD results. Polymers exhibit chiral amplification effects, with the chirality of the polymer backbone playing a crucial role in catalytic reactions. We further investigated the effect of water content changes on catalytic reactions. In Table 2 (Entries 13-15), Poly(A-Ru 1 )-r-(B-Cu 8 ) exhibited good catalytic activity and selectivity in THF/H 2 O v/v 4:1, with a dr value of 99:1 and an ee value of 99%. Poly(A-Ru 1 )-r-(B-Cu 1.5 ) yielded another set of chiral products ((S,S)-1c), with a dr value of 4:96 and an ee value of -92%, consistent with CD results. This indicates that copolymerization can induce different chiral helical structures, catalyzing the generation of different chiral products, which is significant for catalyst design. Liu et al discovered that two products, R, R-1c and S, S-1c, using (R, R)-Cu/PhBox or (S, S)-Cu/PhBox as co catalyst systems, respectively 62 . Here, we can obtain two different chiral products using the same chiral catalyst, which is of great significance for the synthesis of catalysts and asymmetric reactions. We also investigated the catalytic performance of Poly(A-Ru 1 )-r-(B-Cu 8 ) in different solvents (Table S2). Except for no reaction in DMF, Poly(A-Ru 1 )-r-(B-Cu 8 ) achieved an ee value of 99% and a dr value of 99:1 in both methanol and THF. We conducted in-depth research on the catalytic reaction of Poly(A-Ru 1 )-r-(B-Cu 8 ). 10 different reaction substrates were expanded, after 5 hours at -20 ℃ and 18 hours at 60 ℃ in THF/H 2 O v/v 4/1, yielding products in good yields (>80%) with good dr and ee values (Figure 6). We investigated the cyclic performance of Poly(A-Ru 1 )-r-(B-Cu 8 ) in THF/H 2 O v/v 4:1 (Figure 6). The catalyst was recycled and reused 10 times without significant decrease in catalytic activity and selectivity, which can still maintain a separation yield of 82%, a 99:1 dr value, and a 99% ee value after 10 uses, demonstrating excellent catalytic stability. Discussion Mechanism study The catalytic mechanism of chiral copolymers in the DMR/ATH cascade reaction was investigated. As shown in Figure 7, in the first step of transition metal-catalyzed asymmetric decarboxylation Mannich reaction, under the action of HCONH 4 , 3-oxo-3-(p-toluene) propionic acid mainly adopts enol form in the presence of Cu PhBox, transforming into a square planar Cu/(enol)PhBox complex. Due to steric hindrance, Cu chirality on copolymers with different helical configurations (P or M) attacks the enol from above or below the plane, forming Si and Re planes, thereby generating two different chiral cyclic amines based on Cu’s chiral selectivity 62 . In the second step of asymmetric reduction reaction, the intermediate state of benzoxone is stabilized by the CH-p interaction between Ru and the substrate. The diamine ligand’s NH effect, where the oxygen atom on C=O forms a hydrogen bond with NH, facilitates Ru’s collaboration with hydrogen atoms to attack C=O carbon atoms, forming an intermediate complex state that facilitates the formation of highly selective chiral alcohols. The two different homochiral structures of the copolymer result in the first step asymmetric DMR reaction products (I) being R and S configurations, respectively. During the second step of asymmetric ATH reaction, different homochirality resulted in products (II) being R, R, and S, S configuration product respectively 54 . In summary, two different chiral metal catalysts were introduced into the polymer backbone through simple copolymerization. Compared to block copolymers, random copolymers more effectively achieve chiral amplification. For Poly(A-Ru 1 )-r-(B-Cu 1.5 ) in THF, as water content changes, the polymer undergo reversible chiral regulation and obtain two different types of P and M super helix structures. With increasing concentration, Poly(A-Ru 1 )-r-(B-Cu 1.5 ) follow a layered assembly process and aggregate to form a super helical 3D structure. We applied the catalyst to the DMR/ATH cascade reaction, finding that chirality amplification and reversal determine catalytic reaction outcome, efficiently and selectively yielding two chiral products with different configurations. We screened the best catalyst, Poly(A-Ru 1 )-r-(B-Cu 8 ), and conducted substrate expansion and cycling studies. The catalyst showed good ee and dr values across different substrates and maintained excellent catalytic stability after 10 cycles. This work demonstrates the advantages of polymer chiral catalysts, providing a new approach for regulating super-helical structures. Declarations Competing financial interests The authors declare no competing financial interests. Acknowledgement This work was supported by the National Natural Science Foundation of China (No. 52373004) and the National Natural Science Foundation of Henan Province (No. 232300421202). References Blackmond, D. G. The origin of biological homochirality. Cold Spring Harb. Perspect. 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Topological transformation of a metal−organic framework triggered by ligand exchange. Inorg. Chem. 56 , 4576−4583 (2017). Tang, Y. et al. Single-operation decarboxylative mannich reaction/asymmetric transfer hydrogenation cascade process directly accesses 1,3-distereocentered β-sulfonamido alcohols. Adv. Synth. Catal . 364, 994-1001 (2022). Table Table 2 is available in the Supplementary Files section. Scheme Scheme 1 is available in the Supplementary Files section. Additional Declarations There is NO Competing Interest. Supplementary Files SIFINAL.0312doubleblind.docx Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process Table.docx scheme1.png Scheme1. A decarboxylative Mannich reaction/asymmetric transfer hydrogenation enantioselective cascade reaction for the direct preparation of 1,3-distereocentered β-sulfonamido alcohols using chiral copolymer Ru-Cu catalytic systems. