This study reports a methodology of leveraging highly accessible relative X-ray diffraction peak intensities for the fast identification of reactive facets of polycrystalline catalysts. Specifically, taking polycrystalline α-Fe2O3 as an example, we demonstrate that the ambient-condition X-ray diffraction intensity ratio of (110) to (104) facets (denoted as I(110)/I(104)) of α-Fe2O3 exhibits a strong linear correlation (R2 ≈ 0.9) with catalytic rates across diverse temperatures and flow conditions for methane oxidation. Both linear and nonlinear statistical validations via Pearson correlation, permutation importance, and greedy deletion analyses confirm the exclusive dominance of this feature over conventional physicochemical parameters. Complementary characterizations and mechanistic investigations including X-ray photoelectron spectroscopy (XPS), Raman, electron paramagnetic resonance (EPR), and CH4-TPSR reveal that I(110)/I(104) highly correlates with the preferential exposure of (110) facets vs the competitive (104) facet, as well as enhanced oxygen vacancy formations to facilitate C−H and O2 activation. This finding strongly implies a dominant reactivity of (110) facets among various crystal facets. Critically, this linear relationship was also established in both ethane and propane catalytic lean combustion and can be used to predict the reactivities of unseen structures, indicating a mechanistic consistency across light alkane oxidations dominated by (110) facets. The correlation between the relative diffraction peak intensity and catalytic performance is posited to be generalizable to polycrystalline catalysts for surface-sensitive reactions. Such an experimental quantity will not only be highly accessible for practical activity predictions but more importantly be surface-informative to identify reactive facets via routine XRD measurements, which otherwise require intricate investigations on well-defined model systems through controlled surface sciences and/or theoretical modelings.
{"title":"Linear Scaling Relationships between Relative Diffraction Peak Intensity and Catalytic Oxidation of Light Alkanes","authors":"Yuan Gao, Mengyao Bao, Changquan Zhao, Jake Heinlein, Zhuo Li, Beien Zhu, Xiao-Ming Cao, Cheng Hua, Yulian He","doi":"10.1021/acscatal.5c07646","DOIUrl":"https://doi.org/10.1021/acscatal.5c07646","url":null,"abstract":"This study reports a methodology of leveraging highly accessible <i>relative X-ray diffraction peak intensities</i> for the fast identification of reactive facets of polycrystalline catalysts. Specifically, taking polycrystalline α-Fe<sub>2</sub>O<sub>3</sub> as an example, we demonstrate that the ambient-condition X-ray diffraction intensity ratio of (110) to (104) facets (denoted as <i>I</i><sub>(110)</sub>/<i>I</i><sub>(104)</sub>) of α-Fe<sub>2</sub>O<sub>3</sub> exhibits a strong linear correlation (<i>R</i><sup>2</sup> ≈ 0.9) with catalytic rates across diverse temperatures and flow conditions for methane oxidation. Both linear and nonlinear statistical validations via Pearson correlation, permutation importance, and greedy deletion analyses confirm the exclusive dominance of this feature over conventional physicochemical parameters. Complementary characterizations and mechanistic investigations including X-ray photoelectron spectroscopy (XPS), Raman, electron paramagnetic resonance (EPR), and CH<sub>4</sub>-TPSR reveal that <i>I</i><sub>(110)</sub>/<i>I</i><sub>(104)</sub> highly correlates with the preferential exposure of (110) facets vs the competitive (104) facet, as well as enhanced oxygen vacancy formations to facilitate C−H and O<sub>2</sub> activation. This finding strongly implies a dominant reactivity of (110) facets among various crystal facets. Critically, this linear relationship was also established in both ethane and propane catalytic lean combustion and can be used to predict the reactivities of unseen structures, indicating a mechanistic consistency across light alkane oxidations dominated by (110) facets. The correlation between the relative diffraction peak intensity and catalytic performance is posited to be generalizable to polycrystalline catalysts for surface-sensitive reactions. Such an experimental quantity will not only be highly accessible for practical activity predictions but more importantly be surface-informative to identify reactive facets via routine XRD measurements, which otherwise require intricate investigations on well-defined model systems through controlled surface sciences and/or theoretical modelings.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"26 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651291","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Upgrading the renewable bioplatform molecules to high-value compounds has garnered significant attention. The synergistic effect among various metal components often enhances the catalytic performance of a composite catalyst. However, the ingenious integration of multifunctional sites into a single catalyst remains a critical challenge. Herein, this work developed a simply prepared nickel-inserted praseodymium oxide (Pr6O11) magnetic catalyst that realized the selective conversion of levulinic acid (LA) to γ-valerolactone (GVL) using low temperature and H2 pressure. By tailoring the electron-deficient Ni species within the Nix–PrOy (0.5 ≤ x ≤ 2) catalysts, more highly dispersed active Ni0 sites became exposed on the surface, accompanied by a substantial enrichment of oxygen vacancies (Vö) and Lewis acidic sites. The optimal Ni1–PrOy catalyst with multifunctional site integration achieved a 100% yield of GVL at 110 °C under 1 MPa of H2 after 4 h. Notably, it also delivered an intrinsic turnover frequency of 241.1 h–1 under milder conditions, remarkably outperforming typical Ni-based catalysts reported to date. The enhanced intrinsic activity of Ni1–PrOy stemmed from the synergistic catalysis among the active Ni0 sites, defective Vö sites, and Lewis acidic sites, provoked by the adjacent Pr6O11. Specifically, Vö defects and Ni0 sites promoted the adsorption and activation of LA and H2 molecules, while Lewis acidic sites facilitated the conversion of 4-hydroxypentanoic acid (i.e., the reaction intermediate) to the desired GVL. In addition, the Ni1–PrOy catalyst enabled a facile regeneration via magnetic separation and showed satisfactory reusability.
