Nature CatalysisPub Date : 2025-02-25DOI: 10.1038/s41929-025-01300-1
Jun Wang, Kang Liu, Wanru Liao, Yicui Kang, Hanrui Xiao, Yingkang Chen, Qiyou Wang, Tao Luo, Jiawei Chen, Hongmei Li, Ting-Shan Chan, Shanyong Chen, Evangelina Pensa, Liyuan Chai, Fangyang Liu, Liangxing Jiang, Changxu Liu, Junwei Fu, Emiliano Cortés, Min Liu
{"title":"Metal vacancies in semiconductor oxides enhance hole mobility for efficient photoelectrochemical water splitting","authors":"Jun Wang, Kang Liu, Wanru Liao, Yicui Kang, Hanrui Xiao, Yingkang Chen, Qiyou Wang, Tao Luo, Jiawei Chen, Hongmei Li, Ting-Shan Chan, Shanyong Chen, Evangelina Pensa, Liyuan Chai, Fangyang Liu, Liangxing Jiang, Changxu Liu, Junwei Fu, Emiliano Cortés, Min Liu","doi":"10.1038/s41929-025-01300-1","DOIUrl":"10.1038/s41929-025-01300-1","url":null,"abstract":"Achieving efficient carrier separation in transition-metal-oxide semiconductors is crucial for their applications in optoelectronic and catalytic devices. However, the substantial disparity in mobility between holes and electrons heavily limits device performance. Here we develop a general strategy for enhancing hole mobility via reducing their effective mass through metal vacancy (VM) management. The introduction of VM yields remarkable improvements in hole mobility: 430% for WO3, 350% for TiO2 and 270% for Bi2O3. To illustrate the importance of this finding, we applied the VM concept to photoelectrochemical water splitting, where efficient carrier separation is highly coveted. In particular, VM-WO3 achieves a 4.4-fold enhancement in photo-to-current efficiency, yielding a performance of 4.8 mA cm−2 for both small- and large-scale photoelectrodes with exceptional stability for over 120 h. Efficient charge carrier separation is a substantial roadblock to achieving high performance in photoelectrochemical systems based on transition-metal oxides. Here a metal vacancy strategy is used to enhance hole mobility, resulting in general enhancement of photocurrent density in WO3, TiO2 and Bi2O3 photoanodes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 3","pages":"229-238"},"PeriodicalIF":42.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-025-01300-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Electron and proton storage on separate Ru and BaO domains mediated by conductive low-work-function carbon to accelerate ammonia synthesis","authors":"Yaejun Baik, Seunghyuck Chi, Kyeongjin Lee, DongHwan Oh, Kyungho Lee, Minkee Choi","doi":"10.1038/s41929-025-01302-z","DOIUrl":"10.1038/s41929-025-01302-z","url":null,"abstract":"Ammonia (NH3) has gained attention as a carbon-free fuel and hydrogen carrier, making its energy-efficient production increasingly important. Here we demonstrate that Ru and BaO, connected by conductive carbon, can separately store e− and H+, like a chemical capacitor under NH3 synthesis conditions. H atoms generated on the Ru surface by H2 activation polarize into H+/e− pairs. Subsequently, H+ migrates over the carbon surfaces to neutralize basic BaO, while e− accumulates in conductive Ru/carbon. As the work function of carbon decreases, Ru gradually becomes enriched with e−, facilitating N2 activation via π-backdonation and alleviating H2 poisoning. Thus, an optimized catalyst synthesized using N-doped MWNT with the lowest work function, exhibited 7.4 times higher activity than a reference Ba–Ru/MgO catalyst. The results show that charge distribution within catalysts can be markedly altered under reaction conditions, and its rational control can enable the design of active NH3 synthesis catalysts. Ru and Ba are common partners within ammonia synthesis catalysts, but the mechanism by which the base promotes the metal is not fully understood. Here the use of conductive carbon supports reveals intriguing mechanistic aspects of this promotion effect and enables the generation of an advanced ammonia synthesis catalyst.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 3","pages":"248-256"},"PeriodicalIF":42.8,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-025-01302-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477557","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nature CatalysisPub Date : 2025-02-13DOI: 10.1038/s41929-024-01288-0
Claire Dooley, Francesco Ibba, Bence B. Botlik, Chiara Palladino, Christopher A. Goult, Yuan Gao, Andrew Lister, Robert S. Paton, Guy C. Lloyd-Jones, Véronique Gouverneur