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6242430","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":439384494,"identity":"a4ab0e70-d12e-4056-9cf6-a4c3751d6106","order_by":0,"name":"Xinjuan 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08:21:01","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6242430/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6242430/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":80115213,"identity":"fad95487-ed42-494f-8f65-4eb2f64e0ea3","added_by":"auto","created_at":"2025-04-08 06:03:21","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":126170,"visible":true,"origin":"","legend":"\u003cp\u003eCatalysts synthesis.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/8d1baa128d8a99fec1f8b86b.png"},{"id":80115215,"identity":"f5c9d6a3-2a47-48a0-bfd0-b167a572d369","added_by":"auto","created_at":"2025-04-08 06:03:22","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":220420,"visible":true,"origin":"","legend":"\u003cp\u003eCD spectra of various polymers in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1 (a), CD spectra of copolymer Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF with varying water content (b) and the relationship between Cu chirality content and CD signal (at 438 nm) in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1 (c), and trend of CD signal (438 nm) with varying water content (d) CD spectra recorded at 25 ℃, polymer concentration c=1.54*10\u003csup\u003e-3\u003c/sup\u003e mM.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/5e64463a7e526c73de08d571.png"},{"id":80115842,"identity":"9e02025a-e1c6-4518-aaa8-597a5168ae8c","added_by":"auto","created_at":"2025-04-08 06:11:21","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":107244,"visible":true,"origin":"","legend":"\u003cp\u003eChiral relationships of copolymers in polar solvent.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/12279f2ee22caeb49a2cb16b.png"},{"id":80115843,"identity":"295ac872-265e-42b2-bf92-92729040f9d1","added_by":"auto","created_at":"2025-04-08 06:11:22","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":869389,"visible":true,"origin":"","legend":"\u003cp\u003e3 D AFM image of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 8:1 c=1.54*10\u003csup\u003e-3\u003c/sup\u003e mM (a), Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 8:1 c=1.54*10\u003csup\u003e-3\u003c/sup\u003e mM (b), Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO 4:1 v/v c=1.54*10\u003csup\u003e-2\u003c/sup\u003e mM (c), Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO 4:1 v/v c=1.54*10\u003csup\u003e-3\u003c/sup\u003e mM (d), Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO 1:4 v/v c=1.54*10\u003csup\u003e-3\u003c/sup\u003e mM (e), and Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO 4:1 v/v c=1.54*10\u003csup\u003e-2\u003c/sup\u003e mM (TEM image in the upper right corner) (f).\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/3bef77da39c7b335fdecaca7.png"},{"id":80115220,"identity":"fc5d214f-5440-4fd1-8018-7b9ce79888f0","added_by":"auto","created_at":"2025-04-08 06:03:22","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":271467,"visible":true,"origin":"","legend":"\u003cp\u003eRepresentation of the self-assembly pathway leading to different super-helical formation on Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO solvent (a), and UFF optimize molecule simulation of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) (b).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/7351a9000adefc7fad7233ce.png"},{"id":80115218,"identity":"b7479bec-fb85-4f6c-9b47-515818870984","added_by":"auto","created_at":"2025-04-08 06:03:22","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":128350,"visible":true,"origin":"","legend":"\u003cp\u003eScope of the enantioselective of the DMR/ATH cascade reaction in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1catalyzed by\u0026nbsp; Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e), and the results for recycling Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) in the DMR/ATH cascade reaction with 1a and 1b, reaction conditions: 0.0004 mmol of Ru, THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4/1 1.2 mL, 0.04 mmol of amine, 0.06 mmol of acid, S/C=1000, reaction at -20 ℃ for 5 hours, reaction at 60 ℃ for 18 hours.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/f85a607283073002ae08baed.png"},{"id":80115244,"identity":"aa109e56-da50-4fc8-b321-159f354e7ee6","added_by":"auto","created_at":"2025-04-08 06:03:22","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":179669,"visible":true,"origin":"","legend":"\u003cp\u003ePossible mechanism of copolymer catalyzed DMR/ATH cascade reaction\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/05a6e18d6af3a408346a3077.png"},{"id":84286477,"identity":"42da528c-fefc-43de-aca8-5da6e76fa8f7","added_by":"auto","created_at":"2025-06-10 07:48:30","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2510726,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/89ca5785-18c3-407d-a8bc-95ddb804ae73.pdf"},{"id":80115975,"identity":"225b9948-bccb-455e-ae16-5d367c6d52ec","added_by":"auto","created_at":"2025-04-08 06:19:22","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4676972,"visible":true,"origin":"","legend":"Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process","description":"","filename":"SIFINAL.0312doubleblind.docx","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/eb69e4aa092838b7e3ff4f63.docx"},{"id":80115212,"identity":"fcf69f21-311e-4fef-8028-8c0d94873eb1","added_by":"auto","created_at":"2025-04-08 