将可再生生物平台分子升级为高价值化合物已经引起了人们的广泛关注。各种金属组分之间的协同作用往往能提高复合催化剂的催化性能。然而，将多功能位点巧妙地整合到单一催化剂中仍然是一个关键的挑战。本研究开发了一种简单制备的嵌镍氧化镨（Pr6O11）磁性催化剂，在低温和H2压力下实现了乙酰丙酸（LA）向γ-戊内酯（GVL）的选择性转化。通过剪裁Nix-PrOy（0.5≤x≤2）催化剂中的缺电子Ni，更多高度分散的活性Ni0位点暴露在表面，伴随着大量的氧空位（Vö）和刘易斯酸位点的富集。最优的多功能位点集成Ni1-PrOy催化剂在110°C、1 MPa H2条件下，4 h后GVL产率达到100%。值得注意的是，在较温和的条件下，它的固有周转率为241.1 h - 1，显著优于目前报道的典型ni基催化剂。Ni1-PrOy的内在活性增强是由于活性Ni0位点、缺陷Vö位点和相邻Pr6O11激发的Lewis酸位点之间的协同催化作用。具体来说，Vö缺陷和Ni0位点促进了LA和H2分子的吸附和活化，而Lewis酸位点则促进了4-羟基戊酸（即反应中间体）向所需GVL的转化。此外，Ni1-PrOy催化剂通过磁分离实现了容易的再生，并表现出令人满意的可重复使用性。
{"title":"Electron-Deficient Nickel Sites Provoked by the Adjacent Praseodymium Oxide Enable High-Performance Biomass Derivative Hydrogenation","authors":"Yaowei Lu, Botao Fan, Runze Zhang, Wanjin Xue, Shipeng Wu, Qinghu Tang, Feng Qiu, Wenhao Fang","doi":"10.1021/acscatal.5c06389","DOIUrl":"https://doi.org/10.1021/acscatal.5c06389","url":null,"abstract":"Upgrading the renewable bioplatform molecules to high-value compounds has garnered significant attention. The synergistic effect among various metal components often enhances the catalytic performance of a composite catalyst. However, the ingenious integration of multifunctional sites into a single catalyst remains a critical challenge. Herein, this work developed a simply prepared nickel-inserted praseodymium oxide (Pr<sub>6</sub>O<sub>11</sub>) magnetic catalyst that realized the selective conversion of levulinic acid (LA) to γ-valerolactone (GVL) using low temperature and H<sub>2</sub> pressure. By tailoring the electron-deficient Ni species within the Ni<sub><i>x</i></sub>–PrO<sub><i>y</i></sub> (0.5 ≤ <i>x</i> ≤ 2) catalysts, more highly dispersed active Ni<sup>0</sup> sites became exposed on the surface, accompanied by a substantial enrichment of oxygen vacancies (V<sub>ö</sub>) and Lewis acidic sites. The optimal Ni<sub>1</sub>–PrO<sub><i>y</i></sub> catalyst with multifunctional site integration achieved a 100% yield of GVL at 110 °C under 1 MPa of H<sub>2</sub> after 4 h. Notably, it also delivered an intrinsic turnover frequency of 241.1 h<sup>–1</sup> under milder conditions, remarkably outperforming typical Ni-based catalysts reported to date. The enhanced intrinsic activity of Ni<sub>1</sub>–PrO<sub><i>y</i></sub> stemmed from the synergistic catalysis among the active Ni<sup>0</sup> sites, defective V<sub>ö</sub> sites, and Lewis acidic sites, provoked by the adjacent Pr<sub>6</sub>O<sub>11</sub>. Specifically, V<sub>ö</sub> defects and Ni<sup>0</sup> sites promoted the adsorption and activation of LA and H<sub>2</sub> molecules, while Lewis acidic sites facilitated the conversion of 4-hydroxypentanoic acid (i.e., the reaction intermediate) to the desired GVL. In addition, the Ni<sub>1</sub>–PrO<sub><i>y</i></sub> catalyst enabled a facile regeneration via magnetic separation and showed satisfactory reusability.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-02DOI: 10.1021/acscatal.5c07431
Nicholas East, Anastasios Polyzos, Colin Scott
Photobiocatalysis merges enzymatic selectivity with the synthetic versatility of light, enabling complex transformations under mild, aqueous conditions. However, advances in this field remain primarily focused on the adaptation of native flavoproteins and known oxidoreductases, such as ene-reductases, with limited exploration of non-natural cofactors or engineered proteins. This perspective examines the current progress in photobiocatalysis, in addition to design constraints that limit the scope of photobiocatalysis, including narrow cofactor compatibility, short excited-state lifetimes, and the instability of enzyme–chromophore systems under irradiation. We highlight the overreliance on a small subset of light-responsive enzyme complexes and propose a broader, modular framework for photoenzyme development. By dissecting the interplay between chromophore identity, protein structure, and reaction environment, we outline strategies to extend the reactivity, stability, and tunability of photoenzymes beyond their native roles. Together, these strategies provide a blueprint for the systematic design, benchmarking, and application of photobiocatalytic systems for broader use and industrial applications.
