Qian–Qian Xu , Qing Li , Zong‐Bo Xie , Huo‐Yu Rao , Zhang‐Gao Le , Zhen–Zhen Xu , Zhi‐Qiang Zhu
Tuning multiple noncovalent interactions to form multicomponent photoactive electron donor−acceptor (EDA) complexes for driving chemical reactions presents significant challenges yet holds profound implications. Hantzsch ester (HE) is recognized as an exceptional EDA donor, while it typically forms binary EDA complexes requiring stoichiometric amounts. Ternary EDA complexes involving HE in catalytic EDA systems remain scarce. Herein, we developed a H‐bonding‐assisted catalytic ternary EDA complex strategy employing HE for the synthesis of diverse isoquinoline‐1,3(2H,4H)‐diones. This operationally simple, visible‐light‐mediated platform efficiently converted primary, secondary, and tertiary carboxylic acids‐derived NHP esters into structurally diverse alkylated isoquinoline‐1,3(2H,4H)‐diones.
{"title":"Catalytic Photoactive Ternary Electron Donor–Acceptor Complex Enabled Synthesis of Isoquinoline‐1,3(2H,4H)‐Diones","authors":"Qian–Qian Xu , Qing Li , Zong‐Bo Xie , Huo‐Yu Rao , Zhang‐Gao Le , Zhen–Zhen Xu , Zhi‐Qiang Zhu","doi":"10.1002/adsc.70207","DOIUrl":"10.1002/adsc.70207","url":null,"abstract":"<div><div>Tuning multiple noncovalent interactions to form multicomponent photoactive electron donor−acceptor (EDA) complexes for driving chemical reactions presents significant challenges yet holds profound implications. Hantzsch ester (HE) is recognized as an exceptional EDA donor, while it typically forms binary EDA complexes requiring stoichiometric amounts. Ternary EDA complexes involving HE in catalytic EDA systems remain scarce. Herein, we developed a H‐bonding‐assisted catalytic ternary EDA complex strategy employing HE for the synthesis of diverse isoquinoline‐1,3(2H,4H)‐diones. This operationally simple, visible‐light‐mediated platform efficiently converted primary, secondary, and tertiary carboxylic acids‐derived NHP esters into structurally diverse alkylated isoquinoline‐1,3(2H,4H)‐diones.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 1","pages":"Article e70207"},"PeriodicalIF":4.0,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145455206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peng Qian , Xiyuan Li , Wenjing Xiong , Jinxiu Liu , Tongtong Zhu , Yuting Ren , Jiasheng Wang , Qinyao Wei , Yanan Li
An electrochemical cross coupling for ketones and methanol is developed, providing an efficient access to β‐hydroxy ketones. In this protocol, the biofuel methanol is readily used as a hydroxymethylating reagent to couple with ketones with hydrogen as the only by product. This sustainable reaction proceeds smoothly in an aqueous medium, giving diverse β‐hydroxy ketones in 26%–92% yields at room temperature in the absence of exogenous oxidants.
{"title":"Electrosynthesis of β‐Hydroxy Ketones Directly from Ketones with Methanol as a Hydroxymethylating Reagent","authors":"Peng Qian , Xiyuan Li , Wenjing Xiong , Jinxiu Liu , Tongtong Zhu , Yuting Ren , Jiasheng Wang , Qinyao Wei , Yanan Li","doi":"10.1002/adsc.70104","DOIUrl":"10.1002/adsc.70104","url":null,"abstract":"<div><div>An electrochemical cross coupling for ketones and methanol is developed, providing an efficient access to β‐hydroxy ketones. In this protocol, the biofuel methanol is readily used as a hydroxymethylating reagent to couple with ketones with hydrogen as the only by product. This sustainable reaction proceeds smoothly in an aqueous medium, giving diverse β‐hydroxy ketones in 26%–92% yields at room temperature in the absence of exogenous oxidants.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 1","pages":"Article e70104"},"PeriodicalIF":4.0,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145478310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A rhodium‐catalyzed asymmetric hydrogenation of gem‐difluorocyclopropenyl esters or ketones has been achieved, affording the disubstituted cis‐gem‐difluorocyclopropanes with high enantio‐ and diastereoselectivities (up to 99% ee and >20:1 dr). Furthermore, the hydrogenation proceeds smoothly at gram scale without erosion of activity and enantioselectivity. The chiral gem‐difluorocyclopropane products could be transformed into chiral building blocks and bioactive molecule.