06:03:21","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":29389,"visible":true,"origin":"","legend":"","description":"","filename":"Table.docx","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/f5f0bee5f04abc055bc8604b.docx"},{"id":80115216,"identity":"83b228b3-d0f3-4357-8756-5888fa091eb6","added_by":"auto","created_at":"2025-04-08 06:03:22","extension":"png","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":188787,"visible":true,"origin":"","legend":"\u003cp\u003eScheme1. A decarboxylative Mannich reaction/asymmetric transfer hydrogenation enantioselective cascade reaction for the direct preparation of 1,3-distereocentered β-sulfonamido alcohols using chiral copolymer Ru-Cu catalytic systems.\u003c/p\u003e","description":"","filename":"scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-6242430/v1/25856e984af55561bf69b081.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process","fulltext":[{"header":"Introduction","content":"\u003cp\u003eHomochirality is one of the most prominent characteristics of biomolecules \u003csup\u003e1\u003c/sup\u003e. Biopolymers express their chirality by twisting into single handed helices, such as the alpha helix of proteins and the double helix of DNA \u003csup\u003e2\u003c/sup\u003e. The application of chirality in biological systems, such as L-amino acids and D-sugars, leads to the adoption of ordered helical structures in biomolecules, such as the right-handed helix in proteins and the right-handed double helix in DNA \u003csup\u003e3\u003c/sup\u003e. The high efficiency and stereospecificity of enzyme catalysis depend on the chirality of biomacromolecules \u003csup\u003e4\u003c/sup\u003e. Inspired by the biological spirals, numerous artificial helical polymers have been developed \u003csup\u003e5-7\u003c/sup\u003e. These polymers exhibit significant optical activity due to excessive single-handed helicity\u0026nbsp;\u003csup\u003e8\u003c/sup\u003e.\u0026nbsp;Chiral catalysts immobilzied on helical polymers provide a model system for elucidating the origin of natural chirality and offer a pathway for developing chiral catalysts. The enantioselectivity can be adjusted by\u0026nbsp;modifying\u0026nbsp;the helicity of the polymer\u0026nbsp;\u003csup\u003e9-23\u003c/sup\u003e. However,\u0026nbsp;the regulation of polymer chirality is a challenging task. In addition, current research primarily focuses on immobilizing catalysts on helical polymers to form homochiral polymers, while immobilizing catalysts on\u0026nbsp;non-helical C-C polymers\u0026nbsp;to construct catalysts with controllable chirality remains challenging \u003csup\u003e9, 22\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;Chiral structures can be formed at different length scales, from the molecular level to the hierarchical level \u003csup\u003e24-49\u003c/sup\u003e. Molecules that cannot be superimposed on their mirror image are referred to as having molecular chirality or conformational chirality \u003csup\u003e35\u003c/sup\u003e. With the introduction of symmetric chiral centers, polymer chains exhibit a helical shape due to intramolecular interactions, and the conformation has exclusive chirality (conformational chirality) \u003csup\u003e40\u003c/sup\u003e. The chiral stereocenter can be located on the main chain or side chain. For polymers without inherent chiral centers (achiral polymers), induced conformational chirality can be achieved by binding with chiral dopants, a behavior known as induced circular dichroism (ICD) \u003csup\u003e32-34\u003c/sup\u003e. Due to intermolecular interactions between chiral or achiral polymers and ICD self-assembly, the stacking of helical chains may lead to the formation of single-handed helical superstructures or layered chirality. The transfer of chiral information (chiral evolution) from molecular chirality to hierarchical chirality is crucial for molecular processes in nature, such as communication, replication, and enzyme catalysis, as well as for controlling the functionality and complexity of self-assembled structures \u003csup\u003e49\u003c/sup\u003e. The self-assembly of chiral polymers has become a powerful strategy for constructing chiral nanostructures, and the chirality of nanostructures can be regulated by the polymer structure \u003csup\u003e31, 34\u003c/sup\u003e. Although significant progress has been made in the self-assembly of chiral polymers, the chiral evolution from polymers to nanostructures, as well as the simultaneous observation of both homochirality and chirality, has not been well-defined \u003csup\u003e2, 39, 48\u003c/sup\u003e.\u0026nbsp;The formation mechanism of superhelical chirality is complex, especially for assembly systems containing multiple chiral components \u003csup\u003e51-53\u003c/sup\u003e. Revealing the contribution of each chiral component to superhelical chirality remains a challenge.