{"title":"Beyond Flavoproteins: Toward the Industrialization of Photobiocatalysis","authors":"Nicholas East, Anastasios Polyzos, Colin Scott","doi":"10.1021/acscatal.5c07431","DOIUrl":"https://doi.org/10.1021/acscatal.5c07431","url":null,"abstract":"Photobiocatalysis merges enzymatic selectivity with the synthetic versatility of light, enabling complex transformations under mild, aqueous conditions. However, advances in this field remain primarily focused on the adaptation of native flavoproteins and known oxidoreductases, such as ene-reductases, with limited exploration of non-natural cofactors or engineered proteins. This perspective examines the current progress in photobiocatalysis, in addition to design constraints that limit the scope of photobiocatalysis, including narrow cofactor compatibility, short excited-state lifetimes, and the instability of enzyme–chromophore systems under irradiation. We highlight the overreliance on a small subset of light-responsive enzyme complexes and propose a broader, modular framework for photoenzyme development. By dissecting the interplay between chromophore identity, protein structure, and reaction environment, we outline strategies to extend the reactivity, stability, and tunability of photoenzymes beyond their native roles. Together, these strategies provide a blueprint for the systematic design, benchmarking, and application of photobiocatalytic systems for broader use and industrial applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-02DOI: 10.1021/acscatal.5c07930
Seokmin Kang, Wentao Cen, Achyut Ranjan Gogoi, Jeanette Piña, Adhya Suresh, Fernando Ramirez, Osvaldo Gutierrez, Andy A. Thomas
Transmetalation is a pivotal step in the Kumada–Tamao–Corriu cross-coupling reaction, yet its mechanistic details have remained relatively unexplored compared to other palladium-catalyzed processes. Herein, we systematically investigate how diverse phosphine ligands influence the transmetalation rate, using rapid injection NMR (RI-NMR) to directly monitor the formation of the cross-coupling product. The study reveals that both ligand electronic and steric effects significantly affect kobs, with electron-rich ligands tending to slow down the reaction and heteroatom-substituted ligands (CPhos) dramatically accelerating transmetalation. Computational studies suggest that the relatively lower transmetalation transition state barriers for CPhos over SPhos oxidative addition complexes are due to both increased electrophilicity of the Pd-atom as well as the ability to access a more favorable square-pyramidal transition state geometry. Finally, we leverage these kinetic findings to guide the synthesis of poly(3-hexylthiophene) (P3HT) by catalyst-transfer polymerizations. Fast transmetalation ligands, such as CPhos, give higher-molar-mass polymers with controlled dispersities, whereas slower ligands afford inferior control. These results collectively emphasize the centrality of transmetalation in dictating overall cross-coupling performance and pave the way for the rational design of palladium catalysts for both small-molecule synthesis and advanced polymer applications.
