Advanced Synthesis & Catalysis最新文献

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Continuous‐Flow Biocatalysis of UDP‐Glucuronic Acid: Engineering the Rate‐Limiting Enzyme and Optimizing Multienzyme Immobilization UDP -葡萄糖醛酸的连续流生物催化:设计限速酶和优化多酶固定化
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-27 DOI: 10.1002/adsc.70469
Shuang Zheng, Jin‐Qi Yu, Xiao‐Rui Zhang, De‐Qing Wang, Jian‐Qun Deng, Li‐Li Sheng, Juan Liu, Jin Hou, Ju‐Zheng Sheng
{"title":"Continuous‐Flow Biocatalysis of UDP‐Glucuronic Acid: Engineering the Rate‐Limiting Enzyme and Optimizing Multienzyme Immobilization","authors":"Shuang Zheng, Jin‐Qi Yu, Xiao‐Rui Zhang, De‐Qing Wang, Jian‐Qun Deng, Li‐Li Sheng, Juan Liu, Jin Hou, Ju‐Zheng Sheng","doi":"10.1002/adsc.70469","DOIUrl":"https://doi.org/10.1002/adsc.70469","url":null,"abstract":"UDP‐GlcA, the activated form of glucuronic acid, is essential for glycosylation and polysaccharide biosynthesis. Despite advances in UDP‐GlcA synthesis, economical and scalable production methods remain limited. Here, we developed a multienzyme immobilization system for the continuous‐flow synthesis of UDP‐GlcA. We first constructed a UDP‐glucose synthesis module that maintained stable operation for over 200 h with a space‐time yield of 3.9 g·L <jats:sup>−1</jats:sup> ·h <jats:sup>−1</jats:sup> . To address the bottleneck of the rate‐limiting enzyme UDP‐glucose dehydrogenase (TuaD), we obtained the mutant TuaD M8, using a combined strategy of protein repair one‐stop shop engineering and rational reversion of synergistic deleterious mutations, achieving significantly enhanced activity and stability. Integration of both modules yielded a UDP‐GlcA flow synthesis system with a space‐time yield of 1.3 g·L <jats:sup>−1</jats:sup> ·h <jats:sup>−1</jats:sup> and 220 h continuous operation, demonstrating strong industrial potential. This strategy provides an efficient, sustainable, and cost‐effective approach for large‐scale UDP‐GlcA production and establishes a framework for biosynthesizing other high‐value nucleotide sugars via immobilized enzyme systems.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751607","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}
引用次数: 0
Trimethylsilyl Triflate‐Promoted Synthesis of Enone Functionalized Benzo‐1,3‐Thiazines via Formal [4 + 2] Heteroannulation of Azadienes with β‐Ketodithioesters at Room Temperature 三甲基硅基三氟酸盐在室温下通过偶氮二烯与β -酮二硫酯的正[4 + 2]杂环反应促进烯酮功能化苯并1,3 -噻嗪的合成
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-27 DOI: 10.1002/adsc.70467
Ganesh Kumar, Nimisha Gupta, Keshav Raghuvanshi, Maya Shankar Singh
{"title":"Trimethylsilyl Triflate‐Promoted Synthesis of Enone Functionalized Benzo‐1,3‐Thiazines via Formal [4 + 2] Heteroannulation of Azadienes with β‐Ketodithioesters at Room Temperature","authors":"Ganesh Kumar, Nimisha Gupta, Keshav Raghuvanshi, Maya Shankar Singh","doi":"10.1002/adsc.70467","DOIUrl":"https://doi.org/10.1002/adsc.70467","url":null,"abstract":"An efficient approach for the direct synthesis of previously inaccessible enone functionalized benzo‐1,3‐thiazines has been developed via formal [4 + 2] heteroannulation of azadienes (generated in situ from 2‐aminobenzyl alcohol) with β‐ketodithioesters in acetonitrile at room temperature, facilitated by trimethylsilyl triflate (TMSOTf). This strategy is distinguished by transition‐metal and additive‐free mild conditions, convenient operation, wide functional group compatibility with no steric and electronic constraints, accessible scalability, high yields, and practical transformations. A combination of controlled experiments and HRMS studies corroborated the proposed mechanism.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"31 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751606","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}
引用次数: 0
Bis(oxazoline)–Nickel(II)‐Catalyzed Asymmetric Photochemical Hydroxylation of β‐Keto Esters With Nitrones 双(恶唑啉)-镍(II)‐催化β -酮酯与硝酮的不对称光化学羟基化反应