\u003c/p\u003e\n\u003cp\u003eThe use of two chiral catalysts to achieve excellent catalytic results in a one pot multi catalytic reaction has attracted widespread attention \u003csup\u003e52-58\u003c/sup\u003e. Although there have been some studies on the synergistic catalytic mechanism of the two catalysts, the research on the combination mechanism of this dual handed catalyst is not deep enough \u003csup\u003e52\u003c/sup\u003e. In addition, there is a lack of research on the chiral synergy mechanism, assembly, and catalytic mechanism of introducing two different chiral catalysts into polymer structures simultaneously. Inspired by this, we developed a series of polymer-supported chiral catalysts by immobilizing two chiral metal catalysts on a non-helical C-C polymer. The correlation between the chirality and copolymer structure of bimetallic catalysts in different solvents was systematically studied. We found that the copolymer structure significantly impacts chirality. Introducing another chiral structure into the side chain of a chiral polymer results in significant chiral amplification and reversal effects. Compared to block copolymers, random copolymers exhibit more pronounced chiral amplification and reversal effects. By studying assembly in different solvents, a clear correlation between superhelical chirality and solvent polarity was established. Additionally, the concentration of the polymer solution significantly affects the superhelical structures of polymers. A close correlation has been established between the chirality and catalytic selectivity of the cocatalyst in the DMR/ATH cascade reaction. We effectively achieved chiral amplification and reversal of the catalyst by adjusting the copolymer structure and solvent, resulting in two chiral products produced by a single catalyst in a cascade reaction, achieving the \u0026quot;one stone, two birds\u0026quot; effect. Moreover, the catalyst exhibits superior catalytic stability.\u0026nbsp;\u003c/p\u003e"},{"header":"Results and discussion ","content":"\u003cp\u003e\u003cstrong\u003eSynthesis and characterization of chiral copolymers\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFigure 1 illustrates the synthesis of copolymers through RAFT copolymerization using monomers (1R, 2R) A-Ru and S-B-Cu. The RAFT reagent employed 4-cyanopentanoic acid dithiobenzoate\u0026nbsp;(CPADB), polymerized in DMF at 70 ℃ for 24 h. The ratios of monomer to CPADB and AIBN were 35:3:1, with the mole ratios of the two monomers detailed in Table 1. The polymerization reaction yielded both random and block copolymers with high molar mass (Mn) and low dispersion indices. Supplementary information (SI) provides additional details (Figures S1-11). Size exclusion chromatography (SEC) measurement revealed that the dispersions (Mw/Mn) of bimetallic copolymers was relatively narrow, less than 1.29, indicating a low distribution index. Notably, the copolymer Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e0\u003c/sub\u003e), synthesized S-B without Cu complex and A-Ru, exhibited a relatively higher molecular weight distribution index of 2.03.\u003c/p\u003e\n\u003cp\u003eTable. 1 Yield, molecular weight, and molecular weight distribution of each polymer\u003c/p\u003e\n\u003cdiv align=\"\"\u003e\n \u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" width=\"536\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003erun\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003eMonomer mole ratios (S-B-Cu/(1R, 2R)A-Ru)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003ePolymers\u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003eYield\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e\u003cem\u003eM\u003csub\u003en\u003c/sub\u003e\u003c/em\u003e\u003csup\u003ea\u0026nbsp;\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e\u003cem\u003eM\u003csub\u003ew\u003c/sub\u003e/M\u003csub\u003en\u003c/sub\u003e\u003c/em\u003e\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e\u0026nbsp;1:2 \u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003ePoly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e0\u003c/sub\u003e) \u003csup\u003ee\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e26.0%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e888464\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e2.03\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e1:2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003e\u0026nbsp; Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-b-(B-Cu\u003csub\u003e2.2\u003c/sub\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e72.0%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e905523\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.21\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e1:2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003e\u0026nbsp; Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e30.0%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e752316\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e1:3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003e\u0026nbsp; Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-b-(B-Cu\u003csub\u003e2.6\u003c/sub\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e4.8%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e705277\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.21\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e2:1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003e\u0026nbsp;Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-b-(B-Cu\u003csub\u003e5\u003c/sub\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e61.0%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e69049\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.36\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e2.5:1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003e\u0026nbsp;Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e5.6\u003c/sub\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e69.0%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e39329\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.15\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e3:1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003ePoly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e42.5%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e31513\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.09\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003eS-B-Cu\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003e\u0026Rho;-[Cu-pyox(\u003csup\u003ei\u003c/sup\u003ePr)]\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e82.5%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e76618\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.29\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 