{"title":"Mechanistically Driven Development of Kumada Catalyst-Transfer Polymerizations: A Rapid Injection NMR Study","authors":"Seokmin Kang, Wentao Cen, Achyut Ranjan Gogoi, Jeanette Piña, Adhya Suresh, Fernando Ramirez, Osvaldo Gutierrez, Andy A. Thomas","doi":"10.1021/acscatal.5c07930","DOIUrl":"https://doi.org/10.1021/acscatal.5c07930","url":null,"abstract":"Transmetalation is a pivotal step in the Kumada–Tamao–Corriu cross-coupling reaction, yet its mechanistic details have remained relatively unexplored compared to other palladium-catalyzed processes. Herein, we systematically investigate how diverse phosphine ligands influence the transmetalation rate, using rapid injection NMR (RI-NMR) to directly monitor the formation of the cross-coupling product. The study reveals that both ligand electronic and steric effects significantly affect <i>k</i><sub>obs</sub>, with electron-rich ligands tending to slow down the reaction and heteroatom-substituted ligands (CPhos) dramatically accelerating transmetalation. Computational studies suggest that the relatively lower transmetalation transition state barriers for CPhos over SPhos oxidative addition complexes are due to both increased electrophilicity of the Pd-atom as well as the ability to access a more favorable square-pyramidal transition state geometry. Finally, we leverage these kinetic findings to guide the synthesis of poly(3-hexylthiophene) (P3HT) by catalyst-transfer polymerizations. Fast transmetalation ligands, such as CPhos, give higher-molar-mass polymers with controlled dispersities, whereas slower ligands afford inferior control. These results collectively emphasize the centrality of transmetalation in dictating overall cross-coupling performance and pave the way for the rational design of palladium catalysts for both small-molecule synthesis and advanced polymer applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-02DOI: 10.1021/acscatal.5c07552
Xiaocong Wu, Haodong Wu, Yida Gao, Guofeng Gu, Xianwei Liu
Chemoenzymatic assembly of complex glycans is hindered by the high cost of sugar nucleotides (SNs) and product inhibition from released nucleoside phosphates. Here, we report a versatile polyphosphate-driven regeneration system that overcomes these limitations. Central to this system is the class III polyphosphate kinase EbPPK, which converts all four canonical nucleoside monophosphates (NMPs) into nucleoside triphosphates (NTPs) in situ, permitting one-pot cascades that start from low-cost NMPs supplied at either catalytic or near-stoichiometric levels. Except for GDP-Fuc and UDP-GlcA, regeneration of UDP-Gal, UDP-GalNAc, UDP-GlcNAc and CMP-Sia demands only uridine monophosphates (UMP) or cytidine monophosphate (CMP) as a sole cofactor, thereby eliminating the need for adenine nucleotides. Coupling EbPPK with salvage enzymes and Leloir glycosyltransferases created a three-module platform that furnished gram quantities of tumor-associated globo-series glycosphingolipids and five representative human-milk oligosaccharides in isolated yields of 71–98% with cofactor total turnover numbers up to 76 and space-time yields approaching 5.1 g L–1 h–1. The same strategy was extended to medium-molecular-weight hyaluronic acid, delivering 1.2 g at 5.9 g L–1. The approach relies on inexpensive polyphosphate and monosaccharide inputs, avoids extra kinases and is readily scalable, offering a cost-effective route to complex carbohydrates for biomedical and nutritional applications.