{"title":"Facile Synthesis of Chiral gem‐Difluorocyclopropanes via Rhodium‐Catalyzed Hydrogenation","authors":"Sai‐Nan Yin , Zheng Liu , Xinsheng Zhang , Yong‐Gui Zhou , Mu‐Wang Chen","doi":"10.1002/adsc.70169","DOIUrl":"10.1002/adsc.70169","url":null,"abstract":"<div><div>A rhodium‐catalyzed asymmetric hydrogenation of <em>gem</em>‐difluorocyclopropenyl esters or ketones has been achieved, affording the disubstituted <em>cis</em>‐<em>gem</em>‐difluorocyclopropanes with high enantio‐ and diastereoselectivities (up to 99% ee and >20:1 dr). Furthermore, the hydrogenation proceeds smoothly at gram scale without erosion of activity and enantioselectivity. The chiral <em>gem</em>‐difluorocyclopropane products could be transformed into chiral building blocks and bioactive molecule.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 1","pages":"Article e70169"},"PeriodicalIF":4.0,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145499342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aimen Al‐Hilfi , E. Alejandro Castellanos Franco , Connor J. Grady , Zinia Mohanta , Michael T. McMahon , Milana Bazayeva , Zhen Li , Kenneth M. Merz , Assaf A. Gilad
Magnetic resonance imaging (MRI) is a cornerstone of modern clinical diagnostics, often enhanced by contrast agents. Traditionally, these agents are chemically synthesized, which can involve complex, costly, and environmentally unfriendly processes. Here, we report a novel biocatalytic approach for the efficient, safe, and eco‐friendly synthesis of 5‐methyl‐5,6‐dihydrothymidine (5‐MDHT), a potent chemical exchange saturation transfer (CEST)‐MRI probe for imaging in vivo expression of the Herpes Simplex Virus Type‐1 Thymidine Kinase (HSV1‐TK) reporter gene. We demonstrate that 5‐MDHT can be biosynthesized via one‐ or two‐step enzymatic reactions using human purine nucleoside phosphorylase (hPNPase) and the SgvMVAV SAM‐dependent methyltransferase. hPNPase catalyzed the base‐exchange reaction with catalytic efficiencies (kcat/KM) between 138 and 316 s−1·M−1, while SgvMVAV methylation of 5,6‐dihydrothymidine yielded 5‐MDHT with a catalytic efficiency of 26 s−1·M−1. Molecular dynamics simulations supported the enzymatic binding and selectivity observed experimentally. The resulting 5‐MDHT was validated using CEST‐MRI, showing a distinct exchangeable imino proton signal at 5.3 ppm. These findings highlight the chemo‐ and regioselectivity of the biocatalysts and establish biocatalysis as a viable platform for producing clinically relevant MRI contrast agents.