{"title":"Enantioconvergent nucleophilic substitution via synergistic phase-transfer catalysis","authors":"Claire Dooley, Francesco Ibba, Bence B. Botlik, Chiara Palladino, Christopher A. Goult, Yuan Gao, Andrew Lister, Robert S. Paton, Guy C. Lloyd-Jones, Véronique Gouverneur","doi":"10.1038/s41929-024-01288-0","DOIUrl":"10.1038/s41929-024-01288-0","url":null,"abstract":"Catalytic enantioconvergent nucleophilic substitution reactions of alkyl halides are highly valuable transformations, but they are notoriously difficult to implement. Specifically, nucleophilic fluorination is a renowned challenge, especially when inexpensive alkali metal fluorides are used as fluorinating reagents due to their low solubility, high hygroscopicity and Brønsted basicity. Here we report a solution by developing the concept of synergistic hydrogen bonding phase-transfer catalysis. Key to our strategy is the combination of a chiral bis-urea hydrogen bond donor (HBD) and an onium salt—two phase-transfer catalysts essential for the solubilization of potassium fluoride—as a well-characterized ternary HBD–onium fluoride complex. Mechanistic investigations indicate that this chiral ternary complex is capable of enantiodiscrimination of racemic benzylic bromides and α-bromoketones, and upon fluoride delivery affords fluorinated products in high yields and enantioselectivities. This work provides a foundation for enantioconvergent fluorination chemistry enabled through the combination of a HBD catalyst with a co-catalyst specifically curated to meet the requirement of the electrophile. The catalytic enantioconvergent nucleophilic fluorination of alkyl halides using inexpensive alkali metal fluorides is a persistent challenge. Now this has been achieved by synergistic hydrogen bonding phase-transfer catalysis combining a chiral bis-urea hydrogen bond donor and an onium salt.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"107-115"},"PeriodicalIF":42.8,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01288-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nature CatalysisPub Date : 2025-02-13DOI: 10.1038/s41929-024-01280-8
Melanie A. Higgins, Xinjie Shi, Jordi Soler, Jill B. Harland, Taylor Parkkila, Nicolai Lehnert, Marc Garcia-Borràs, Yi-Ling Du, Katherine S. Ryan
{"title":"Structure and mechanism of haem-dependent nitrogen–nitrogen bond formation in piperazate synthase","authors":"Melanie A. Higgins, Xinjie Shi, Jordi Soler, Jill B. Harland, Taylor Parkkila, Nicolai Lehnert, Marc Garcia-Borràs, Yi-Ling Du, Katherine S. Ryan","doi":"10.1038/s41929-024-01280-8","DOIUrl":"10.1038/s41929-024-01280-8","url":null,"abstract":"Molecules with nitrogen–nitrogen (N–N) bonds include diverse specialized metabolites from nature, but little is known about the underlying enzymatic mechanisms that have evolved for N–N bond formation. To directly form a single N(sp3)–N(sp3) bond, enzymes must reverse the typical nucleophilicity of one nitrogen. Here we report the structure of PipS, a haem-dependent enzyme that catalyses N–N bond formation in the cyclization of N5-OH-l-ornithine, giving l-piperazic acid. Our work reveals the role of a Lys–Thr dyad early in the mechanism and shows that PipS catalyses either N–N bond formation or imine-group formation in a substrate-specific manner, which may stem from a shared nitrenoid intermediate that effectively reverses the nucleophilicity of the hydroxylamine nitrogen. Our work expands knowledge of enzymatic N–N bond formation and delineates the catalytic versatility of a haem cofactor, paving the way for genetically encoded biocatalysts for N–N bond formation. Despite the existence of many N–N-containing natural metabolites, little is known about the enzymatic mechanisms of N–N bond formation. Now, a catalytically relevant X-ray crystal structure of an N–N-bond-forming enzyme, PipS, is reported and detailed insights into its catalytic mechanism are provided.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 3","pages":"207-217"},"PeriodicalIF":42.8,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01280-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nature CatalysisPub Date : 2025-02-13DOI: 10.1038/s41929-025-01298-6
Yan Zhang, Ziqi Liu, Nan Zhou, Fuhu Guo, Haotian Guo, Xinyue Chen, Shengnan Qin, Peng R. Chen, Xinyuan Fan