复杂聚糖的化学酶组装受到糖核苷酸（SNs）的高成本和释放的核苷磷酸盐的产物抑制的阻碍。在这里，我们报告了一种多用途的多磷酸盐驱动再生系统，克服了这些限制。该系统的核心是III类多磷酸激酶EbPPK，它将所有四种典型的核苷单磷酸（nmp）就地转化为核苷三磷酸（NTPs），允许从催化或接近化学计量水平的低成本nmp开始的一锅级联反应。除了GDP-Fuc和UDP-GlcA外，UDP-Gal、UDP-GalNAc、UDP-GlcNAc和CMP- sia的再生只需要单磷酸尿苷（UMP）或单磷酸胞苷（CMP）作为唯一的辅助因子，从而消除了对腺嘌呤核苷酸的需求。将EbPPK与挽救酶和Leloir糖基转移酶结合，创建了一个三模块平台，提供克量的肿瘤相关的global -series糖磷脂和5种代表性的人乳低聚糖，分离产量为71-98%，辅因子总周转率高达76，时空产量接近5.1 g L-1 h-1。同样的策略也适用于中等分子量的透明质酸，以5.9 g L-1的速度输送1.2 g。该方法依赖于廉价的多磷酸和单糖输入，避免了额外的激酶，并且易于扩展，为生物医学和营养应用提供了一种具有成本效益的复杂碳水化合物途径。
{"title":"The Coupling of a Universal Polyphosphate Kinase and Glycosyltransferases Enabled In Situ Regeneration of Sugar Nucleotides for Efficient Synthesis of Functional Glycans","authors":"Xiaocong Wu, Haodong Wu, Yida Gao, Guofeng Gu, Xianwei Liu","doi":"10.1021/acscatal.5c07552","DOIUrl":"https://doi.org/10.1021/acscatal.5c07552","url":null,"abstract":"Chemoenzymatic assembly of complex glycans is hindered by the high cost of sugar nucleotides (SNs) and product inhibition from released nucleoside phosphates. Here, we report a versatile polyphosphate-driven regeneration system that overcomes these limitations. Central to this system is the class III polyphosphate kinase EbPPK, which converts all four canonical nucleoside monophosphates (NMPs) into nucleoside triphosphates (NTPs) in situ, permitting one-pot cascades that start from low-cost NMPs supplied at either catalytic or near-stoichiometric levels. Except for GDP-Fuc and UDP-GlcA, regeneration of UDP-Gal, UDP-GalNAc, UDP-GlcNAc and CMP-Sia demands only uridine monophosphates (UMP) or cytidine monophosphate (CMP) as a sole cofactor, thereby eliminating the need for adenine nucleotides. Coupling EbPPK with salvage enzymes and Leloir glycosyltransferases created a three-module platform that furnished gram quantities of tumor-associated globo-series glycosphingolipids and five representative human-milk oligosaccharides in isolated yields of 71–98% with cofactor total turnover numbers up to 76 and space-time yields approaching 5.1 g L<sup>–1</sup> h<sup>–1</sup>. The same strategy was extended to medium-molecular-weight hyaluronic acid, delivering 1.2 g at 5.9 g L<sup>–1</sup>. The approach relies on inexpensive polyphosphate and monosaccharide inputs, avoids extra kinases and is readily scalable, offering a cost-effective route to complex carbohydrates for biomedical and nutritional applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"115 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Silicon-stereogenic architectures are valuable in organosilicon chemistry and medicinal chemistry, but their enantioselective synthesis via silicon-centered chirality transfer remains a challenge. In contrast to well-studied chirality-at-carbon chemistry, the construction of silicon-stereogenic centers has been considered as a challenging topic due to its limited synthetic strategy. Here, we realized a kinetic resolution process to establish a palladium-catalyzed enantioselective ring-expansion-type (4 + 2) silacycloaddition reaction of racemic benzosilacyclobutenes with unsymmetrical internal alkynes via selective Si–C(sp3) bond cleavage. By employing a chiral TADDOL-derived phosphoramidite ligand, we achieved the kinetically controlled catalytic asymmetric construction of silicon-stereogenic benzo[c]silin derivatives with good enantioselectivity. The catalytic system features mild conditions, high chemoselectivity, a broad substrate scope, and good functional group tolerance, demonstrating broad applicability to unsymmetrical alkynes bearing terminal ketone or ester groups. Furthermore, the kinetic studies of racemic substrates corroborate the versatility and applicability of this strategy, offering a robust strategy called the kinetic resolution of racemic substrate in this work to access structurally diverse silicon-stereogenic organosilicon compounds.