41px;\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 143px;\"\u003e\n \u003cp\u003e(1R, 2R) A-Ru\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 171px;\"\u003e\n \u003cp\u003e\u0026Rho;-[V-TsDPEN-Ru]\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e14.7%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 61px;\"\u003e\n \u003cp\u003e241273\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59px;\"\u003e\n \u003cp\u003e1.07\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003e\u003cem\u003e\u003csup\u003ea\u003c/sup\u003e\u003c/em\u003eThe \u003cem\u003eM\u003c/em\u003en and \u003cem\u003eM\u003c/em\u003ew/\u003cem\u003eM\u003c/em\u003en were determined by SEC with equivalent to polystyrene standards. \u003cem\u003e\u003csup\u003eb\u003c/sup\u003e\u003c/em\u003eThe isolated yields of the polymerization, \u003csup\u003ec\u003c/sup\u003erepresent monomer (S-B:(1R, 2R)A-Ru 1:2), \u003cem\u003e\u003csup\u003ed\u003c/sup\u003e\u003c/em\u003erepresent the ratio of (1R, 2R)A-Ru:S-B-Cu:B in copolymer \u003cem\u003e\u003csup\u003ee\u003c/sup\u003e\u003c/em\u003erepresent\u0026nbsp;(1R, 2R)A-Ru:B=1：1.3 in Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e0\u003c/sub\u003e).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eWe initially examined the changes in circular dichroism (CD) signals of various copolymers in different solvents. In DMF, the CD signal of the Ru homopolymer at 445 nm differed from the monomer, indicating the chirality of the polymer main chain (Figure S12). Upon copolymerization with another chiral molecule (oxazoline monomer S-B), the CD signal for copolymer Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e0\u003c/sub\u003e) at 445 nm significantly enhanced, demonstrating chiral amplification (Figure S13a). This exemplifies the \u0026ldquo;sergeant-and-soldiers\u0026rdquo; principle, where a secondary chirality induces amplification of the primary chiral peak signal \u003csup\u003e56\u003c/sup\u003e. We further investigated the effect of adding Cu to oxazoline chiral molecule on the polymer\u0026rsquo;s chirality. Both block and random copolymers exhibited a gradual decrease in CD signal with increasing Cu chiral content (Figure S13b). However, compared to Ru homopolymers, the CD signal still increases, indicating a chiral amplification effect. Surprisingly, in the random copolymerization Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e), the CD signal at 445 nm nearly disappeared, and the signal shifted from positive to negative Conton effect. Simultaneously, the oxazoline Cu signal at 290 nm underwent a complete reversal, resulting in a single-configuration copolymer.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFurther investigations into the chirality of copolymers in non-polar solvent THF revealed less clear correlations (Figure S14). However, upon adding a small amount of water (THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1), the chirality correlation mirrored that in polar solvents (Figure 2a). The random copolymer Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) exhibited a clear CD signal at 438 nm, showing significant chiral amplification compared to Ru chiral homopolymers. A decrease in Cu chiral content reduced the CD signal. Random copolymerization demonstrating a more pronounced amplification effect than block copolymerization (Figure 2b and 2c). The CD variation trend of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) with varying water content was also studied (Figure 2d). As the water ratio increased, the CD signal became negative at a water volume fraction of f=0.14, reaching maximum negativity at f=0.20. Further increases in water content shifted the signal from negative to positive Cotton effect at f=0.67, with maximum positivity at f=0.80, equivalent to the signal strength in THF (Figure 2d). Significant polymer precipitation occurred at f\u0026gt;0.80. These CD results indicated that bimetallic copolymers exhibit signal amplification and inversion in polar solvents. The chiral signal of Ru is transferred to the copolymer main chain, with the two chiral centers establishing a correlation, achieving amplification and inversion of the polymer main chain unpon introducing Cu chirality (Figure 3) \u003csup\u003e53, 55\u003c/sup\u003e. To further elucidate the correlation between chirality and copolymer structure, we studied the CD of blended chiral \u0026nbsp; homopolymers, finding that blending did not establish effective correlation with a weak signal at 438 nm. Even at a 2:1 molar ratio of Cu chiral homopolymer to Ru polymer, the CD signal at 438 nm remained weak, indicating that the structural correlation between chirality and copolymers is crucial (Figure S14). The coexistence of two chiral structures synergistically regulates copolymer chirality, exhibiting amplification and reversal.