{"title":"In situ lysosomal proteomics enabled by bioorthogonal photocatalytic proximity labelling","authors":"Yan Zhang, Ziqi Liu, Nan Zhou, Fuhu Guo, Haotian Guo, Xinyue Chen, Shengnan Qin, Peng R. Chen, Xinyuan Fan","doi":"10.1038/s41929-025-01298-6","DOIUrl":"10.1038/s41929-025-01298-6","url":null,"abstract":"In situ deciphering of lysosome proteomes is crucial for understanding cellular processes and diseases, but is challenging due to its digestive, acidic environment that renders proximity labelling enzymes incompatible. Here we have developed a photocatalytic proximity labelling technique, CAT-Lyso, for in situ lysosomal proteomics. By employing a lysosome-targeting photocatalyst/thioquinone methide labelling probe pair, CAT-Lyso enables the generation of a reactive thioquinone methide intermediate via photoredox catalysis, facilitating efficient lysosomal proteome labelling in diverse cell lines, including hard-to-transfect macrophages (RAW264.7) and B lymphocytes (Raji). CAT-Lyso successfully identified cell type-specific lysosomal proteomic patterns and uncovered previously unrecognized lysosomal proteins, such as SCAMP3, NAGPA, GLG1 and MFSD14B. Furthermore, CAT-Lyso enabled quantitative profiling of lysosomal proteome dynamics under perturbations such as rapamycin-mediated mTOR inhibition, revealing pronounced ferritinophagy that evokes a coordinated labile iron-resisting program in cancer cells. With its in situ labelling, non-genetic operation, high specificity and photocontrollability, CAT-Lyso provides a powerful tool for investigating lysosome proteome dynamics in living systems. In situ profiling of lysosomal proteomes is impeded by the acidic and digestive environment of lysosomes. Now, a bioorthogonal photocatalytic system (CAT-Lyso) is developed that is compatible with these conditions, enabling the proximity labelling of lysosomal proteomes within living cells.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"162-177"},"PeriodicalIF":42.8,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401417","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}
Nature CatalysisPub Date : 2025-02-11DOI: 10.1038/s41929-025-01299-5
Qingyun Dan, Yan Chiu, Namil Lee, Jose Henrique Pereira, Behzad Rad, Xixi Zhao, Kai Deng, Yiou Rong, Chunjun Zhan, Yan Chen, Seokjung Cheong, Chenyi Li, Jennifer W. Gin, Andria Rodrigues, Trent R. Northen, Tyler W. H. Backman, Edward E. K. Baidoo, Christopher J. Petzold, Paul D. Adams, Jay D. Keasling
{"title":"A polyketide-based biosynthetic platform for diols, amino alcohols and hydroxy acids","authors":"Qingyun Dan, Yan Chiu, Namil Lee, Jose Henrique Pereira, Behzad Rad, Xixi Zhao, Kai Deng, Yiou Rong, Chunjun Zhan, Yan Chen, Seokjung Cheong, Chenyi Li, Jennifer W. Gin, Andria Rodrigues, Trent R. Northen, Tyler W. H. Backman, Edward E. K. Baidoo, Christopher J. Petzold, Paul D. Adams, Jay D. Keasling","doi":"10.1038/s41929-025-01299-5","DOIUrl":"10.1038/s41929-025-01299-5","url":null,"abstract":"Medium- and branched-chain diols and amino alcohols are important industrial solvents, polymer building blocks, cosmetics and pharmaceutical ingredients, yet biosynthetically challenging to produce. Here we present an approach that uses a modular polyketide synthase (PKS) platform for the efficient production of these compounds. This platform takes advantage of a versatile loading module from the rimocidin PKS and nicotinamide adenine dinucleotide phosphate-dependent terminal thioreductases. Reduction of the terminal aldehyde with alcohol dehydrogenases enables the production of diols, oxidation enables the production of hydroxy acids and specific transaminases allow the production of various amino alcohols. Furthermore, replacement of the malonyl-coenzyme A-specific acyltransferase in the extension module with methyl- or ethylmalonyl-coenzyme A-specific acyltransferase enables the production of branched-chain diols, amino alcohols and carboxylic acids in high titres. Use of our PKS platform in Streptomyces albus demonstrated the high tunability and efficiency of the platform. Medium- and branched-chain diols and amino alcohols are important industrial feedstocks, but they are biosynthetically challenging to produce. Here the authors introduce a modular polyketide synthase platform for the efficient production of these compounds.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"147-161"},"PeriodicalIF":42.8,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-025-01299-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nature CatalysisPub Date : 2025-02-07DOI: 10.1038/s41929-025-01289-7