{"title":"Regio- and Enantioselective Palladium-Catalyzed (4 + 2) Silacycloaddition of Unsymmetrical Internal Alkynes with Racemic Benzosilacyclobutenes","authors":"Xing-Ben Wang, Jun-Jie Guo, Cheng Chen, Jia-Wei Si, Zheng Xu, Zhi-Yuan Zhao, Zhuangzhi Shi, Fuk Yee Kwong, Li-Wen Xu","doi":"10.1021/acscatal.5c06885","DOIUrl":"https://doi.org/10.1021/acscatal.5c06885","url":null,"abstract":"Silicon-stereogenic architectures are valuable in organosilicon chemistry and medicinal chemistry, but their enantioselective synthesis via silicon-centered chirality transfer remains a challenge. In contrast to well-studied chirality-at-carbon chemistry, the construction of silicon-stereogenic centers has been considered as a challenging topic due to its limited synthetic strategy. Here, we realized a kinetic resolution process to establish a palladium-catalyzed enantioselective ring-expansion-type (4 + 2) silacycloaddition reaction of racemic benzosilacyclobutenes with unsymmetrical internal alkynes via selective Si–C(sp<sup>3</sup>) bond cleavage. By employing a chiral TADDOL-derived phosphoramidite ligand, we achieved the kinetically controlled catalytic asymmetric construction of silicon-stereogenic benzo[c]silin derivatives with good enantioselectivity. The catalytic system features mild conditions, high chemoselectivity, a broad substrate scope, and good functional group tolerance, demonstrating broad applicability to unsymmetrical alkynes bearing terminal ketone or ester groups. Furthermore, the kinetic studies of racemic substrates corroborate the versatility and applicability of this strategy, offering a robust strategy called the kinetic resolution of racemic substrate in this work to access structurally diverse silicon-stereogenic organosilicon compounds.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"143 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651294","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01DOI: 10.1021/acscatal.5c06702
Guitao Bai, Tangliang Shen, MohammadHossein Shabahang, Shumin Bao, Shuquan Fan, Hongshuai Lv, Lei Li
Type-1 glycan unit, Galβ1-3GlcNAc, is one of the two major backbones from which the large glycan determinant repertoire is derived. Numerous type-1 glycan determinants, including Lewis-series antigens, have been identified, often featuring fucosylation and sialylation. In this study, we achieved efficient synthesis of 30 type-1 determinants using a divergent enzymatic strategy. The synthetic efficiency of eight fucosyltransferases (FucTs) was evaluated for the installation of fucose at every step of the type-1 determinant synthesis. Using selected FucTs and a few additional robust glycosyltransferases, 22 basic type-1 determinants were constructed at preparative scales in no more than three steps, starting from the type-1 unit. Additionally, 8 extended type-1 Lewis antigens were successfully synthesized in no more than five steps. Subsequent glycan microarray assays of these glycan determinants revealed intriguing recognitions by glycan-binding proteins and anti-type-1 Lewis antigen monoclonal antibodies.
{"title":"Divergent Enzymatic Synthesis of a Comprehensive Type-1 Glycan Determinant Library","authors":"Guitao Bai, Tangliang Shen, MohammadHossein Shabahang, Shumin Bao, Shuquan Fan, Hongshuai Lv, Lei Li","doi":"10.1021/acscatal.5c06702","DOIUrl":"https://doi.org/10.1021/acscatal.5c06702","url":null,"abstract":"Type-1 glycan unit, Galβ1-3GlcNAc, is one of the two major backbones from which the large glycan determinant repertoire is derived. Numerous type-1 glycan determinants, including Lewis-series antigens, have been identified, often featuring fucosylation and sialylation. In this study, we achieved efficient synthesis of 30 type-1 determinants using a divergent enzymatic strategy. The synthetic efficiency of eight fucosyltransferases (FucTs) was evaluated for the installation of fucose at every step of the type-1 determinant synthesis. Using selected FucTs and a few additional robust glycosyltransferases, 22 basic type-1 determinants were constructed at preparative scales in no more than three steps, starting from the type-1 unit. Additionally, 8 extended type-1 Lewis antigens were successfully synthesized in no more than five steps. Subsequent glycan microarray assays of these glycan determinants revealed intriguing recognitions by glycan-binding proteins and anti-type-1 Lewis antigen monoclonal antibodies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"152 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651293","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Diphenoquinones (DPQs) were developed as a type of photocatalyst capable of dual hydrogen atom transfer (HAT) within a single catalytic cycle. This capability arises from the specific conjugated π-system of DPQs, which enables radical resonance from the ketyl carbon-centered position to the oxygen-centered position for the generation of a dioxygen-centered radical species. This strategy was successfully exploited in the photochemical dehydrogenation of amides to enamides by sequential abstraction of α-C(sp3)–H and β-C(sp3)–H, offering broad substrate scope and high regioselectivity under mild conditions.