{"title":"Biocatalytic Construction of a Chemical Exchange Saturation Transfer Magnetic Resonance Imaging Nucleoside Probe: Synthesis and Evaluation of 5‐Methyl‐5,6‐Dihydrothymidine","authors":"Aimen Al‐Hilfi , E. Alejandro Castellanos Franco , Connor J. Grady , Zinia Mohanta , Michael T. McMahon , Milana Bazayeva , Zhen Li , Kenneth M. Merz , Assaf A. Gilad","doi":"10.1002/adsc.70200","DOIUrl":"10.1002/adsc.70200","url":null,"abstract":"<div><div>Magnetic resonance imaging (MRI) is a cornerstone of modern clinical diagnostics, often enhanced by contrast agents. Traditionally, these agents are chemically synthesized, which can involve complex, costly, and environmentally unfriendly processes. Here, we report a novel biocatalytic approach for the efficient, safe, and eco‐friendly synthesis of 5‐methyl‐5,6‐dihydrothymidine (5‐MDHT), a potent chemical exchange saturation transfer (CEST)‐MRI probe for imaging in vivo expression of the Herpes Simplex Virus Type‐1 Thymidine Kinase (HSV1‐TK) reporter gene. We demonstrate that 5‐MDHT can be biosynthesized via one‐ or two‐step enzymatic reactions using human purine nucleoside phosphorylase (hPNPase) and the SgvM<sup>VAV</sup> SAM‐dependent methyltransferase. hPNPase catalyzed the base‐exchange reaction with catalytic efficiencies (<em>k</em><sub>cat</sub><em>/K</em><sub>M</sub>) between 138 and 316 s<sup>−1</sup>·M<sup>−1</sup>, while SgvM<sup>VAV</sup> methylation of 5,6‐dihydrothymidine yielded 5‐MDHT with a catalytic efficiency of 26 s<sup>−1</sup>·M<sup>−1</sup>. Molecular dynamics simulations supported the enzymatic binding and selectivity observed experimentally. The resulting 5‐MDHT was validated using CEST‐MRI, showing a distinct exchangeable imino proton signal at 5.3 ppm. These findings highlight the chemo‐ and regioselectivity of the biocatalysts and establish biocatalysis as a viable platform for producing clinically relevant MRI contrast agents.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 1","pages":"Article e70200"},"PeriodicalIF":4.0,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145535937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ranran Wu , Fei Li , Kaiyang Lian , Dingyu Liu , Huifeng Jiang , Zhiguang Zhu
The global demand for amino acids continues to rise, yet traditional synthesis methods face environmental and safety challenges. To contribute to a sustainable future vision, we herein report a novel cofactor‐neutral in vitro multienzyme cascade that directly converts methanol, a renewable C1 feedstock, into glycine under mild conditions. A two‐step strategy achieves 82.2% methanol‐to‐glycolaldehyde and 86.0% glycolaldehyde‐to‐glycine conversion, respectively. At 500 mM methanol, it yields 18.8 mM glycine after 6 h, which represents a 26.8‐fold improvement over the one‐pot approach. These results demonstrate the potential of modular in vitro multienzyme catalysis for efficient C1‐to‐amino acid transformation and establish a foundation for the synthesis of many other complex nitrogen‐containing molecules.
全球对氨基酸的需求持续增长，但传统的合成方法面临环境和安全挑战。为了促进可持续的未来愿景，我们在此报道了一种新的辅助因子中性体外多酶级联，可在温和条件下直接将甲醇（一种可再生的C1原料）转化为甘氨酸。两步策略分别实现了82.2%的甲醇制乙醇醛和86.0%的乙醇醛制甘氨酸的转化率。在500 mM的甲醇条件下，6小时后产生18.8 mM的甘氨酸，这比单罐方法提高了26.8倍。这些结果证明了模块化体外多酶催化高效C1 - to -氨基酸转化的潜力，并为许多其他复杂含氮分子的合成奠定了基础。
{"title":"Glycine Synthesis From Methanol by a Cofactor‐Neutral In Vitro Multienzyme Cascade","authors":"Ranran Wu , Fei Li , Kaiyang Lian , Dingyu Liu , Huifeng Jiang , Zhiguang Zhu","doi":"10.1002/adsc.70238","DOIUrl":"10.1002/adsc.70238","url":null,"abstract":"<div><div>The global demand for amino acids continues to rise, yet traditional synthesis methods face environmental and safety challenges. To contribute to a sustainable future vision, we herein report a novel cofactor‐neutral in vitro multienzyme cascade that directly converts methanol, a renewable C1 feedstock, into glycine under mild conditions. A two‐step strategy achieves 82.2% methanol‐to‐glycolaldehyde and 86.0% glycolaldehyde‐to‐glycine conversion, respectively. At 500 mM methanol, it yields 18.8 mM glycine after 6 h, which represents a 26.8‐fold improvement over the one‐pot approach. These results demonstrate the potential of modular in vitro multienzyme catalysis for efficient C1‐to‐amino acid transformation and establish a foundation for the synthesis of many other complex nitrogen‐containing molecules.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 1","pages":"Article e70238"},"PeriodicalIF":4.0,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145554631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Manuel Kirchhof , Sanja Krause , Liam Rautenbach , Jakoba Wacker , Ann‐Katrin Beurer , Hoang‐Huy Nguyen , Wolfgang Frey , Yvonne Traa , Deven P. Estes , Anna Zens , Sabine Laschat
We report a copper‐free alkynone‐amine click reaction as a versatile strategy for the immobilization of chiral norbornadiene‐based ligands. This methodology was applied to both soluble amines and amino‐functionalized mesoporous silica support materials. Therefore, a series of (E)‐ and (Z)‐configured enaminones were synthesized, revealing a strong substituent‐dependent stereoselectivity: primary amines exclusively formed (Z)‐enaminones, while secondary amines afforded (E)‐isomers with high selectivity (>99:1). The resulting enaminone‐functionalized diene ligands were subsequently applied in Rh catalysis both under homogeneous and heterogeneous conditions. Regarding the enantioselectivity it was found that the catalysts performed well under homogeneous conditions for 1,2‐additions while heterogeneous conditions gave the best results for the Rh‐catalyzed isoxazole ring contraction.