Jason J. Huang, Yao Yang, Daniel Weinstock, Colin R. Bundschu, Qihao Li, Suchismita Sarker, Jacob P. C. Ruff, Tomás A. Arias, Héctor D. Abruña, Andrej Singer
{"title":"Multimodal in situ X-ray mechanistic studies of a bimetallic oxide electrocatalyst in alkaline media","authors":"Jason J. Huang, Yao Yang, Daniel Weinstock, Colin R. Bundschu, Qihao Li, Suchismita Sarker, Jacob P. C. Ruff, Tomás A. Arias, Héctor D. Abruña, Andrej Singer","doi":"10.1038/s41929-025-01289-7","DOIUrl":"10.1038/s41929-025-01289-7","url":null,"abstract":"Co–Mn spinel oxide is a promising next-generation electrocatalyst that has previously shown oxygen reduction reaction activity that rivals that of Pt in alkaline fuel cells. Although the performance is encouraging, understanding the catalytic mechanisms in the oxygen reduction reaction is critical to advancing and enabling low-cost alkaline fuel cell technology. Here we use multimodal in situ synchrotron X-ray diffraction and resonant elastic X-ray scattering to investigate the interplay between the structure and oxidation state of a Co–Mn spinel oxide electrocatalyst. We show that the Co–Mn spinel oxide electrocatalyst exhibits a kinetically limited cubic-to-tetragonal phase transition, which is correlated to a reduction in both the Co and Mn valence states. Additionally, the electrocatalyst exhibits a reversible and rapid increase in tensile strain at low potentials during cyclic voltammetry, and joint density-functional theory is used to provide insight into how reactive adsorbates induce strain in spinel oxide nanoparticles. Co–Mn spinel oxides are the most promising precious-metal-free catalysts for oxygen reduction in alkaline electrolytes, but their structure–activity properties are not yet fully understood. Now, in situ XRD and REXS performed on MnCo2O4 identify surface tensile strain at low potentials and a reversible transformation between cubic and tetragonal structures.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"116-125"},"PeriodicalIF":42.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258669","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}
{"title":"Iron-catalysed alkenylzincation of allenes via electrophilicity reversal","authors":"Jun-Jia Chen, Mu-Han Guan, Peng He, Ming-Yao Huang, Xin-Yu Zhang, Shou-Fei Zhu","doi":"10.1038/s41929-025-01293-x","DOIUrl":"10.1038/s41929-025-01293-x","url":null,"abstract":"Given the structural characteristics of allenes, nucleophilic additions usually occur at the electron-deficient central carbon atom of allene. Here we report an iron-catalysed alkenylzincation reaction of terminal allenes that shows abnormal regioselectivity, wherein the electrophilic zinc moiety from an organozinc reagent is incorporated at the electron-deficient central carbon atom of the allene. This alkenylzincation reaction shows broad functional group compatibility and excellent regio- and stereoselectivities. Using this method, we accessed cis-1,4-dienylzinc reagents and their corresponding polysubstituted 1,4-diene derivatives, which are notoriously challenging to prepare via conventional routes. Mechanistic studies revealed that an unexpected reversal of the electrophilicity of the allene carbons is realized through the electron donation from the Fe(0) to the allene via π back-bonding, resulting in the observed abnormal regioselectivity. Allenes are versatile substrates in synthetic chemistry. Now an iron catalyst enables unusual regioselectivity by mediating an electrophilicity reversal of allenes for stereoselective alkenylzincation reactions affording 1,4-diene zinc products.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"178-186"},"PeriodicalIF":42.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258734","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}
Nature CatalysisPub Date : 2025-02-07DOI: 10.1038/s41929-025-01291-z
Yangguang Hu, Can Yu, Song Wang, Qian Wang, Marco Reinhard, Guozhen Zhang, Fei Zhan, Hao Wang, Dean Skoien, Thomas Kroll, Peiyuan Su, Lei Li, Aobo Chen, Guangyu Liu, Haifeng Lv, Dimosthenis Sokaras, Chao Gao, Jun Jiang, Ye Tao, Yujie Xiong