{"title":"Diphenoquinone-Catalyzed Dual HATs Enable Visible Light-Induced Sequential Dehydrogenation of Amides to Enamides","authors":"Yunhong Yang, Chuanwang Liu, Mi Jie, Jiaqian Zhang, Endiao Zhu, Zhiqiang Pan, Chengfeng Xia","doi":"10.1021/acscatal.5c06397","DOIUrl":"https://doi.org/10.1021/acscatal.5c06397","url":null,"abstract":"Diphenoquinones (DPQs) were developed as a type of photocatalyst capable of dual hydrogen atom transfer (HAT) within a single catalytic cycle. This capability arises from the specific conjugated π-system of DPQs, which enables radical resonance from the ketyl carbon-centered position to the oxygen-centered position for the generation of a dioxygen-centered radical species. This strategy was successfully exploited in the photochemical dehydrogenation of amides to enamides by sequential abstraction of α-C(sp<sup>3</sup>)–H and β-C(sp<sup>3</sup>)–H, offering broad substrate scope and high regioselectivity under mild conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"53 4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01DOI: 10.1021/acscatal.5c07430
Xuejiao Li, Yu Gan, Hao-Nan Chen, Shengjie Gao, Baihua Ye
Cross-electrophile coupling of two distinct organic halides has emerged as a powerful strategy for expanding chemical spaces. In this context, stereoselective nickel catalysis holds high synthetic value, yet remains relatively underdeveloped.. Herein, we report a zirconaaziridine-mediated cross-electrophile coupling protocol catalyzed by a tripyridyl-ligated nickel complex, enabling the diastereoselective synthesis of substituted cyclohexyl, tetrahydropyranyl, and piperidyl scaffolds with high levels of stereocontrol and broad functional group tolerance. Experimental investigations including kinetic and computational studies support a “sequential reduction” mechanism, wherein redox-transmetalation between a Ni(II) dihalide complex and zirconaaziridine is proposed to generate a monovalent Ni(I) halide species alongside a Cp2Zr(III) intermediate that facilitates the conversion of an alkyl iodide into the corresponding C(sp3) radical.
{"title":"Harnessing a Tripyridyl Ligand in Zirconaaziridine-Mediated Ni-Catalyzed Cross-Electrophile Couplings","authors":"Xuejiao Li, Yu Gan, Hao-Nan Chen, Shengjie Gao, Baihua Ye","doi":"10.1021/acscatal.5c07430","DOIUrl":"https://doi.org/10.1021/acscatal.5c07430","url":null,"abstract":"Cross-electrophile coupling of two distinct organic halides has emerged as a powerful strategy for expanding chemical spaces. In this context, stereoselective nickel catalysis holds high synthetic value, yet remains relatively underdeveloped.. Herein, we report a zirconaaziridine-mediated cross-electrophile coupling protocol catalyzed by a tripyridyl-ligated nickel complex, enabling the diastereoselective synthesis of substituted cyclohexyl, tetrahydropyranyl, and piperidyl scaffolds with high levels of stereocontrol and broad functional group tolerance. Experimental investigations including kinetic and computational studies support a “sequential reduction” mechanism, wherein redox-transmetalation between a Ni(II) dihalide complex and zirconaaziridine is proposed to generate a monovalent Ni(I) halide species alongside a Cp<sub>2</sub>Zr(III) intermediate that facilitates the conversion of an alkyl iodide into the corresponding C(sp<sup>3</sup>) radical.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-30DOI: 10.1021/acscatal.5c06762
Siyu Ma, Shufei Wang, Shuguang Wang, Xinze Chen, Hongyuan He, Xiaoxin Zhang, Shuo Zhai, Qingyang Han, Pengfei Zhang, Kai Zhao, Ning Yan, Yue Tie, Ding Ding, Xingyu Chen, Yingru Zhao, Meidan Ye, Abdullah N. Alodhayb, Zhou Chen, Yanping Zheng, Jianhui Li, Yifei Sun
Perovskite oxides are promising anodic electrocatalysts for alkaline saline water electrolysis, yet their performance is often limited by sluggish oxygen evolution reaction kinetics and competing chloride corrosion. Building on Pr0.1Sr0.9Co0.5Fe0.5O3 (PSCF), a candidate previously identified via our transfer learning paradigm, we further leveraged data-driven compositional searching of the A-site configuration, which led to an optimized catalyst with a proper Ce/Sr/Pr ratio (Ce-PSCF). The asymmetric Ce–O–Co motifs invoked a negative charge-transfer regime and activated the evolution of nonbonding oxygen (ONB) states, which reconciled the activity-stability trade-off and promoted a dual-site intramolecular lattice oxygen mechanism, as evidenced by promoted 18O–18O evolution. The electrolyzer with Ce-PSCF lowered the overpotential of the PSCF-based one by 100 mV at 300 mA cm–2 and exhibited 15-fold greater durability. Electrochemical analysis revealed a higher reaction order, promoted *OH coverage, and faster surface reconstruction on the Ce-incorporated electrocatalyst, indicating *OH-controlled chemical-step kinetics. Theoretical insight inferred a variation of the rate-determining step from O–O coupling to secondary OH– refilling with a reduced energy barrier from 0.68 to 0.54 eV. Moreover, ab initio molecular dynamics simulations visualized a dynamically strengthened affinity for OH– and significant repulsion of Cl–, arising from its intrinsic Lewis acidic and basic microenvironment.