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-27 DOI: 10.1002/adsc.70480
Jian‐Peng Tai, Yan‐Ping Luo, Bao‐Gui Cai, Zi‐Yi Xie, Hao‐Ting Duan, Zi‐Xuan Dong, Wen‐Chao Mo, Chongqing Pan, Jun Xuan
{"title":"Bis(oxazoline)–Nickel(II)‐Catalyzed Asymmetric Photochemical Hydroxylation of β‐Keto Esters With Nitrones","authors":"Jian‐Peng Tai, Yan‐Ping Luo, Bao‐Gui Cai, Zi‐Yi Xie, Hao‐Ting Duan, Zi‐Xuan Dong, Wen‐Chao Mo, Chongqing Pan, Jun Xuan","doi":"10.1002/adsc.70480","DOIUrl":"https://doi.org/10.1002/adsc.70480","url":null,"abstract":"Nitrones have been extensively employed as electrophiles, 1,3‐dipoles, and radical acceptors in organic chemistry. In contrast, their photochemical transformations, especially in the context of asymmetric catalysis, have remained elusive. Herein we disclose the first enantioselective phototransformation of nitrones for the hydroxylation of β‐keto esters under bis(oxazoline)–Ni(II) catalysis. This photocatalyst‐free method affords chiral α‐hydroxy β‐keto esters in high yields and excellent enantioselectivity (up to 94% yield, 93% ee). This work opens new chemical space for asymmetric photochemistry of nitrones.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751608","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}
引用次数: 0
O 2 ‐Mediated Cu‐Catalyzed Dehydrogenative Sulfilimination of Tyrosines and Bioactive Phenols O - 2介导的Cu -催化酪氨酸和生物活性酚的脱氢磺化反应
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-27 DOI: 10.1002/adsc.70420
Fang Xiao, Frederic W. Patureau
{"title":"O 2 ‐Mediated Cu‐Catalyzed Dehydrogenative Sulfilimination of Tyrosines and Bioactive Phenols","authors":"Fang Xiao, Frederic W. Patureau","doi":"10.1002/adsc.70420","DOIUrl":"https://doi.org/10.1002/adsc.70420","url":null,"abstract":"The bioconjugation of unmodified native peptides, in particular at their tyrosine units with the dehydrogenative phenochalcogenazination reaction, has attracted much attention lately due to potential click type applications. In our quest to bring this oxidative coupling concept beyond phenothiazines and its derivatives, we report herein the case of sulfenamides and their mild O <jats:sub>2</jats:sub> ‐mediated Cu‐catalyzed dehydrogenative sulfilimination of diverse bioactive phenols.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"28 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751603","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}
引用次数: 0
Unexpected Discovery of an Inverse‐Electron‐Demand (5 + 4) Cycloaddition of Oxidopyridinium With Trifluoromethylated o ‐Quinone Methide Yielding a Bridged N, O‐Acetal Scaffold 意外发现氧化吡啶与三氟甲基化的o -醌甲基的反电子需求(5 + 4)环加成,生成桥接N, o -缩醛支架
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-27 DOI: 10.1002/adsc.70470
Yuto Ide, Takeshi Yasui, Yoshihiko Yamamoto
{"title":"Unexpected Discovery of an Inverse‐Electron‐Demand (5 + 4) Cycloaddition of Oxidopyridinium With Trifluoromethylated o ‐Quinone Methide Yielding a Bridged N, O‐Acetal Scaffold","authors":"Yuto Ide, Takeshi Yasui, Yoshihiko Yamamoto","doi":"10.1002/adsc.70470","DOIUrl":"https://doi.org/10.1002/adsc.70470","url":null,"abstract":"We investigated the reaction of in situ generated 1‐(pyrimidin‐2‐yl)‐3‐oxidopyridiniums with a trifluoromethylated <jats:italic>o</jats:italic> ‐quinone methide and discovered that unexpected bridged N‐heterocycles bearing an N, O‐acetal moiety were predominantly formed via a (5 + 4) cycloaddition occurring at the 2‐ and 6‐positions of the oxidopyridinium ring. To rationalize the unusual regioselectivity, a non‐concerted mechanism was proposed based on density functional theory calculations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751604","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}
引用次数: 0