{"title":"Identifying a highly efficient molecular photocatalytic CO2 reduction system via descriptor-based high-throughput screening","authors":"Yangguang Hu, Can Yu, Song Wang, Qian Wang, Marco Reinhard, Guozhen Zhang, Fei Zhan, Hao Wang, Dean Skoien, Thomas Kroll, Peiyuan Su, Lei Li, Aobo Chen, Guangyu Liu, Haifeng Lv, Dimosthenis Sokaras, Chao Gao, Jun Jiang, Ye Tao, Yujie Xiong","doi":"10.1038/s41929-025-01291-z","DOIUrl":"10.1038/s41929-025-01291-z","url":null,"abstract":"Molecular metal complexes offer opportunities for developing artificial photocatalytic systems. The search for efficient molecular photocatalytic systems, which involves a vast number of photosensitizer–catalyst combinations, is extremely time consuming via a conventional trial and error approach, while high-throughput virtual screening has not been feasible owing to a lack of reliable descriptors. Here we present a machine learning-accelerated high-throughput screening protocol for molecular photocatalytic CO2 reduction systems using multiple descriptors incorporating the photosensitization, electron transfer and catalysis steps. The protocol rapidly screened 3,444 molecular photocatalytic systems including 180,000 conformations of photosensitizers and catalysts during their interaction, enabling the prediction of six promising candidates. Then, we experimentally validated the screened photocatalytic systems, and the optimal one achieved a turnover number of 4,390. Time-resolved spectroscopy and first-principles calculation further validated not only the relevance of the descriptors within certain screening scopes but also the role of dipole coupling in triggering dynamic catalytic reaction processes. High-throughput computational screening of multicomponent molecular photocatalytic systems offers a strategy to minimize the screening of large numbers of photosensitizer–catalyst combinations. Here a machine learning-accelerated approach using multiple descriptors shows strong predictive power in experimentally validated systems for CO2 reduction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"126-136"},"PeriodicalIF":42.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258670","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}
Nature CatalysisPub Date : 2025-02-06DOI: 10.1038/s41929-025-01294-w
Zuodong Sun, Xin Zang, Qingyang Zhou, Masao Ohashi, K. N. Houk, Jiahai Zhou, Yi Tang
{"title":"Iminium catalysis in natural Diels–Alderase","authors":"Zuodong Sun, Xin Zang, Qingyang Zhou, Masao Ohashi, K. N. Houk, Jiahai Zhou, Yi Tang","doi":"10.1038/s41929-025-01294-w","DOIUrl":"10.1038/s41929-025-01294-w","url":null,"abstract":"Iminium-catalysed cycloaddition is one of the most prominent examples of organocatalysis, yet a biological counterpart has not been reported, despite the widespread occurrence of iminium adducts in enzymes. Here we present biochemical, structural and computational evidence for iminium catalysis by the natural Diels–Alderase SdnG, which catalyses norbornene formation in sordarin biosynthesis. A Schiff-base adduct between the ε-nitrogen of active site K127 and the aldehyde group of the enal dienophile is revealed by structural analysis and captured under catalytic conditions via borohydride reduction. This Schiff-base adduct positions the substrate into near-attack conformation and decreases the transition-state barrier of Diels–Alder cyclization by 8.3 kcal mol−1 via dienophile activation. A hydrogen-bond network consisting of a catalytic triad is proposed to facilitate the proton transfer required for iminium formation. This work establishes an intriguing mode of catalysis for Diels–Alderases and points the way to the design of iminium-based (bio)catalysts. Iminium-catalysed cycloaddition is a prominent example of organocatalytic reactivity, yet a biological counterpart has not been identified. Now, the authors report biochemical, structural and computational evidence for iminium catalysis by the natural Diels–Alderase SdnG.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 3","pages":"218-228"},"PeriodicalIF":42.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-025-01294-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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