\u003c/p\u003e\n\u003cp\u003eTransmission electron microscopy (TEM) was used to study polymer assembly in different solvents. In THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 8:1, Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e), which exhibited the most significant chiral amplification in bimetallic system can observe a super-helical fiber structure (Figure S15), while other block copolymers assembled into different spherical micelle morphologies (Figure S16). Atomic force microscopy (AFM) revealed that the dominant structure in the super helical fiber of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) was the P helix, with a small amount of M helix coexisting (Figure 4a). Similarly, Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) exhibited a super-helix fiber structure in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 8:1 (Figure 4b). In THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1, the copolymer Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) formed a cross-shaped nanowire assembly structure, with AFM revealing nanowires dominated by M-helice. Interestingly, in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 1:4, the copolymer\u0026rsquo;s chirality reversed, forming a helical structure dominated by the P configuration. The molecular chirality and super-helical structure of the copolymer underwent reversible changes with varying water content, consistent with CD results. The copolymer with a positive Cotton signal formed a super-helical structure with P as the dominant configuration. Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) formed two types of super-helical structures, predominantly P or M, in different solvents. The M configuration dominated in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1, while the P configuration dominated in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 1:4 (Figure 4d and 4e). This fascinating phenomenon of reversible helical structure reversal with water content change has not been previously reported. The chirality of helical structures is influenced by both copolymer structures and solvents. Increasing the concentration of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1 from 1.54\u0026times;10\u003csup\u003e-3\u003c/sup\u003e mmol/L to 1.54\u0026times;10\u003csup\u003e-2\u0026nbsp;\u003c/sup\u003emmol/L resulted in polymer chain entanglement, forming a knitting wool ball-like structure observed in AFM as an M-shaped helical structure winding into a 3D super-helix (Figure 4f). The phenomenon of forming a super helical 3D structure with increasing concentration was also observed in the assembly of the copolymer Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e), except that two types of helices, P and M, coexisted in the structure (Figure 4c).\u003c/p\u003e\n\u003cp\u003eTo further elucidate the configuration reversal process of copolymers, \u003csup\u003e1\u003c/sup\u003eH NMR analysis was conducted. The NMR results showed that with a slight increase in water content, the NMR signal in copolymer Poly (A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) significantly enhanced (Figure S17). The solubility of the copolymer also significantly increased with the addition of a small amount of water in THF. New NMR signals appeared at 5.30-6.20 ppm compared with Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B\u003csub\u003e1.3\u003c/sub\u003e), indicating possible ligand exchange between ligands and metals \u003csup\u003e60, 61\u003c/sup\u003e. As the water content increases, the peaks of the copolymer at 6.35 ppm and 8.17 ppm shift towards lower fields, and the signal peak of D\u003csub\u003e2\u003c/sub\u003eO also shifts towards lower fields, indicating a significant interaction between the hydrogen of water molecules and chiral ligand groups.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eBased on these results, we propose that the assembly structure changes of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) follow a layered assembly process (Figure 5). Initially, chiral copolymers form secondary chiral structures containing right-handed helices (P-helicity). As water content increases, loose and twisted copolymer chains lead to left-handed stacking (M-helicity). With further concentration increases, left-handed chains aggregate to form a super-helical 3D yarn ball structure. The TEM results also confirmed the process of forming a 3D yarn ball structure by entanglement of polymer fibers with increasing concentration (Figure S15). Significant increases in water content return the structure to right-handed, possibly due to further twisting and driving of the polymer chains after helix release. At a deeper level, super-helix formation results from two natural combination effects: weak interactions caused by rapid exchange of different functional chiral ligands due to chain mismatches, and hydrogen bonding between water and chiral ligands. This super-helix formation process follows a \u0026quot;chain twist growth\u0026quot; mechanism of bimetallic materials \u003csup\u003e59\u003c/sup\u003e. Lower energy conformations were screened from UFF optimize molecule simulation established conformations for Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) consisting of 10 monomer units. Simulation results (Figure 5b) show that the asymmetric arrangement of polymer side chains induces P and M configurations in Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e). When the copolymer forms a stable P configuration, the chiral side chains are in a loose and stretched state. When the M configuration is formed, the chiral side chains are in a relatively contracted and tightly packed state. This is consistent with the previous CD and AFM results, and water also affects the dissolution and binding state of the polymer side chains, ultimately determining the distortion of the copolymer main chain and forming two different helical structures. Meanwhile, from the simulation results, it can also be seen that, Cu chirality, closer to the polymer main chain than Ru chirality, plays a crucial role in the polymer main chain configuration, following the \u0026ldquo;sergeant-and-soldiers\u0026rdquo; principle.