Highly Diastereoselective (4 + 3)‐Cycloannulation of Carbonyl Ylides and 3‐Aryl‐1‐(2‐(1‐Arylvinyl)phenyl)prop‐2‐Yn‐1‐Ones Enabled by Silver Catalysis 高非对映选择性(4 + 3)‐环环羰基酰和3‐芳基‐1‐(2‐(1‐芳基乙烯基)苯基)prop‐2‐Yn‐1‐的银催化作用
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-25 DOI: 10.1002/adsc.70449
Gaurav Jaiswal, Jyotish Barman, Ritesh Majhi, Subhas Chandra Pan
{"title":"Highly Diastereoselective (4 + 3)‐Cycloannulation of Carbonyl Ylides and 3‐Aryl‐1‐(2‐(1‐Arylvinyl)phenyl)prop‐2‐Yn‐1‐Ones Enabled by Silver Catalysis","authors":"Gaurav Jaiswal, Jyotish Barman, Ritesh Majhi, Subhas Chandra Pan","doi":"10.1002/adsc.70449","DOIUrl":"https://doi.org/10.1002/adsc.70449","url":null,"abstract":"A highly diastereoselective (4 + 3)‐cycloannulation of in situ generated carbonyl ylides and 3‐aryl‐1‐(2‐(1‐arylvinyl)phenyl)prop‐2‐yn‐1‐ones enabled by silver catalysis is described. This study is the first to report the synthesis of naphthalenes with an oxa‐bridged motif using silver catalysis. The reaction's scope is broad and the oxa‐bridged naphthalene products were obtained in good to high yields and with excellent diastereoselectivities.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147739222","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}
引用次数: 0
Synthesis of ß‐Substituted Dehydroamino Acids via Formal C–H Functionalization of Dehydroalanine with Diazo Precursors 重氮前体脱氢丙氨酸C-H官能化合成β -取代脱氢氨基酸
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-25 DOI: 10.1002/adsc.70332
Xiaoshen Ma, Stephen J. Sujansky
{"title":"Synthesis of ß‐Substituted Dehydroamino Acids via Formal C–H Functionalization of Dehydroalanine with Diazo Precursors","authors":"Xiaoshen Ma, Stephen J. Sujansky","doi":"10.1002/adsc.70332","DOIUrl":"https://doi.org/10.1002/adsc.70332","url":null,"abstract":"Recent advances in peptide drug discovery inspired the discovery of novel synthetic methods to access diverse noncanonical amino acids (ncAAs). Dehydroamino acids (ΔAAs) provide opportunities for not only the generation of ncAA building blocks but also late‐stage functionalizations of the α,ß‐desaturation via diverse transformations. Herein, we report a general synthetic method accessing ß‐substituted ΔAAs via formal C–H functionalization of dehydroalanine derivatives. The mild reaction conditions allow broad functional group compatibility and the products provide entries into the novel chemical space of ncAAs.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"5 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147739224","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}
引用次数: 0
Enantioselective Synthesis of C–N Atropisomeric Pyrazole–Pyrroles via Asymmetric Paal–Knorr Reaction 不对称Paal-Knorr反应对映选择性合成C-N阿托罗二聚体吡唑吡咯
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-25 DOI: 10.1002/adsc.70431
Wenxuan Zhang, Chen Dong, Wenjing Qiu, Yuhuan Yang, Tao Liu
{"title":"Enantioselective Synthesis of C–N Atropisomeric Pyrazole–Pyrroles via Asymmetric Paal–Knorr Reaction","authors":"Wenxuan Zhang, Chen Dong, Wenjing Qiu, Yuhuan Yang, Tao Liu","doi":"10.1002/adsc.70431","DOIUrl":"https://doi.org/10.1002/adsc.70431","url":null,"abstract":"The catalytic asymmetric construction of bis‐five‐membered C–N axially chiral scaffolds remains challenging, owing to their low rotational energy barriers. Herein, we describe a chiral phosphoric acid‐catalyzed asymmetric Paal–Knorr reaction between <jats:italic>N</jats:italic> ‐alkyl 5‐aminopyrazoles and 1,4‐diketones, affording <jats:italic>ortho</jats:italic> ‐trisubstituted C–N axially chiral pyrazole–pyrroles in high yield and excellent enantioselectivity. Moreover, the successful construction of <jats:italic>ortho</jats:italic> ‐trisubstituted pyrazole–pyrrole atropisomers is attributed to the strategic use of sterically bulky <jats:italic>N</jats:italic> ‐alkyl pyrazoles for effective stereocontrol. This protocol not only expands the repertoire of bis‐five‐membered C–N axially chiral scaffolds but also exhibits facile scale‐up and diverse late‐stage functionalizations, underscoring its synthetic utility.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"67 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147739227","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}