{"title":"Development of a Copper‐Free Click Reaction for Asymmetric Rh Diene Catalysis Under Confinement","authors":"Manuel Kirchhof , Sanja Krause , Liam Rautenbach , Jakoba Wacker , Ann‐Katrin Beurer , Hoang‐Huy Nguyen , Wolfgang Frey , Yvonne Traa , Deven P. Estes , Anna Zens , Sabine Laschat","doi":"10.1002/adsc.70213","DOIUrl":"10.1002/adsc.70213","url":null,"abstract":"<div><div>We report a copper‐free alkynone‐amine click reaction as a versatile strategy for the immobilization of chiral norbornadiene‐based ligands. This methodology was applied to both soluble amines and amino‐functionalized mesoporous silica support materials. Therefore, a series of (<em>E</em>)‐ and (<em>Z</em>)‐configured enaminones were synthesized, revealing a strong substituent‐dependent stereoselectivity: primary amines exclusively formed (<em>Z</em>)‐enaminones, while secondary amines afforded (<em>E</em>)‐isomers with high selectivity (>99:1). The resulting enaminone‐functionalized diene ligands were subsequently applied in Rh catalysis both under homogeneous and heterogeneous conditions. Regarding the enantioselectivity it was found that the catalysts performed well under homogeneous conditions for 1,2‐additions while heterogeneous conditions gave the best results for the Rh‐catalyzed isoxazole ring contraction.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 1","pages":"Article e70213"},"PeriodicalIF":4.0,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145485082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Skeletal editing has been achieved through triflic anhydride‐mediated O‐to‐N swapping reaction of 3,3‐diarylbenzofuranones with benzonitriles/benzyl/alkyl nitriles, successfully affording 3,3‐diarylisoindolinones. A possible reaction mechanism with triflic anhydride serving as a key mediator is proposed to explain this conversion. The present reaction features a broad substrate scope, excellent functional group tolerance and high yields, expanding the structural diversity of isoindolinones.
骨架编辑是通过三酸酐介导的3,3 -二芳基苯并呋喃酮与苯并腈/苄基/烷基腈的O - to - N交换反应实现的，成功地生成3,3 -二芳基异吲哚酮。提出了一种以三酸酐为主要介质的反应机理来解释这种转化。该反应具有底物范围广、官能团耐受性好、产率高等特点，扩大了异吲哚酮的结构多样性。
{"title":"An O‐to‐N Swapping Reaction via Triflic Anhydride‐Mediated Lactamization of 3,3‐Diarylbenzofuranones with Nitriles","authors":"Tehmina Akram , Chuang Niu , Wen‐Jie Qiu , Guan‐Wu Wang","doi":"10.1002/adsc.70230","DOIUrl":"10.1002/adsc.70230","url":null,"abstract":"<div><div>Skeletal editing has been achieved through triflic anhydride‐mediated O‐to‐N swapping reaction of 3,3‐diarylbenzofuranones with benzonitriles/benzyl/alkyl nitriles, successfully affording 3,3‐diarylisoindolinones. A possible reaction mechanism with triflic anhydride serving as a key mediator is proposed to explain this conversion. The present reaction features a broad substrate scope, excellent functional group tolerance and high yields, expanding the structural diversity of isoindolinones.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 1","pages":"Article e70230"},"PeriodicalIF":4.0,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145554633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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