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCatalytic performance of\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ecatalysts in DMR/ATH cascade reaction\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo further investigate the catalytic advantages of this dual metal catalyst, we applied it to catalyze the DMR/ATH cascade reaction. The reaction was conducted out at -20 ℃ for 5 hours, followed by heating to 60 ℃ for 18 hours. The raw materials were completely converted for all catalysts in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 8:1 (Table 2, Entry 1-15). The dr value of the catalyst obtained by blending small molecule Cu pyox (iPr) and V-TsDPEN-Ru in a 1:1 ratio was 56:44. Although the ee values of both diastereomers were high (95%/97%), the stereoselectivity was not ideal. In the Ru-Cu copolymerization catalytic system, the random copolymer Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) exhibited superior catalytic performance compared to the monomer, affording (R,R)-1c\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003ewith a dr value of 97:3 and an ee value of 98%. Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) had good ee value (99%/77%), but poorer dr values (43:57) (Table 2, Entry 8). Mixing the two chiral homopolymers in different proportions resulted in complete reaction conversion, with good dr values (98:2 or 99:1), but poor ee values (Table 2, Entry 10-12). Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e0\u003c/sub\u003e), with two chiral centers but no metal Cu, had a dr value of 38/62 and ee values of 96%/97% (Table 2, Entry 1), highlighting the importance of Cu in controlling stereoselectivity. These results indicate that Cu synergizes with Ru to control chiral reaction selectivity, with the chiral amplification effect induced by copolymerization enhancing catalyst enantioselectivity. Random copolymerization of bimetallic materials is more advantageous for synergistic catalysis, yielding excellent products. The structural ratio of the two chiral metals in the Ru/Cu bimetallic catalytic system significantly impacts the catalytic reaction, consistent with CD results. Polymers exhibit chiral amplification effects, with the chirality of the polymer backbone playing a crucial role in catalytic reactions.\u003c/p\u003e\n\u003cp\u003eWe further investigated the effect of water content changes on catalytic reactions. In Table 2 (Entries 13-15), Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) exhibited good catalytic activity and selectivity in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1, with a dr value of 99:1 and an ee value of 99%. Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) yielded another set of chiral products ((S,S)-1c), with a dr value of 4:96 and an ee value of -92%, consistent with CD results. This indicates that copolymerization can induce different chiral helical structures, catalyzing the generation of different chiral products, which is significant for catalyst design. Liu et al discovered that two products, R, R-1c and S, S-1c, using (R, R)-Cu/PhBox or (S, S)-Cu/PhBox as co catalyst systems, respectively \u003csup\u003e62\u003c/sup\u003e. Here, we can obtain two different chiral products using the same chiral catalyst, which is of great significance for the synthesis of catalysts and asymmetric reactions. We also investigated the catalytic performance of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) in different solvents (Table S2). Except for no reaction in DMF, Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) achieved an ee value of 99% and a dr value of 99:1 in both methanol and THF.\u003c/p\u003e\n\u003cp\u003eWe conducted in-depth research on the catalytic reaction of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e). 10 different reaction substrates were expanded, after 5 hours at -20 ℃ and 18 hours at 60 ℃ in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4/1, yielding products in good yields (\u0026gt;80%) with good dr and ee values (Figure 6). We investigated the cyclic performance of Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e) in THF/H\u003csub\u003e2\u003c/sub\u003eO v/v 4:1 (Figure 6). The catalyst was recycled and reused 10 times without significant decrease in catalytic activity and selectivity, which can still maintain a separation yield of 82%, a 99:1 dr value, and a 99% ee value after 10 uses, demonstrating excellent catalytic stability.