引用次数: 0
Design, Synthesis, and Structural Analysis of Binaphthyl‐Based Chiral Benzindenes 联萘基手性联苯醚的设计、合成及结构分析
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-25 DOI: 10.1002/adsc.70478
Marko Gobin, Nikola Topolovčan
{"title":"Design, Synthesis, and Structural Analysis of Binaphthyl‐Based Chiral Benzindenes","authors":"Marko Gobin, Nikola Topolovčan","doi":"10.1002/adsc.70478","DOIUrl":"https://doi.org/10.1002/adsc.70478","url":null,"abstract":"Chiral benzindenes are an unexplored structural motif in the realm of organic synthesis. This is a result of a lack of synthetic protocols for constructing these compounds in which chirality does not arise from additional chiral substituents. This work introduces an unprecedented route toward chiral benzindenes as a new potential structural motif for further exploratory studies. Starting from readily available ( <jats:italic>R</jats:italic> )‐BINOL, the convergent synthesis over 9 steps culminated in benzindene with embedded chirality into the binaphthyl framework. The synthetic challenges associated with structural decoration are addressed and evaluated, while DFT and NMR structural analysis of the prepared chiral benzindene revealed its molecular characteristics.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"34 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147739223","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}
引用次数: 0
Asymmetric Transformations of α,β‐Unsaturated Oxazolidinones Catalyzed by C 2 ‐Symmetric Chiral Iron Triad Complexes c2 -对称手性铁三元配合物催化α,β -不饱和恶唑烷酮的不对称转化
IF 5.4 2区 化学
Advanced Synthesis & Catalysis Pub Date : 2026-04-25 DOI: 10.1002/adsc.70440
Arthur David, Thierry Ollevier
{"title":"Asymmetric Transformations of α,β‐Unsaturated Oxazolidinones Catalyzed by C 2 ‐Symmetric Chiral Iron Triad Complexes","authors":"Arthur David, Thierry Ollevier","doi":"10.1002/adsc.70440","DOIUrl":"https://doi.org/10.1002/adsc.70440","url":null,"abstract":"<jats:italic>C</jats:italic> <jats:sub>2</jats:sub> ‐symmetric ligands demonstrate outstanding efficiency in coordinating iron, cobalt, and nickel salts to generate highly active catalysts for asymmetric transformations. Chiral complexes derived from these iron triad metals exhibit excellent performance in stereoselective reactions involving α,β‐unsaturated oxazolidinones, consistently affording high enantio‐ and diastereoselectivities. In the Diels–Alder reaction of cyclopentadiene and aliphatic dienes, enantiomeric and diastereomeric excesses of up to 99% are produced. 1,3‐Dipolar cycloadditions run with nitrones, azomethine imines, nitrile oxides, and diazo esters lead to high levels of selectivity mostly using Ni catalysts. The thia‐Michael addition of thiols to α,β‐unsaturated oxazolidinones successfully affords products with enantiomeric excesses of up to 97% <jats:italic>ee</jats:italic> . Chiral Ni complexes are efficient catalysts for other highly asymmetric transformations, such as Michael addition and α‐chlorination reactions. Fe catalysts provide excellent results of asymmetric conjugate radical addition reaching 98% <jats:italic>ee</jats:italic> . Coordinated iron triad metals are investigated through transition‐state analyses, which support the stereoselectivity observed with multidentate, sterically hindered catalysts. The bidentate BOX, tridentate PyBOX and DBFOX, tetradentate BINIM, and bipyridine diol ligands are particularly valuable in these stereoselective transformations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147739226","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}
引用次数: 0
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