钙钛矿氧化物是一种很有前途的碱性盐水电解阳极电催化剂，但其性能往往受到析氧反应动力学缓慢和氯离子腐蚀竞争的限制。在Pr0.1Sr0.9Co0.5Fe0.5O3 （PSCF）的基础上，我们进一步利用数据驱动的a位结构组成搜索，从而优化了具有适当Ce/Sr/Pr比（Ce-PSCF）的催化剂。不对称的Ce-O-Co基序激活了负电荷转移机制，激活了非键氧（ONB）态的演化，这调和了活性与稳定性的权衡，促进了分子内双点阵氧机制，并促进了18O-18O的演化。使用Ce-PSCF的电解槽在300 mA cm-2下将pscf电解槽的过电位降低了100 mV，耐久性提高了15倍。电化学分析表明，ce掺杂电催化剂的反应顺序更高，*OH覆盖率提高，表面重建速度更快，表明*OH控制化学步骤动力学。理论见解推断了从O-O耦合到二次OH -再填充的速率决定步骤的变化，能量势垒从0.68 eV降低到0.54 eV。此外，从头算分子动力学模拟显示，由于其固有的刘易斯酸碱性微环境，对OH -具有动态增强的亲和力和对Cl -的显著排斥。
{"title":"Machine Learning Unveils Ce–O–Co Motifs in Perovskite with Lewis Acidic–Basic Microenvironment for Dual-Site Intramolecular Oxygen Evolution in Saline Water","authors":"Siyu Ma, Shufei Wang, Shuguang Wang, Xinze Chen, Hongyuan He, Xiaoxin Zhang, Shuo Zhai, Qingyang Han, Pengfei Zhang, Kai Zhao, Ning Yan, Yue Tie, Ding Ding, Xingyu Chen, Yingru Zhao, Meidan Ye, Abdullah N. Alodhayb, Zhou Chen, Yanping Zheng, Jianhui Li, Yifei Sun","doi":"10.1021/acscatal.5c06762","DOIUrl":"https://doi.org/10.1021/acscatal.5c06762","url":null,"abstract":"Perovskite oxides are promising anodic electrocatalysts for alkaline saline water electrolysis, yet their performance is often limited by sluggish oxygen evolution reaction kinetics and competing chloride corrosion. Building on Pr<sub>0.1</sub>Sr<sub>0.9</sub>Co<sub>0.5</sub>Fe<sub>0.5</sub>O<sub>3</sub> (PSCF), a candidate previously identified via our transfer learning paradigm, we further leveraged data-driven compositional searching of the A-site configuration, which led to an optimized catalyst with a proper Ce/Sr/Pr ratio (Ce-PSCF). The asymmetric Ce–O–Co motifs invoked a negative charge-transfer regime and activated the evolution of nonbonding oxygen (O<sub>NB</sub>) states, which reconciled the activity-stability trade-off and promoted a dual-site intramolecular lattice oxygen mechanism, as evidenced by promoted <sup>18</sup>O–<sup>18</sup>O evolution. The electrolyzer with Ce-PSCF lowered the overpotential of the PSCF-based one by 100 mV at 300 mA cm<sup>–2</sup> and exhibited 15-fold greater durability. Electrochemical analysis revealed a higher reaction order, promoted *OH coverage, and faster surface reconstruction on the Ce-incorporated electrocatalyst, indicating *OH-controlled chemical-step kinetics. Theoretical insight inferred a variation of the rate-determining step from O–O coupling to secondary OH<sup>–</sup> refilling with a reduced energy barrier from 0.68 to 0.54 eV. Moreover, ab initio molecular dynamics simulations visualized a dynamically strengthened affinity for OH<sup>–</sup> and significant repulsion of Cl<sup>–</sup>, arising from its intrinsic Lewis acidic and basic microenvironment.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"122 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145645237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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