\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003e\u003cstrong\u003eMechanism study\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe catalytic mechanism of chiral copolymers in the DMR/ATH cascade reaction was investigated. As shown in Figure 7, in the first step of transition metal-catalyzed asymmetric decarboxylation Mannich reaction, under the action of HCONH\u003csub\u003e4\u003c/sub\u003e, 3-oxo-3-(p-toluene) propionic acid mainly adopts enol form in the presence of Cu PhBox, transforming into a square planar Cu/(enol)PhBox complex. Due to steric hindrance, Cu chirality on copolymers with different helical configurations (P or M) attacks the enol from above or below the plane, forming Si and Re planes, thereby generating two different chiral cyclic amines based on Cu\u0026rsquo;s chiral selectivity \u003csup\u003e62\u003c/sup\u003e. In the second step of asymmetric reduction reaction, the intermediate state of benzoxone is stabilized by the CH-p interaction between Ru and the substrate. The diamine ligand\u0026rsquo;s NH effect, where the oxygen atom on C=O forms a hydrogen bond with NH, facilitates Ru\u0026rsquo;s collaboration with hydrogen atoms to attack C=O carbon atoms, forming an intermediate complex state that facilitates the formation of highly selective chiral alcohols. The two different homochiral structures of the copolymer result in the first step asymmetric DMR reaction products (I) being R and S configurations, respectively. During the second step of asymmetric ATH reaction, different homochirality resulted in products (II) being R, R, and S, S configuration product respectively \u003csup\u003e54\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eIn \u0026nbsp;summary, two different chiral metal catalysts were introduced into the polymer backbone through simple copolymerization. Compared to block copolymers, random copolymers more effectively achieve chiral amplification. For Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) in THF, as water content changes, the polymer undergo reversible chiral regulation and obtain two different types of P and M super helix structures. With increasing concentration, Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e1.5\u003c/sub\u003e) follow a layered assembly process and aggregate to form a super helical 3D structure. We applied the catalyst to the DMR/ATH cascade reaction, finding that chirality amplification and reversal determine catalytic reaction outcome, efficiently and selectively yielding two chiral products with different configurations. We screened the best catalyst, Poly(A-Ru\u003csub\u003e1\u003c/sub\u003e)-r-(B-Cu\u003csub\u003e8\u003c/sub\u003e), and conducted substrate expansion and cycling studies. The catalyst showed good ee and dr values across different substrates and maintained excellent catalytic stability after 10 cycles. This work demonstrates the advantages of polymer chiral catalysts, providing a new approach for regulating super-helical structures.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCompeting financial interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing financial interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the National Natural Science Foundation of China (No. 52373004) and the National Natural Science Foundation of Henan Province (No. 232300421202).\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eBlackmond, D. G. The origin of biological homochirality.\u003cem\u003e\u0026nbsp;Cold Spring Harb. Perspect. Biol.\u003c/em\u003e\u003cstrong\u003e2,\u003c/strong\u003e a002147 (2010).\u003c/li\u003e\n \u003cli\u003eWen, T., Wang, H.-F., Li, M.-C. \u0026amp; Ho, R.-M. 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Catal\u003c/em\u003e. \u003cstrong\u003e364,\u003c/strong\u003e 994-1001 (2022).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Table","content":"\u003cp\u003eTable 2 is available in the Supplementary Files section.\u003c/p\u003e"},{"header":"Scheme","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6242430/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6242430/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eDesigning heterogeneous catalysts to mimic complicated biological processes and exploring methods to precisely modulate their chirality is crucial for asymmetric reactions. In this study, two chiral catalysts were immobilized on the non-helical C-C polymers, achieving amplification and reversible reversal of polymer chirality by altering the copolymer structure and solvent. Additionally, the copolymer undergoes a layered assembly process with solvent changes, resulting in reversible regulation of its superhelical fiber structure (P or M configuration). At high concentrations, it aggregates to form a knitting wool ball-like hyperhelical three-dimensional structure. A strong correlation has been established between the chirality and catalytic selectivity of the catalyst in the decarboxylative Mannich reaction/asymmetric transfer hydrogenation enantioselective cascade reaction. This bimetallic catalyst produces two chiral products in catalytic asymmetric cascade reactions with high catalytic activity and excellent enantioselectivity, achieving the \"one stone, two birds\" effect. It can be reused 10 times without significant losss of catalytic activity or stereoselectivity. This copolymerization synthesis strategy may contribute to the development of new polymer catalyst with controllable chirality and superhelical structure.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e","manuscriptTitle":"Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-04-08 06:03:17","doi":"10.21203/rs.3.rs-6242430/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"9568c591-7d28-4d93-ba1c-a3c779113395","owner":[],"postedDate":"April 8th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":46774179,"name":"Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis"},{"id":46774180,"name":"Physical sciences/Chemistry/Polymer chemistry/Supramolecular polymers"}],"tags":[],"updatedAt":"2025-06-10T07:40:22+00:00","versionOfRecord":[],"versionCreatedAt":"2025-04-08 06:03:17","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6242430","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6242430","identity":"rs-6242430","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}